Chemistry, Technology, Pharmacology, Medicine’’

The main conference: ‘‘Renewable Wood and Plant Resources: Chemistry, Technology, Pharmacology, Medicine’’

Satellite conferences: Youth school-conference: ‘‘Physical-Chemical Analysis of Organic Compounds of Plant Origin’’

Thematic Symposium of Nonprofit Partnership

‘‘OrCheMed’’ (Organic Chemistry and Medicine) ‘‘Novel Drugs Based on Plant Substances’’

1 2 3 CONTENTS

Renewable Wood and Plant Resources: Chemistry, Technology, Pharmacology, Medicine...... 5

Physical-Chemical Analysis of Organic Compounds of Plant Origin...... 263

Novel Drugs Based on Plant Substances ...... 277

Russian-Austrian Seminar on Cellulose Chemistry...... 298

INDEX ...... 308

4 RENEWABLE WOOD AND PLANT RESOURCES: CHEMISTRY, TECHNOLOGY, PHARMACOLOGY, MEDICINE

CONTENTS OF PIGMENTS AND ALKALOIDS IN THE INTRODUCED PLANT CROTALARIA ALATA

Z.Ch. Abraeva1, V.I. Akhmedjanova1, N.K. Rakhimova2, A.K. Safarov2 1 - S. Yu. Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences, Republic of Uzbekistan, Tashkent 2 - Scientific-Industrial Center “Botany”, Academy of Sciences, Republic of Uzbekistan [email protected]

Crotalaria alata L. (Fabaceae) is one year herbaceous plant known by its honey-bearing and fodder properties. The plant, growing in Australia and countries of America, was introduced to the Botanical garden, Academy of Sciences, Uzbekistan. We studied for the first time the contents of pigments in leaves and alkaloids in different organs of C. alata collected at the Botanical garden in the phase of flowering-fruiting. An each air-dried organ of the plant was extracted separately with ethanol. Isolation of pigments from leaves and total alkaloids from beans, leaves, seeds, flowers, roots, and stems was carried out by known methods. The content of green pigments (chlorophylls) in leaves was 8.32 mg/g damp weight and yellow pigments (carotenoids), 2.04 mg/g, i.e., more than 4 times less. Chlorophyll “a” predominated among chlorophylls (a+b). The highest content of alkaloids was found in beans (0.49% of dry weight of raw material) and leaves (0.48%). Seeds contained alkaloids (0.24%) about 2 times less than beans and leaves; flowers, 0.19%. Significant decrease of an alkaloid amount was observed in roots (0.04%) and stems (0.03%). Thus, Crotalaria alata, introduced to Uzbekistan, has been found to contain alkaloids, which in the phase of flowering-fruiting accumulate mainly in beans and leaves.

MULTIASPECT CHEMICAL AND PHARMACOLOGICAL RESEARCHES OF RAW MATERIAL OF KAZAKHSTAN

S.M. Adekenov International research and production holding Phytochemistry [email protected]

The unique and rich flora of Republic of Kazakhstan is a renewed source of biologically active compounds for development of the new original preparations with wide spectrum of action. More 6000 species of plants are numbered, from which 667 species are endemic. The various chemical compositions of plants develop the certain difficulties at isolation of individual compounds and demand the adaptation of technological processes for the obtaining of the biologically active substances. Thus, the complex processing of raw material as a renewed material with application of ecologic safe methods and innovation technologies is one of the priority approaches at the multiaspect chemical study of plants by way of the obtaining of compounds with the practically valuable properties. Thus, the endemic plan of Kazakhstan of Artemisia glabella Kar. et Kir. is a source of the biologically active compounds such as, arglabin, argolid, bonansin, pectolinarigenin, cyrsilineole, casticin, luteolin, 1,8-cineole, linalool, terpineol-4, -terpineol, sabinol, umbelliferone, glutamine, triptophan, arginin, tirosin, prolin, leicin, glutamic acid, glucose, dulcit, rhamnose, gallic, protocathechuic, caffeic and salicylic acids.

5 Other species of Artemisia leucodes Schrenk. is a perspective source of compounds such as, camphor, camphene, 1,8-cineole, chrysanthenylacetate, chrysanthenon, nerylacetate, austricin, leucomisin, parishin C, anhydroaustricin, matricarin, artelin, 5(Н)-austricin. The investigations on the isolation of sesquiterpene lactones are carried out by the supercritical fluid extraction method from Artemisia glabella Kar. et Kir. and Artemisia leucodes Schrenk. at the International research and production holding “Phytochemistry”. It is determined that CO2 - extraction provides the exhaustive extraction of the sum of the biologically active substances of the hydrophobic nature, with full absence of solvent in the finished product. It permits to keep the native structure of molecule and biological activity. The effective, economic, ecologically safe methods of the isolation and purification of the individual sesquiterpene lactones of arglabin and leucomisin with application of the centrifugal partition chromatography in combination with the preparative high-performance liquid chromatography are introduced for the first time. It shows the high efficiency, comparative automation and significant reduction of process duration, toxic solvents’ removal and the conformance to requirements GMP. The unique domestic antitumor preparation “Arglabin” (RК-MD-5-№000726; RF-MD-№001578) are developed on the basis of sesquiterpene lactone arglabin. The essential oil, obtained from СО2- extract of Artemisia glabella Kar. et Kir. after extraction of arglabin, possesses the high antimicrobial and antitubercular activity. As a result the new phytopreparation “Epherol” (RK-MD- 3-№004787) is developed on its basis. After the CO2-extraction the wastes of raw material of Artemisia glabella Kar. et Kir. are presented the natural biopolymer, which is a valuable source for the obtaining of others biologically active materials, for example, the phenolic compounds (bonansin, pectolinarigenin, cyrsilineole, casticin, luteolin and others). This has permitted to offer the regulation of the complex waste-free method of the obtaining of the essential oil, arglabin and phenolic compounds from raw material of Artemisia glabella Kar. et Kir. The hypolipidemic drug “Aterolid” (RK-MD-3-№000711) is developed on the basis of leucomisin, isolated from CO2-extract of Artemisia leucodes Schrenk. In addition, the CO2-extraction of Artemisia leucodes Schrenk. permits to isolate quantitatively leucomisin and others pharmacologically active compounds such as, camphor and sesquiterpene lactones from raw material. They are renewed material for the obtaining of new compounds with the expressed biological activity. As a result of the multiple-aspect approach at the chemical and pharmacological research of plant objects at holding “Phytochemistry”, more 1700 compounds are isolated and identified from more 500 species of plants: 1500 mono- and sesquiterpenoids essential oils, 120 sesquiterpene lactones, more 50 ecdysteroids, 25 alkaloids and 40 flavonoids. On basis of their molecules about 2000 new compounds with practically valuable properties are synthesized. At holding “Phytochemistry” the developed laboratory and trial regulations of the complex processing of raw material have permitted to organize the production of the original phytopreparations such as, “Arglabin”, “Salsocollin”, “Epherol”, “Darmenin”, “Aterolid”, “Sausalin” and “Ecdyphyt”, totally 43 names at the Karaganda pharmaceutical factory. Thus, the raw material of Republic of Kazakhstan is renewed resource for the obtaining of materials with practically valuable properties, which can be used at the complex processing for development of the new original preparations with wide spectrum action, biologically active additives, perfumery-cosmetic means, etc.

6 USE THE SPECIAL WASTE PAPER FOR PRODUCTION CARBOXYMETHYL CELLULOSE, SODIUM SALT

M.A. Ageev, I.A. Blinova, A.Ya. Ageev The Ural state forest engineering university, Ekaterinburg, Russia [email protected]

The special waste paper (МБС) – it shabby monetary banknotes doesn't find now rational application. At the same time composite structure МБС on a fibre, represents a great interest to possibility of use for production carboxymethyl cellulose, sodium salt (Na-CMC) instead of traditional raw materials – cotton and viscose cellulose. Characteristic МБС is presented in table 1. Table 1 – Characteristic МБС

Polymerization Structure on a fibre α - cellulose, % Ash content, % degree, in limits

Cotton, sulfate and sulfite bleached pulp of deciduous 1000 – 1500 90,5 ± 0,2 3,81 ± 0,2 and coniferous woods

On the department of chemistry of wood and technology of pulp-and-paper production (ХД и ТЦБП) Urals state forest engineering university (УГЛТУ) the way of production Na-CMC from МБС is developed. For the purpose inturgescence and removal of paint МБС have subjected to hydrothermal processing NaOH solution. A printing ink particles have removed a flotation method. The waste paper weight subjected to powdering in 18 % NaOH solution with the subsequent dehydration to frequency rate 2,65. Powdering МБС mixed with CH2ClCOONa. Reaction end spent without hashing in special devices. The received technical product dried up hot air. The carried out analysis of properties of a product from МСБ in comparison with commodity products is presented in table 2. Table 2 – Indicators of quality technical carboxymethyl cellulose, sodium salt Na-CMC Na-CMC Na-CMC The name of indicators («Carbokam») («Biya-Chim») from МБС Appearance and color Fine-grained loose Fine-grained fibrous Fine-grained loose material from light or powdery from material from light yellow to beige color white to cream color blue to blue-green color Mass fraction of water, 10 12 10 % Replacement degree on 75-90 65-90 65-75 carboxyl groups Polymerization degree 700-800 400-1200 650-750 Solubility in water in recalculation on 97 97 97 absolutely dry technical product, %

Am visible that the technical product from МБС on quality is similar to a commodity product. Thus, possibility of processing МБС in carboxymethyl cellulose, sodium salt (Na-CMC) is established.

7 THE ANALYSIS OF THE FATTY ACID COMPOSITION OF SEED OIL OF FENUGREEK

A.D. Ahabalayeva1, E.D. Skakovskii2, L.Yu. Tychinskaya2, O.A. Gaidukevich2, S.A. Lamotkin2, V.N. Reshetnikov1 1 - Central Botanical Garden of the NAS of Belarus, Minsk, Belarus 2 - Institute of physical organic chemistry of the NAS of Belarus, Minsk, Belarus [email protected]

Fenugreek (Trigonella foenum graecum L.) is a valuable medicinal plant. A medicinal raw materials are the seeds, the extracts from which possess anti-inflammatory, hypocholesterolemic, antioxidantive and other therapeutic effects. According to the literature data the seeds contain 6-10 % lipids which structure was studied insufficiently. The purpose of this work is the analysis of the fatty acid composition of seed oil of the various cultivars of fenugreek which have been cultivated in the Republic of Belarus (B) and Hungary (H) by methods of GC and NMR spectroscopy on nucleus 1Н and 13C. The seeds of following cultivars Ovary Gold, B, 2009 (I); Ovary Gold, H, 2008 (II); Ovary 4, B, 2009 (III); Ovary 4, H, 2008 (IV); PSZ.G.SZ B, 2009 (V); Ovary Gold, H, 2008 (VI) were analyzed. Oil was extracted with boiling hexane in the Soxhlet extractor for 10 hours, and then hexane was deleted. The oil content in the samples was 6,0% (I), 5,5% (II), 6,0% (III), 6,0% (IV), 6,3% (V), 5,5% (VI). For GC analysis the derivatisation of the samples of oil for generation of methyl ethers of fatty acids was spent. The chromatograph Crystal 5000.1 with a quartz capillary column 60 m long was used. The record of NMR was carried out on a spectrometer with operating frequency of 500 MHz 1 13 for nucleus Н and 126 MHz for C. 10 % solutions were analyzed in CDCl3. 36 fatty acids have been identified, basic ones of which are presented in the table.

Table 1 - The fatty acid composition of seed oil of fenugreek

Acid Contain (%) in the samples of oil I II III IV V VI Myristic 0,1 0,1 0,1 0,1 0,1 0,1 Palmitic 12,3 11,4 12,8 9,6 12,7 9,8 Margaric 0,2 0,3 0,2 0,2 0,2 0,3 Stearic 2,6 3,9 3,4 4,4 3,0 5,0 Oleic 11,6 16,5 12,9 17,6 13,4 17,2 Vaccenic 0,3 0,6 0,4 0,1 0,3 0,6 Linoleic 33,2 39,9 32,9 37,1 33,9 46,8 Arachic 1,0 1,4 2,3 1,3 0,8 1,0 γ-Linolenic 0,1 0,1 0,1 0,1 0,1 0,1 α-Linolenic 36,6 19,6 30,8 26,2 32,1 15,1 Behenic 0,6 0,9 0,8 0,7 0,7 0,9 Erucic 0,1 0,4 0,1 0,1 0,1 0,1 Arachidonic 0,1 0,4 0,2 0,1 0,1 0,2 Lignoceric 0,1 0,4 0,2 0,2 0,2 0,3

It has been established by NMR method, that oils consist mainly of triglycerides (96%) of fatty acids. Oleic and linoleic acids attach to the molecule of triglyceride in the central position while α- linolenic acid in the lateral one. The seeds of a crop of 2008 (Hungary) contain less oil and α- linolenic acid, but more oleic and linoleic acids, than the seeds of 2009 (Belarus).

8 THE INFLUENCE OF THE CONTENTS OF CHLOROPHYLL AND ITS DERIVATIVES ON THE QUALITY OF THE COTTONSEED OIL

A.N. Ahmedov, F.U. Suvanova Karshi engineering-economic institute [email protected]

In the process of cottonseed oil production the oily raw materials of the dark colour are obtained, where equally with gossypol and its derivatives are present the pigments of the chlorophyll. Between burning of the oil and containing chlorophyll there is a tight relationship. The chlorophyll can play the role of photosensibilizator at finding масел on light. According to this chlorophyll on light is a stimulator of the oxidation, then as in the absence of the light it does not influence upon the oxidizing process. The accelerating action of the chlorophyll to the oxidizing burning of fats remain the additive antioxidants. The content of chlorophyll and its derivatives in oils were studied by us, obtained from usual (I and II sorts) and low-grade (III and IV sort) cotton seeds. The comparison of the data between the two enterprises has shown that at conversion of low-graded cotton seeds in the kernel, the pressed kernel and the roasted kernel, the contents of the husk increases in comparing with usual ones approximately on 5-7%. This negatively tells on qualitative indexes of the obtained oil, in particular, increases the content of the chlorophyll and its derivatives. (Table)

Table Changes in the mass share of the chlorophyll and its derivatives in oils, got from usual and low- grade cottonseed by the method of pressing

Names of the enterprises Mass share of chlorophyll and its derivatives in oils, obtained from % Ordinary (of 1st and 2nd sorts) Lowe-sorted (of 3rd and 4th cotton seeds sorts) cotton seeds Joint-venture “Karshi oil 0,5 – 0,6 1,1 – 1,2 extraction” Open stockholding company 0,6 – 0,7 1,2 – 1,3 “Koson oil extraction”

The analysis has shown that in oils, obtained from ordinary middle-fibrous cotton seed, the mass share of chlorophyll and its derivatives is kept within 0,5-0,7%, but in the oil, obtained from low- graded cotton seed - within 1,1-1,3%. The raised contents of green pigments in the composition of the damp cottonseed oil make difficult the process of its alkaline refinery and blanching of activated adsorbents. Regrettably in practice often do not regulate the contents of the husk in the kernel, the roasted kernel and others, at the expense of which vastly grows worse the colour of the obtained oily raw materials. The acknowledgement is served by the followings: the colour of the oil, obtained from low-graded cottonseed on approximately 20-21 red and 7-8 blue units higher, in comparison with the colour of the oil, obtained from the usual (I-II sort) cottonseed. The main attention must be paid to the difference in the contents of pigments in blue units, which make difficult the processes of alkaline refinery of the obtained oils and their blanching of the activated adsorbents. Thereby, for the improvement of the processes alkaline refinery of the cotton oil and their blanching, it is necessary to stabilize the contents of the husk in the composition of kernel, the pressed kernel and the roasted kernel. Herewith it is necessary to produce the selection of the optimum amount of the inversed products, carried in roasting pan since in its composition also is contained the material, painting obtained oil in red and blue colours. High temperature processing

9 of the kernel results in the form of the new derived chlorophyll with the other components that complicates the following processes of the conversion of the cottonseed oil. Consequently, for increasing the output and quality of the obtained oil it is necessary to improve the processes of the conversion of the low-graded cotton seeds and derivatives from them oil of the different purpose.

SOME PARTICULARITIES OF REACTIONS OF COUMARINES AND 3- ETHOXYCARBONYLCOUMARINE WITH CARBORANYL-CONTAINING NITRONATES

O.A. Aimakov1, D.T. Kaziahmetova1, A.V. Kazantsev2 1 - Valikhanov State University, Chemistry and Biotechnology, Kokshetau, Kazakhstan 2 - E.A.Buketov Karaganda State University, Karaganda, Kazakhstan [email protected]

This work is to extend the previous studies [1, 2] the purpose of which was to synthesize new functional derivatives of carboranes with the potencial to have biological activity and to develop on their basis efficient medicines with the given range of activity. In this regard, we studied interaction of coumarine and 3-ethoxycarbonylcoumarine with nitronates. Carboranyl-containing nitronate (1) formed with high yields in reaction of nitrostyrol and lithiumcarboranes were found to react easily with activated double bond of coumarine and carboranyl-containing nitroderivatives of benzo-4H-pyranes (2) and (3).

RC CLi RC CCHPhCH=NOOLi + PhCH=CHNO2 B10H10 B10H10 1 O OH

RC CCHPhCH=NOOLi H O RC CCHPhCHNO + 2 2 B H B H 10 10 O O 10 10 1 2 O OH

COOEt COOEt RC CCHPhCH=NOOLi H O RC CCHPhCHNO2 + 2

B10H10 O O B10H10 1 3 The structures of the compounds synthesized (2) and (3) were confirmed by IR- and NMR1H- spectral data.

Ref. [1]. A.V. Kazantsev, V.V. Butyaikin, E.A. Otrashchenkov, Z.M. Muldakhmetov, Izv. AN, Ser. Chem., 1995, №10, P. 2058-2059 [2]. A.V. Kazantsev, S.M.Adekenov, Zh. Org. Chem., 2002, v. 38, P 1691-1696.

10 ALKALOIDS OF HAPLOPHYLLUM FOLIOSUM

V.I. Akhmedjanova1, L. Angenot2 1 - S. Yu. Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences, Republic of Uzbekistan, Tashkent 2 - Liege University, Liege, Belgium [email protected]

Haplophyllum foliosum Vved. (Rutaceae) is an endemic species of Central Asia. The plant is used in folk medicine for treatment of many diseases. We continued studies of alkaloids from the plant [1]. Methanolic extract of the air-dried aerial part collected in the phase of flowering beginning (Alimtai village, Tajikistan) was partitioned into basic (total alkaloids), neutral, and acidic fractions. The known quinoline alkaloids dubinidine (1), skimmianine (2), and foliosidine (3) were isolated from the total alkaloids; flindersine (4), haplamine (5), and preskimmianine (6), from the neutral fraction. Compounds 4, 5, and 6 were found in the plant H. foliosum for the first time.

O OMe R

N O MeO N O HH MeO

4: R = H 6 5: R = OMe

Flindersine and haplamine showed a cytotoxicity against HeLa and HCT-116 cancer cell lines in vitro experiments (IC50 < 100 μM).

Reference

1. V. I. Akhmedjanova, Kh. A. Rasulova, I. A. Bessonova, A. S. Shashkov, N. D. Abdullaev, Khimiya Prirod. Soedin., No. 1, 49 (2005).

SEWING TOGETHER LOW SUBSTITUTED ACETYL CELLULOSE WITH PYROMELLITIC DIANHYDRIDE

G.U. Akmalova, G.R. Rakhmanberdiev Tashkent Chemical Technology Institute [email protected]

Etherification natural cellulose in most cases begins in heterogeneous conditions and on a surface of fibers. Introduction cross-section covalent communications between cellulose macromolecules at etherification of multifunctional acids limits their mobility and by that complicates diffusion an etherification reagent deep into cellulose fibers. Partially replaced ethers of the cellulose, capable to be dissolved in organic solvents are the most suitable objects and modeling connections for studying of features cellulose sewing together by multifunctional acids. Homogeneous reactions low substituted cellulose acetates (C3=0.5) and above with pyrromellitic dianhydride were spent in solution dimethyl formamide. 11 Pyromellitic dianhydride, in homogenous conditions, starts to react with acetyl cellulose at a room temperature. Mix keeping acetyl cellulose - pyromellitic dianhydride in dimethyl formamid in a current of two days is accompanied by formation of transparent gel. Reaction etherification of cellulose at the first stages of increase in concentration free hydroxyl groups. At increase OH with 60 to 110 sorption exchange unit increases approximately three times, and at increase with 110 to 160 sorption exchange units increases approximately twice. However, further increase of concentration free hydroxyl groups a little bit increases sorption exchange unit. At increase with 160 to 210 and with 210 to 260 sorption exchange unit increases 1,2 and 1,1 times accordingly. Sharp increases in degree of updating at increase in degree of updating at increase OH with 60 to 160 is connected with dimensions of molecule pyromellitic dianhydride. As it was already marked, primary cetyl groups get hydrolyzed predominately at acid saponification acetyl cellulose (at atom C6). At the first stages of reaction etherification low substituted acetyl cellulose dia nhydride gets etherification with these groups. Thus the essential increase in degree of updating is observed. With increase in time of hydrolysis acetyl cellulose gradually saponifies secondary (at atom C2 and C3) acetyl groups. However secondary hydroxyl groups steric are less accessible to voluminous molecule dianhydride pyromellitic. Thereof, despite homogeneity of conditions reaction carrying out is observed reduction of speed of updating. The aforesaid the assumption will be co-ordinated with literary data about availability and reactionary ability hydroxyl cellulose groups. At sewing together acetone-soluble acetates of cellulose with dimetilethylenurea has been shown, what even at concentration minor alteration hydroxyl groups in cellulose availability remained too much more low, than in the initial sample.

CARBOXYMETHYLATED XYLAN FROM BIRCH PULP AS PAPER ADDITIVE

M. Alekhina, H. Sixta Department of Forest Product Technology, Aalto University, Espoo, Finland [email protected]

The development of new products and materials from renewable resources in connection with emerging biorefinery strategies has been discussed for several decades. However, up to now it has been a great challenge to design a production process which allows the utilization of all components of lignocellulosic material. Among the several potential biomass sources, birch wood is one of the most promising materials in the Northern countries for the supply of relevant amounts of xylan. Bleached birch kraft pulp constitutes an economically attractive source for xylan because it is easily accessible in high purity. Xylan is considered to be a valuable raw material for the manufacture of high value-added products in the food, the chemical and the pharmaceutical industries. However, the hemicelluloses have hardly been utilized as a raw material in industrial production. In pulping process the main utilization route of the hemicelluloses is the incineration and energy production during recovery of chemicals. As the calorific value of hemicelluloses is considerable lower than that of lignin, their application as chemical feedstock might offer much better economical opportunities. So far, industrial utilization of xylan has mainly included converting it into furfural and xylitol. Isolation of xylan can be carried out in several different ways, for example from hardwood chips prior to the pulping process by alkaline or neural-neutral process. Xylan can also be removed by ultrafiltration and precipitation from hardwood black liquor. However, it might be beneficial to remove the hemicellulose after pulping for the purpose of getting purified xylan in high yield. The xylan extracted from pulp after the kraft process doesn’t require additional purification steps as it is free of lignin and other contaminants. Adsorption of xylans to cellulose fibers has been shown to improve pulp properties, such as tensile strength, beatability and resistance to hornification. One major advantage of using xylan in pulp fiber modification is the inherent affinity of xylan to cellulose, yielding an irreversible adsorption. However if a high degree of adsorption is desired, the polymeric xylan may be modified to improve

12 the interactions with the pulp fibers. Similar to the addition of starch and CMC in the papermaking process, this improvement can be achieved by carboxymethylation of the adsorbing biopolymer. In this study, xylan was isolated by cold caustic extraction from a commercial bleached birch kraft pulp. The resulting hemicellulose-lean pulp reveals a narrow molecular weight distribution and thus can be favourably used as a dissolving pulp in different conversion processes. The purified xylan has been derivatized to carboxymethylxylan by adjusting the degree of substitution to three different levels following known protocols. Both the xylan and the carboxymethylxylans were blended with a commercial softwood kraft pulp to evaluate their effects on the development of papermaking properties upon refining.

ANTIOXIDANT ACTIVITY OF SAUSSUREA GENUS (ASTERACEA) PLANT EXTRACTS

L.I. Alekseeva1, Е.V. Bystrushkina2, A.G. Bystrushkin2 1 - Institute of Biology, Komi Research Center, Ural Division, Russian Academy of Sciences, Syktyvkar, Russia 2 - Botanic garden, Ural Division, Russian Academy of Sciences, Ekaterinburg, Russia [email protected]

Antioxidant properties of plants are used to create broad-spectrum pharmaceuticals. Saussurea genus specimen are widespread in Eurasian mountains, widely used in official and folk medicine. The study on the antioxidant activity of Saussurea sp. growing in the Urals has not previously been conducted. For the study we collected leaf samples of Saussurea sp. in natural habitats in the North, Middle and South Urals. The dried leaf samples were extracted with 70% methanol. To determine the antioxidant activity of extracts the reaction with the stable free radical diphenylpicrylhydrazyl was used. The highest antioxidant activity was determined in plant extracts of rare endemic mountain- tundra South Ural populations of S. uralensis. High antioxidant activity is shown for the species growing in the high mountain tundra and sub-loach habitats (S. alpina and S. uralensis), compared with a significantly lower activity of samples of medicinal mountain-forest species S. controversa. The effect observed is due to higher natural antioxidant compound content in plants adapted to alpine growth conditions with intensive solar radiation and significant daily and seasonal temperature range. Previously identified antioxidant activity for the Central Asian species is close in meaning with the extracts of the Ural Saussurea sp. Thus, South Ural population plants of S. uralensis can be considered as a valuable natural antioxidant source due to the originality of the biochemical properties, in particular of the high level of antioxidant activity.

This work was supported by MOB_ST_2010_II № 10-04-90802 Grant.

NOVEL BIOLOGICALLY ACTIVE TETRACOORDINATED PHOSPHORUS THIOACIDS AND THEIR DERIVAVATIVES WITH CHIRAL CENTRES

L.A. Almetkina1, G.T. Gabdullin1, Ye.M. Martianov1, I.S. Nizamov2, A.V. Sofronov1, R.A. Cherkasov1 1 - Kazan (Volga region) Federal University, Kazan 2 - Kazan (Volga region) Federal University, Kazan; A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan [email protected]

Substantial interest in tetracoordinated phosphorus thioacids and their derivatives is due to their high reactivity and their use as synthetic intermediates in the preparation of new organothiophosphorus compounds with a great variety of useful application. Dithiophosphoric acids as well as their esters and salts have found an expanding application as oil lubricant additives, corrosion inhibitors, surface-active agents, detergents, dispersing agents, household chemicals including pesticides, antitumour agents, analytical reagents, and for regeneration of cracking catalysts. We

13 deemed it to be necessary to prepare novel tetracoordinated phosphorus thioacids containing asymmetric centers in organic substituents bearing pharmacophoric functionalities. We have synthesized dithiophosphoric, aryldithiophosphonic and bisaryldithiophosphonic acids with pharmacophoric functionalities in O-organyl groups. We have tried to develop enantioselective methods of synthesis of organothiophosphorus derivatives of some chiral natural terpenols, terpene diols and tartrates such as D- и L-menthols, (1R)-endo-(+)-fenchyl alcohol, (1S)-endo-(-)-borneol, (1R)-(-)-nopol, (1R,2S,3S,5R)-(+)-isopinocampheol, trans-3,4-pinanediol and (+)-dimethyl L- tartrate. Optically active O,O-diterpenyl dithiophosphoric, O-terpenyl aryldithiophosphonic and bisdithiophosphonic acids acids were obtained when these chiral terpenols were involved in reactions with tetraphosphorus decasulfide or 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides. The thioacids obtained were transformed into the corresponding ammonium salts when ammonia and chiral R- or S--phenylethylamine were used. The treatment of the ammonium salts prepared with benzoyl chloride, methyl chloroacetate or epichlorohydrin results in S-organyl O,O-diterpenyl dithiophosphates and O-terpenyl aryldithio- phosphonates with optically activities. New chiral bistriorganylgermyl, stannyl and plumbyl, cyclic diphenylsilyl and diphenylplumbyl derivatives of O,O-diterpenyl dithiophosphoric and O-terpenyl aryldithiophosphonic acids were also prepared from these salts. It is noteworthy to compare the biological activity of enantiomeric pure dithiophosphates with the corresponding racemic dithiophosphoric acids and their ammonium salts. The tetraphosphorus decasulfide has brought about to react with R,S--phenylethanol with the formation of the racemic O,O-di(-phenylethyl) dithiophosphoric acid transformed into the corresponding ammonium salt in the reaction with (S)-(-)-(-phenylethyl) amine. The molecular structure of R,S--phenylethylam- monium salts of O,O-diethyl dithiophosphoric acid was established by single crystal X-ray analysis. Since dithiophosphoric, aryldithiophosphonic and bisaryldithiophosphonic acids and their derivatives prepared involve pharmacophoric functionalities, their genotocity, mutagenic, bactericidal and fungicidal activities were tested against Salmonella typhimurium TA 100, Escherichia coli PQ37, Candida albicans, Rhodotorula rubra, Alternaria tenus, Mucor pusillus, Aspergillus fumigatus, Aspergillus flavus, Epidermophiton flocosum.Penicillium tardum and Penicillium chrysogenum. Thiophorylatedy moronotepenes showed appreciable antimicrobial activity.

PERSPECTIVES OF USING ROSIN RESIN ACIDS FOR BIOLOGICALLY ACTIVE SUBSTANCES SYNTHESIS

M.V. Andrukhova, V.L. Fleisher Belarusian State Technological University, Minsk, Republic of Belarus [email protected]

One of the most intensively developed directions in the field of chemistry and technology of plant origin substances is connected with investigation of biological activity of isolated and modified natural low-molecular compounds. The particular interest is caused by the works devoted to the study of biological activity of resin acids derivatives. Rosin is a widely used natural product that may still have an unknown potential. It is used industrially as an agent in paper sizing, printing inks, soup, cosmetics, adhesives, emulsifiers and medical supplies. It possesses hypocholesteromic activity, antigastric ulcer activity, blood glucose lowering effect and macrocyte clumping activity. Besides, rosin is a renewable source of resin acids – tricyclic diterpene monocarboxylic acids. They possess unique structure (the structure of resin acids molecules is similar to that of steroids) and biological activity. Moreover, they are a promising object for chemical modification.

14 Recently scientists of the different countries have synthesized variety of new derivatives of abietic, levopimaric and dehydroabietic acids, exhibiting a wide spectrum of biological activity, and have proposed new effective ways of obtaining previously synthesized bioactive compounds. So, peroxides are synthesized from abietic acid, possess potential antimalarial activity; catehols, carnosic acid analogues, show fungal, antitumor, antimutagenic and antiproliferative activity, and salts of benzo[f]quinone spiro-derivatives with abietic acid – antitumor activity in the case of leukemia, melanomas, cancer of thick gut, kidney, mammary gland. It is established that some derivatives of 12-hydroxyabietic (picealactone C) and 14-hydroxyabietic acids (quinone, triptolide, triptonide) are bioactive compounds. Relation between the chemical structure and biological activity in the series of С18-oxygenated derivatives of abietic acid, C18-oxygenated derivatives of dehydroabietic acid and heterocyclic derivatives of abietic acid is proved. From the point of view of biological activity new functionally substituted N- and P-containing salts of abietic acid as well as the complex of Cu2+ with abietic acid as copper-containing enzyme are of interest. Alongside with abietic acid derivatives scientific and practical importance is given to some 15- hydroxydehydroabietic acid derivatives (diols, ketoester, lactones, etc.). Azomethines, amids and quaternary ammonium compounds based on dehydroabietic acid show bactericidal and fungicidal activity. It is proved that halogenated oximes of dehydroabietic acid can perform the function of BK channel openers. Diene adducts of levopimaric acid with benzoquinone and maleic anhydride, quinopimaric and maleopimaric acids respectively, are prepared via Diels–Alder reaction are of interest as objects for chemical modification. In particular, previously inaccessible nontrivial quinopimaric acid derivatives are synthesized by oxidation with dimethyldioxirane are found to be moderately active against influenza virus type A and the papilloma virus. Bioactive amids, imids, amidoimids and alkaloids of new structural type based on maleopimaric acid are of great value too. Besides, a highly effective synthetic method for potentially biologically active functionally substituted N- and P-containing salts of levopimaric and maleopimaric acids with aromatic and heterocyclic amines and triphenylphosphine is developed. Thus, the literature analysis has shown that synthesis of analogues of natural biologically active substances and derivatives of synthetic substances on the resin acids basis is a perspective direction in the field of chemistry and technology of low-molecular substances of plant origin.

DIENE CONDENSATION OF ALPHA-TERPINENE WITH ACRYLATE DERIVATIVES

N.A. Anisimova1, A.A. Kuzhaeva2, P.V. Zgonnik2, Z.P. Samsonova1, M.A. Ponomareva1 1 - Saint-Petersburg State Technological University of Plant Polymers, Saint-Petersburg, Russia 2 - Saint-Petersburg State Mining Institute, Saint-Petersburg, Russia [email protected]

We have investigated the interaction of α-terpinene with acrylate derivatives - methyl methacrylate (1), butyl acrylate (2) and butyl methacrylate (3) under various conditions. It has been shown that the interaction of α-terpinene with dienophile (1) for 40 hours in boiling benzene was accompanied by the formation of endo- and exo-diastereomers of methyl 1-isopropyl-4-metylbicyclo[2. 2. 2] octene -5-yl-3-carboxylates I, II. Apparently, the less stable exo-isomer II in reaction conditions underwent intramolecular transformation leading to the formation of oligomer IV, the role of monomer in which being performed by bicycloctene II formed during the reaction. Apart from the above mentioned products an aromatic product – p-tsimol III was separated from the reaction mixture. Formation of the latter may be explained by the process of dehydrogenation of the initial α-terpinene under the conditions of the reaction. Diene condensation of α-terpinene with dienophiles (2, 3) was of a similar pattern. As a result, the corresponding endo-V, VIII and exo- bicycloctenes VI, IX , as well as oligomers VII, X were received.

15 IR, NMR (1)H spectroscopy proved the structure of the obtained chemical products as compared to similar studies of the compounds with the same structure. The molecular mass of the oligomer was proved by gel-chromatography.

X COOR C H ,800C 6 6 COOR X + CH2=C COOR 40 h + + X 1-3 endo- exo- I,V,VIII II, VI, IX III

X=R=CH3 1, I, II, IV COOR COOR X=H, R=n-C H 2, V-VII COOR 4 9 X X X X=CH3, R=n-C4H9 3,VIII-X n IV,VII,X Implementation of the reactions under analysis at room temperature in the presence of catalyst (AlCl3) led to a complex mixture of cyclohexadiene and aromatic products of the reaction.

ELECTRONIC MAPPING TECHNIQUE FOR EVALUATION OF EUROPEAN CRANBERRY (OXYCOCCUS PALUSTRIS PERS.) RESOURCES IN KARELIA

V.K. Antipin, P.N. Tokarev Institute of Biology, Karelian research centre, Russian Academy of sciences [email protected]

Assessment of the present condition of essential medicinal and food plant resources (Буданцев, 2005) and developing an information system on Russia’s biological resources (Павлов, Стриганова, 2005) are an important field of fundamental research in evaluation of resources. Karelia’s mire flora is formed of more than 50 medicinal and food plants (Юдина и др., 1988). European cranberry is most popular with the local population and small-fruit purchasing companies. Cranberry resources were mapped by means of the technique developed by the authors (Антипин, Токарев, 2007, 2008, 2009а, 2009б). Using the technique, the cartographer can immediately start mapping berry resources, avoiding a labour- and time-consuming process of making intermediate vegetation maps and to pass directly to mapping of resources. The technique is based on a combination of two methods widely used in cartography: a network of regular equidimensional squares and cartograms (Токарев, 1998б, 2005; Вомперский и др., 2005; Heikinheimo & Raatikainen, 1971; Lappalainen & Hanninen, 1993). Our cartogram of cranberry resources is presented as a network of squares covering an area of 5 ×5 km (the total number of squares is 6139). The network was developed using licensed GIS – MapInfo software and was based on extensive cartographic and remote (aerial photographs and satellite images) materials and the authors’ data from the long-term study of cranberry on model mires in Karelia. Cranberry is confined to mires, and its resources depend directly on mire area. Therefore, the first step was to form the cartographic layer “Paludification of Karelia” in the regular square network. A share of the area of mire sites and cranberry resources (kg/ha) were then estimated for each square of the key area with model mires. Cranberry resource indices were then extrapolated on the entire regular network covering Karelia’s territory, based on GIS-technologies and satellite images.

16 Calculations were performed using minimum cranberry yield values. The authors have found that cranberry yield tends to decrease, depending on the geographic position of a mire site. This trend was taken into account. The structure and contents of table file fields in the cranberry resources geodata were worked out (Антипин, Токарев, 2009а,б, 2010). Cranberry resources at the fruit-bearing mire sites of each square were estimated using an algorithm developed. After filling all the squares of the regular network a Cartogram of Karelia’s Cranberry Resources was constructed. It is an electronic small- scale summary map showing the spatial distribution of cranberry resources in Karelia. The map contains voluminous information on fruit-bearing mire sites, where European cranberries are abundant, and on the geographic distribution of cranberry resources at such sites. The cartogram illustrates the irregular distribution of cranberry resources in Karelia. Most cranberry resources are concentrated in Central and South Karelia, but they are small in North Karelia. At the same time, there are practically no cranberries at some sites in the most densely populated southern areas, especially in the coastal zones of Lakes Ladoga and Onega. The total cranberry resources of Karelia’s mires, estimated from the cartogram using GIS-technologies, are 11,2 thousand tonnes. The cartogram can be used to assess cranberry resources in any administrative district of Karelia and smaller areal units. The study was conducted with financial support from the Programme “Biological resources of Russia: assessment of the condition and the fundamentals of monitoring” (Project 01200955237).

ANTIOXIDANT CAPACITY OF ROSMARINUS OFFICINALIS EXTRACTS AS A FUNCTION OF EXTRACTION TIME, PRESSURE AND FLOW OF SUPERCRITICAL CO2

A.J. Arias, G.P. Arias, C.A. Ruiz, E.A. Ramirez, J.R. Martinez, E.E. Stashenko Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Rosemary has been used in many cultures as an important aid for food preservation. Carnosic acid, carnosol and methyl carnosate are present in rosemary extracts and have been associated with the high antioxidant capacity of rosemary extracts. Their antioxidant capacity has been found to be superior to those of the commercial synthetic antioxidants BHA and BHT. Supercritical fluid extraction with CO2 is an important technique for food and pharmaceutical applications because the resultant extracts are free of solvent residues. Rosemary leaves and stems were dried and milled to a particle size between 0,08 and 0,6 mm. Final drying at 50 °C afforded vegetal material with a moisture content below 8%. A central composite experimental design was used with this material to obtain Rosemarinus officinalis extracts under different conditions of pressure (300, 400, 500 bar), flow (25, 37,5, 50 g/min) and time (30, 75, 120 min). Their ORAC antioxidant capacity determinations produced values between 1,2 and 1,9 μmol Trolox®/mg extract. While pressure, extraction time and CO2 flow had a significant effect on the extract´s antioxidant capacity, their binary or ternary interactions had negligible effect. The extract obtained with the highest yield exhibited the highest antioxidant capacity (1,92 μmol Trolox®/mg extract). Chromatographic analysis (HPLC-DAD, LC-TOFMS) confirmed the presence of carnosic acid and the positive correlation between polyphenols content and antioxidant capacity.

ECOLOGICAL FACTORS INFLUENCING TO BIO-ACTIVE SUBSTANCES IN EMPETRUM HERMAPHRODITUM

N.A. Artemkina, T.T. Gorbacheva Institute of the North industrial ecology problems KSC RAS, Apatity, Russia [email protected]

Bio-active substances including phenolics are of great interest for finding-out of both physiological and biochemical mechanisms of plants adaptation to growing conditions in subarctic region.

17 Northern ecosystems are characterized by a range of ecological loads such as deficiency of nutritional elements, low soil pH, short growing season and pollution influence. In such severe conditions vegetation shares a lot of assimilated carbon to secondary metabolites among which one of the most widespread are phenolics. Many influential ecological theories and generalizations have been based at least in part on phenolics investigation, including the plant apparency theory, optimal defense theory, resource availability hypothesis, carbon-nutrient balance hypothesis, and growth-differentiation balance hypothesis. Empetrum hermaphroditum Hagerup is one of ground vegetation species in North taiga forests of Kola peninsula and dominating in the conditions of pollution by emissions of Cu-Ni smelter "Severonikel". The aim of this study was to extend our understanding concerning to the role of phenolics in adaptation of E. hermaphroditum by the research of phenolics dynamic. The subjects of investigations were 1-year leaves (current-year leaves) (L1), 2-year and older leaves (L2). The investigations were carried out on the stationary monitoring plots represented different stages of technogenic succession of spruce (Picea obovata Ledeb.) and pine (Pinus sylvestris L.) biogeocenoses: a background (270, 260 km from emission source), defoliating forests (31, 48, 28, 100 km), a technogenic sparse (8, 7 km). Total phenolics were determined with the Folin-Ciocalteu reagent. Concentrations of total phenolics were expressed in mg of equivalent gallic acid g-1 of leaf dry weight.

Research spending resulted in determination of spatial (biocenose and parcel) differences in phenolics content in leaves of E. hermaphroditum under pollution. In both pine and spruce forests phenolics accumulated at most in 1-year leaves of E. hermaphroditum. Spruce forests are more abundant in phenolics as concerning to E. hermaphroditum leaves growing in dwarf shrubs parcels. Pine forests are characterized by significant difference in phenolics content: we observed more phenolics in E. hermaphroditum leaves growing under the crowns (p<0.05). In spruce forests phenolics content in 1-year leaves of E. hermaphroditum decreased under technogenic load increasing. Probably that is caused by phenolic biosynthesis suppression in young leaves. We observed phenolics accumulation in 2-year and older leaves of E. hermaphroditum at a stage of a technogenic sparse (8, 7 km) (both under and between the crowns in pine forests such as between the crowns in spruce forests). The data shows that under pollution protective substances content in E. hermaphroditum leaves depends on type of forests and landscape position. The greatest changes of chemical compounds content are characteristic for E. hermaphroditum leaves growing in pine forests.

18 SOYBEAN OIL HYDROGENATION ON NICKEL AND PALLADIUM CATALYST

A.B. Auyezov, Z.A. Bizhanov, S.K. Toktasynov, A. Nurakyshev, A.S. Afanasieva Research Institute of New Chemical Technologies and Materials at Kazakh National University named after al-Farabi, Almaty, Kazakhstan [email protected]

Currently, the hydrogenation of vegetable oils in the industry is carried out on nickel catalysts at temperatures of 180-230 oC. However, under these conditions, nickel can react with components of fats, forming soluble salts that can contaminate food product. In addition, very finely divided nickel catalyst is suspended in a hydrogenated basis of fats, and it is very difficult to separate it from the finished product, which creates a danger of falling nickel in margarine and cooking fats. We have developed low-percentage (0,1-1,0%) inflicted modified palladium catalysts, capable of conducting the process of hydrogenation of vegetable oils at lower temperatures (90-150 oC) and pressure of 0,3-1,0 MPa. Physical and chemical properties of products of soybean oil hydrogenation (i.n.=70) on palladium and nickel catalysts (P = 0.4 MPa) are shown in Table1. Table 1. Pd / catalyst

texp., The max. Tmelting., The Kaminsky Content of Content of oC rate of оС content hardness at stearic acid / linolenic / hydrogena of trans- 15 ° C, g / cm palmitin linoleic / tion., isomers,% acid,% oleic acid,% cm3/min 70 19,8 35,5 30,2 - - - 90 37,0 35,7 33,3 119,0 16,3/9,8 - / 7,0 /67,0 110 50,0 36,0 38,9 206,0 12,1/9,1 - / 2,5 /76,3 120 69,0 36,7 40,8 211,0 12,3/10,2 - / 2,3 /75,2 130 63,0 37,7 43,2 327,0 12,3 /9,1 - / 1,9 /77,1 140 72,0 38,0 44,2 450,0 12,1/9,8 - / 1,9 /76,3 150 88,0 38,2 43,8 420,0 11,7 /9,4 - / 2,0 /76,9 Ni / catalyst (Pricat 10) 70-90 The reaction does not proceed 110 10,1 45,7 22,7 105,0 21,8/11,5 0,9 /14,1 /49,7 120 13,0 42,3 24,3 109,0 18,2/10,6 0,2 /12,3 /58,8 130 28,0 44,2 25,0 129,0 20,9/11,9 0,7 /11,2 /55,3 140 35,0 42,8 25,5 144,0 19,1/10,3 0,2 /10,2 /60,3 150 48,0 42,2 24,4 109,0 16,6/12,6 0,6 / 9,7 / 60,6 Basis of fats obtained with using of nickel catalyst while having a low hardness, high melting point and a high content of saturated acids are not fully conform to state mandatory standards 28414-89. Besides, these standards admit residual nickel content in food fats’ basis. Palladium catalyst eliminates these deficiencies, demonstrating a high selectivity and activity. The catalyst can be reused, easily separated from the oil and do not poison the food preparations.

BIOLOGICALLY ACTIVE SUBSTANCES OF PAPAVER NUDICAULE L

A.M. Babykina, T.P. Antsupova East Siberian State Technological University [email protected]

Papaver nudicaule L. has been used long in ethnomedicine for bloody flux, digestive tract aches; flower tincture is useful for liver diseases. Gruel of immature fruit is given to children as a sedative and tranquilizer. In Tibetan medicine it is applied for pleurisy, pneumonia, as a sudoriferous, and as 19 an obstipant for intestinal upset (Telyatiev, 1985). The grass contains up to 0.5% of alkaloids, flavonoids, besides saponins were found in grass and roots (Shreter, 1975). The objective of the given paper was the study of chemical composition of Iceland poppy, prevalent in Trans-Baikal steppe and forest-steppe zone. Plant specimens were gathered in central regions of Western Trans-Baikalia (the Republic of Buryatia territory) in the years 2008-2010. We have discovered alkaloids, flavonoids, coumarins, iridoids, saponins, tannins in subterraneous and aerial organs of poppy. Since alkaloids are the main representatives of poppy’s biologically active substances, their content was determined depending on plant’s organ, development stage and habitat. It was discovered that the aerial part is more alkaloid rich than the subterraneous part; at that the maximum summary content was registered in flowers with fruits (2.45%) in the stage of blooming and initial fruit-bearing and in leaves (2.38%) in the beginning of vegetation. The minimum content was registered in stalks (0.59%) in the plant’s bud-formation stage. At that, the specimen gathered in forest-steppe zone were more alkaloid rich than the ones gathered in steppe zone. The content of 17 macro- and microelements was also determined. Iceland poppy was discovered to accumulate a significant amount of such microelements as Ti, Cr, Mn, Cu, Zn, Ba, and macroelements as P and S. At that, elemental composition of poppy varies considerably depending on the place and time of gathering.

Bibliography 1. Shreter A.I. Soviet Far East medicinal flora. M.: Medicina.1975. 328 p. 2. Telyatiev V.V. Central Siberia’s useful plants. Irkutsk: East-Sib. book house.1985. 383 p.

EFFECT OF OXYGEN ON LEVOPIMARIC ACID THERMAL AND PHOTOCHEMICAL TRANSFORMATIONS IN SOLUTIONS

M.P. Bei1, Е.D. Skakovskii2, L.Yu. Tychinskaya2, О.А. Gaidukevich2, А.P. Yuvchenko1 1 - Institute of chemistry of new materials NAS of Belarus 2 - Institute of physical-organic chemistry NAS of Belarus [email protected]

Levopimaric acid (LA) is one of the major components of pine turpentine, - an important raw materials for the timber field. However, it is easily isomerized by heating in neoabietic, palustric and abietic acids and after the distillation of turpentine is contained in varying amounts in the rosin, the quality of which depends strongly on the resin acids composition. Despite the widespread use of rosin, the effect of oxygen on the thermal and photochemical reactions of resin acids studied insufficiently. The purpose of this study is the analysis of thermal and photochemical transformations of LA in deaerated and oxygenated solutions using NMR method. LA was isolated from pine turpentine (Pinus silvestris L.) with 2-amino-2-methyl-1-propanol. Major component content was 92%. Kinetic studies to determine the effect of oxygen was carried out with 0.01 M solutions of LA in methanol-d4 and acetone-d6. To facilitate the identification of resin acids forming during the transformation and 13C NMR spectra records the initial concentration of LA in solution was increased to 0.2 M. Spectra were recorded on NMR spectrometer AVANCE- 500 (500 MHz - 1H, 126 MHz - 13C). The assignment of signals was performed using a 2D correlation spectroscopy (COSY, NOESY, HMBC and HSQC). For research solutions were soldered into quartz liners – tubules with outer diameter 4,0-4,2 mm placed for spectra recording in 5 mm NMR ampoules. Kinetic studies were carried out at different temperatures, under the influence of microwave radiation in a household microwave Electronics SP-10 (power - 600 watts, the operating frequency - 2450 MHz) and under radiation with light from a mercury lamp DRSh- 500, passed the filter BS-4 at room temperature . It has been stated that the thermal transformations of LA in methanol-d4 proceed effectively, starting with 443 K, and in acetone-d6 - 423 K. At saturation of solution with oxygen reactions

20 occur efficiently at lower temperatures: 363 K - in methanol-d4, and 343 K - in acetone-d6 It is shown that under the temperature abietic, palustric and neoabietic acids are formed from LA in both solvents and in methanol-d4 abietic prevails, and in acetone-d6 - palustric acid. Oxygen in both solvents promotes the disproportionation reaction to form the main product - dehydroabietic acid. Microwave radiation under these conditions does not affect on the deaerated solutions, but leads to a LA transformations in the oxygenated solutions. In this case the microwave effect is similar to thermal: as a result the same products are formed.. It has been found that photolysis of deaerated methanol-d4 solutions is accompanied by isomerization of the LA to form a new compound – 9-isopropyl-1,5-trans-dimethyltetratcyclo [5,140,6,110,8,110] tetradeka-9-ene-1-carboxylic acid. The presence of oxygen leads to competition between the isomerization and disproportionation. Photochemical transformations of LA in acetone- d6 are much slower than in methanol-d4 with a predominance of disproportionation for oxygenated solutions.

THE SYNTHESIS OF TERPENOID DIACIDS AND THEIR DERIVATIVES

M.P. Bei, A.P. Yuvchenko Institute of chemistry of new materials NAS of Belarus [email protected]

The synthesis of terpenoid diacids 1, 3, 4 from maleopimaric acid (MPA) were been developed. MPA is a terpenoid compound obtained from adduct of rosin and maleic acid anhydride. Diimidodiacid 1 was obtained by reaction of MPA with 1,6-hexanediamine in 1,2-dichlorobenzene at 150ºC during 6 hours (yield 51%) [1].

O O

N 6 N

O O

COOR 1 (R=H) ROOC R = CH3 (1a), C2H5 (1b), CH2CH=CH2 (1c)

The synthesis of aromatic diimidodiacid 3 was been carried out in two stages. At the first stage monoimide 2 was obtained by reaction of MPA with 1,4-phenylenediamine in toluene under reflux. The compound 2 was treated by excess of melting MPA to give aromatic diimidodiacid 3 at the second stage [2].

O O O

N NH2 MPA N N 240-260oC O O O COOH 2 96% COOR 3 (R = H) ROOC

R = CH3 (3a), C2H5 (3b), CH2CH=CH2 (3c)

Aliphatic, aromatic and heterocyclic monoamides of fumaropimaric acid 4 were been synthesized [3] from maleopimaric acid amides. Esters 1a–c, 3a–c, 4a–c of terpenoid diacids 1, 3, 4 were been obtained by treating these compounds with suitable alkylating agents (dimethyl sulfate, diethyl sulfate, allyl bromide) in dimethylformamide at the presence of potassium carbonate.

21 COOR

COOR

R = H (4), CH3 (4a), C2H5 (4b), CONR'R'' CH2CH=CH2 (4c)

The obtained diacids 1, 3, 4 are thermally stable compounds and begin to decompose at the temperature above 290ºC (diacid 3 melt at 350ºC with decomposition). Terpenoid diacids 1, 3, 4 and their esters are probably useful as monomers in a synthesis of polymer compositions, and as ingredients of adhesive compositions, presumably for use in a base of flexographic inks.

References

1. Bei M.P., Azarko V.A., Yuvchenko A.P. // J. Gen. Chem. 2010. Vol. 80. P. 770. 2. Bei M.P., Yuvchenko A.P. // Vesti National. Acad. Sci. Belarus. Chem. Ser. 2010. N1. P. 74. 3. Bei M.P., Yuvchenko A.P. // Vesti National. Acad. Sci. Belarus. Chem. Ser. 2010. N3. P. 84.

CELLULOSE SURFACE CHEMICAL MODIFICATION: RELEVANT ADVANCES IN THE PROCESSES AND THE CHARACTERISATION TECHNIQUES

N. Belgacem Polytechnic Institute of Grenoble (Grenoble INP) Pagora - Laboratoire de Genie des Procedes Papetiers (LGP2), UMR CNRS 5518 Domaine universitaire - 461, rue de la papeterie 38402 Saint-Martin-d’Hиres - FRANCE [email protected]

The last two decades, several approaches of chemical modification of cellulose fibres surface were developed with the aim of providing these renewable natural materials various functionalities, such as:  Hydrophobisation.  Improved adhesion strength to the polymeric matrices in composite materials.  Magnetic features.  Photo-activity.  Fluorescence-emitting substrates.  Antimicrobial properties, etc. Several concrete very promising routes of modification were established, particularly: (i) plasma discharge activation solvent-free grafting; (ii) reversible hydrophobic-hydrophilic tailoring of cellulose surface; (iii) fibre-matrix continuous chemical bonding composites, through click- chemistry, “grafting from” and “grafting onto”; and (iv) layer-by-layer polyelectrolyte system combined by the precipitation of metallic or metal oxides nanoparticles, in order to prepare hybrid materials. The characterisation of the modified surfaces was performed using different characterisation techniques. The modified surfaces were ascertained by contact angle measurements, Scanning Electron Microscopy, CP-MAS 13C-NMR, FTIR, X-ray photoelectron spectroscopy and ToF SIMS. The present talk reports the most relevant advances in the field of surface chemical modification of cellulose fibres achieved both in terms of the modification processes and innovative characterisation techniques.

22 IMPACT OF ACID AND ALKALI PRETREATMENT OF MISCANTHUS GIGANTEUS ON CELL-WALL LIGNIN AND HYDROXYCINNAMIC ACIDS IN RELATION TO DEGRADATION BY POLYSACCHARIDE-ACTIVE ENZYMES

N. Belmokhtar1, A. Habrant1, N. Lopes-Ferreira2, B. Chabbert1 1 - UMR FARE, INRA-URCA, Reims cedex France 2 - IFP Energies nouvelles, Rueil-Malmaison France [email protected]

Miscanthus giganteus is perennial rhizomatous and herbaceous energy crop that gives rise to great biomass yields. However, efficient enzymatic saccharification of cellulose is hindered by many physicochemical, structural, and compositional features. Grass cell walls are characterized by the presence of hydroxycinnamic that play a significant role in cross-linking wall polymers into a cohesive network. Notably, ferulic acid is reported to cross-link hemicellulose and lignin whereas p-coumaric acid mostly esterifies lignin. Generally speaking lignin and phenolic acids are known to hamper bioconversion of polysaccharides. Pretreatments are thus required to overcome the recalcitrance of this lignocellulosic network. In the scope of a better identification of the main limiting factors to saccharification we have compared the effect of dilute acid and ammonium hydroxide pretreatments on the efficiency of a cellulase cocktail produced by Trichoderma reesei on small fragments isolated from miscanthus. To this end, changes in the cell wall phenolic components were addressed at the cell level. Following a 144h enzyme incubation of untreated plant specimen, no alteration of the tissues was evidenced in contrast to acid or alkali pretreated samples. Detailed investigation of lignin and phenolic acids distribution in individual secondary cell walls of epidermic and vascular sclerenchyma, vessels and parenchyma was assessed using UV micro spectrophotometry. Comparing UV absorbance spectra between untreated and pretreated substrates shows a reduction in lignin and phenolic components in all tissues. The heterogeneity of phenolic composition according to the cell types may impacts on the efficiency of pretreatments aiming at improving lignocellulose saccharification.

THE DYNAMICS OF NATURAL GRASS VEGETATION IN THE FORESTS UNDER THE INFLUENCE OF SILVICULTURAL THINNING

N.V. Belyaeva, A.V. Gryazkin, N.V. Kovalev, A.S. Khodachek, A.A. Fetisova The Saint-Petersburg State Forest Technical Academy of S.M.Kirova [email protected]

The article analyzes the structural changes and changes of species composition of the lower layers of vegetation (natural grass vegetation) in forest of spruce-oxalidosum types, passed by felling forest care of varying intensity. The data obtained make it possible to identify how forest ecosystems reacting to the thinning of forest. This allowing predict the development of grass cover. After silvicultural thinning, the lower layer of vegetation keeps the organic and mineral matter and including them in the system of small bio cycle. This is reflects the resource-saving role of herbaceous plants the living cover of ground in forest ecosystems. Natural grasses and the undergrowth supports stability of forest phytocoenosis (Mel’nikov, 1999; Belyaeva NV, 2006). The object of the study is a group permanent plots (PP), that are made in 1929 in the experimental forest "Siversky forest in the Leningrad region (series PP 1). Were investigated a control sites (PP 1A) and objects of test with silvicultural thinning - PP 1B, 1C, 1D, 1E. Area of the sites of 0,25 ha. Our studies show that the higher the intensity of thinning, the greater rise the percentage of the total projective cover of grass, which is associated primarily with increasing illumination under the canopy and with decreasing competition of plants as a result of economic activities. Another scenario after felling it's a strong growth of underbrush. At one of our facilities number of shrubs

23 Mountain ash (Sorbus aucuparia L.) increased to 16393 exemplars on hectare. At such sites projective cover of grasses did not increase. Herbs were depressed. In addition to structural changes in natural grass vegetation is observed dynamics of species composition - increasing the number of species in the 1.5–1.8 times. Increase of projective cover of grass occurs to a greater extent by increasing the number of megatrophic and oligotrophic plants. This allows us to make an assumption about the possibility of increasing species diversity of ground vegetation with the regular holding silvicultural thinning. Increasing the projective cover of grasses is largely due to increase in the number megatrofnyh and oligotrophic plant. Such as Pulmonária obscúra, Pulsatílla pátens, Corydalis solida, Oxalis acetosella, Solidago virgaurea, Polygonatum multiflorum, Latin Bidens tripartíta, Equisetum arvense, Pterídium aquilínum, Elytrígia répens. All of these plants to varying degrees are important non-wood forest products. These herbs can be used in the food, cosmetic and pharmaceutical industries. And given the decline in the quality of grasses material grown in artificial conditions, this information can be very interesting. At this level it is necessary to study the quality of harvest herbs collected in forest where were made silvicultural thinning.

BIOLOGICALLY ACTIVE COMPOUNDS OF SOME RANUNCULACEAE L. FAMILY REPRESENTATIVES OF SOUTH SIBERIA

O.A. Belykh Baikal national university of economics and law. Irkutsk, Russia [email protected]

Nowadays people of all over the world try to solve their health problems using as less chemically synthesized medicine as possible. That’s why the total tendency of pharmacology development is in the further adoption of medical preparation received from the naturals raw materials mainly from the medicinal herbs. The world pharmacological market needs sharply new types of medicinal preparations capable to substitute the existing medicine. More then 200 herbs are successfully used now in national medicine of Eastern Asia countries. They are related not only widely spread and excellently studied species but also to rare and endemic ones the properties of which are not studies by the official medicine. The book Pharmacology of Russia contains 183 species of wild and cultivated herbs [1]. The expansion of such herbs list and studying of their properties opens large perspectives for obtaining new pharmacological products. The Siberian medicinal herbs grooving in the wild are the rich raw basis for the production of pharmacological means and biologically active additives. Owing to the urgency of these problems investigations wild the herbs of Ranunculaceae L. Family have been don at Irkutsk biostation since 1998. The Thalictrum minus L. – is a perennial grassy herb. The phytochemical studying of plant growing in the Siberian part of its area showed that this plant contains triterpenic saponins that possess wide spectrum of medical action. It was found out that they are very positively active in relations to many forms twisted tumours, cytotoxic and contraceptive activity, ability to regulate the level of some hormones [3,4]. Aconitum barbatum Pers. – is a perennial grassy herb. It is widely spread in the meadows of partially wooded steppes of the Siberian region. Alkaloids are found in all parts of this herb. Their contents varies very much. Flavonoids are also found there. In national medicine the water infusion of roots and leaves is used in small doses as sedative for the curing of rheumatic pains and tumours. Our task was to define the contents of biologically active compounds in plant raw from natural and introductive populations, and going into the problem of these resources efficiency in practice. The selection and growing of panmictic introductive population of Thalictrum minus L. Family was held at Irkutsk biostation. During our investigations it was discovered that in panmictic population of Thalictrum minus L. the saponins contents decreases insignificantly. The dynamic saponin studies in ontogenesis showed the increase of a given substance with the age. The four year old generaltive specimens are characterized by the highest saponins content. Beginning with the second year of vegetation, the plants can be used as a raw material as we can watch considerable saponins accumulation in the surface mass of virginal plants. 24 The middle-aged generative plants of the fourth year cultivation give the highest yield of airily dry phytomass – 1430 kg/hect. end contents of individual substance is 26,6 kg/hect. The effective use of Thalictrum minus L., . Aconitum barbatum Pers. of family Ranunculaceae L. and other useful plants as a source of biologically active caponins and alkaloids depends on qualitative and quantitative contents of their group. The accumulation of biologically active substance in ontogenesis is influenced by the method of this culture growing, agrotechnic ways, species peculiarities and local conditions of growth. The introductive method affirms the economic advantage of medicinal herbs cultivation. The method of getting medicinal raw the help of biotechnologies is dozens of times expensive, however, many of the pharmacological corporations went over to this way as it is this highly technological raw which gives us possibility to create highly effective preparations. The result of our investigations will make it possible to enrich arsenal of medicinal means with the new highly effective preparations that will do much to promote the rise of health services level, improvement of the peopl’s quality of life and correction of demographic situation. Literature 1. Biothechnology of medicinal preparation/ edi Head Bykov V.M..-M.- 1999. 2. Vasilyev N.V. Theoretical and practical aspects of plant studing.- 1996. 3. Mats M.N., Korchov V.V., Lutsky V.I. – Triterpene glucosides and their contraceptive activity/ Plant resources.- 1998.- v. 24.- p.570-575.

MELT RHEOLOGY OF NANOCOMPOSITE BASED ON ACRYLIC COPOLYMER AND CELLULOSE WHISKERS

A. Ben Mabrouk1, A. Magnin2, M.N. Belgacem3, S. Boufi1 1 - Laboratoire Sciences des Materiaux et Environnement, LMSE, University of Sfax, BP 802-3018 Sfax, Tunisia 2 - Laboratoire de Rheologie, Grenoble-INP, UJF Grenoble 1, UMR CNRS 5520, BP 53, 38041 Grenoble Cedex 9, France 3 - Polytechnic Institute of Grenoble (Grenoble INP) Pagora - Laboratoire de Genie des Procedes Papetiers (LGP2), UMR CNRS 5518 Domaine universitaire - 461, rue de la papeterie 38402 Saint-Martin-d’Hиres - FRANCE [email protected]

Nanocomposite based on poly(styrene-co-hexylacrylate) copolymer and cellulose whiskers as the nanosize filler were prepared by in situ minemulsion polymerization and their melt rheological behaviour were investigated under dynamic conditions. The effects of -MethacryloxyPropyl triethoxySilane (MPS) content along with the whiskers loading were explored. In the absence of whiskers, an abrupt transition from a liquid- to a solid-like behaviour was observed when the polymer was synthesized in the presence of MPS. When cellulose nanofiller was added, the storage modulus (G’), and the dynamic viscosities of the nanocomposite increased monotonically with whiskers content and the resulting materials dislayed a solid-like behaviour at full frequencies range . Above 3wt% loading, a percolated interconnected whiskers-whiskers network is build up inducing a jump in the storage modulus and shear thinning behaviour of the viscosity. However, as the nanocomposite is prepared in the presence of 3% of MPS, no enhancement neither in the storage modulus nor in the viscosity were observed up to 5wt% of whiskers loading. Such a Phenomenon was ascribed to the inhibition of the build up of the whisker network. The nonlinear viscoelastic behaviour of the nanocomposite was also investigated and analyzed in term of the breakdown of different networks namely the filler-filler and the polymer-filler networks.

25 SYNTHESIS AND CHARACTERIZATION OF WHISKERS/POLYMER NANOCOMPOSITE LATEX PARTICLES USING MINIEMULSION POLYMERIZATION

A. Ben Mabrouk1, M. Rei Vilar2, A. Magnin3, S. Boufi1, M.N. Belgacem4 1 - Laboratoire Sciences des Materiaux et Environnement, LMSE, University of Sfax, Sfax, Tunisia 2 - Interfaces, Traitements, Organisation et Dynamique des Systemes, Universite Paris Diderot, Paris, France 3 - Laboratoire de Rheologie, Grenoble-INP, UJF Grenoble 1, France 4 - Polytechnic Institute of Grenoble (Grenoble INP) Pagora - Laboratoire de Genie des Procedes Papetiers (LGP2), UMR CNRS 5518 Domaine universitaire - 461, rue de la papeterie 38402 Saint-Martin-d’Hиres - FRANCE [email protected]

Stable film-forming nanocomposite particles with diameters ranging from 120 to 300 nm, based on polybutylmethacrylate (PBMA) and cellulose nanowhiskers in water dispersions were successfully synthesized in one step through miniemulsion polymerization. The nanocomposite dispersion with a solid content of 25 wt.-% and up to 5 wt.-% of nanofiller loading was prepared by in situ polymerization, in the presence of the nanowhiskers using dodecylpyridinium chloride (DPC), as a cationic surfactant and 2,2-azobis(isobutyronitrile) (AIBN), as iniciator. The electrostatic interaction between the positively charged droplets and negatively charged nanowhiskers ensured the anchoring of the nanofiller around the polymer particles. The ensuing dispersions were characterized by Dynamic Light Scattering, -Potential Measurements, and Field Emission Scanning Electron Microscopy (FE-SEM). Moreover, the transparency degree and the thermomechanical properties of the film were analysed by UV/Vis transmittance measurement and Dynamic Mechanical Thermal Analysis (DMTA). The reinforced nanowhiskers PBMA nanocomposites maintained high transparency and their storage elastic modulus increased monotonically with the increasing nanowhiskers content.

CATALYTIC OXIDATION OF BETULIN AND BETULIN DIACETATE WITH HYDROGEN PEROXIDE TO PRODUCE THEIR EPOXY DERIVATIVES

P.V. Berdnikova, Yu.V. Mattsat, T.B. Khlebnikova, Z.P. Pai Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia [email protected]

In this work we studied the possibility of implementing the phase-transfer catalysis method in two- phase systems to perform oxidation of betulin and betulin diacetate into their epoxy derivatives. The catalytic systems based on peroxopolyoxometallates are actively and successfully used in the oxidation reactions of different organic substrates by hydrogen peroxide [1, 2]. High efficiency of such bifunctional catalysts makes them attractive for using in the oxidation transformations of labile natural materials, in particular, triterpenes, to yield substances with desired biological activity. Among the most accessible triterpenes is betulin which is found in considerable concentrations (to 30-40 mass. %) in the birch bark [3]. We used efficient homogeneous bifunctional catalysts Q3{PW4O24}, where Q is quaternary + + + ammonium cation [(C4H9)4N] , [C5H5N(n-C16H33)] or [Me(n-C8H17)3N] and an anion is 3- peroxopolyoxotungstate - tetra(oxodiperoxotungsten)phosphate {PO4[WO(O2)2]4} . The regularities of oxidation reactions of betulin and betuline diacetate by a 35% solution of hydrogen peroxide were studied in the presence of catalysts Q3{PO4[WO(O2)2]4} and the production conditions of betulin diacetate epoxides were optimized. It was established that the total conversion of betulin can be achieved only at high catalyst and oxidant concentrations at a reaction temperature higher than 70°С, however, this yields a number of by-products. In addition, at the studied conditions, the oxidation of betulin diacetate proceeds via epoxidation of the terminal double bond, the high substrate conversion is achieved at H2O2/substrate ≥ 10. When the substrate/catalyst ratio is 1000 and the H2O2/substrate ratio is 10, the conversion of betulin diacetate epoxides proceeds during 6 h at 60°С, the conversion degree is 98% and the selectivity is 90%.

26 The work was supported by the Russian Foundation for Basic Research (Project 09-03-00395-а) and Branch of General and Technical Chemistry RAS (Project 5.7.3.).

References: 1. a) Ishii Y. et al, J. Org. Chem., 53, No 15 (1988) 3587-3593; b) C. Venturello and M. Gambaro, J. Org. Chem,. 56, No 20 (1991) 5924-5931. 2. Z.P. Pai et al., Russ. Chem. Bull., Int. Ed., 54, No 8 (2005) 1847-1854. 3. A.N. Kislitsyn, Khim. Drevesiny, No 3 (1994) 3-28.

CONTENT OF PHENOLIC COMPOUNDS IN CRANBERRY AND LINGONBERRY LEAVES

E.V. Berezina, A.A. Brilkina, M.F. Khusainova Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod, Russia [email protected]

Members of the Heath family (Ericaceae Juss.), including cranberry and lingonberry, are rich in phenolic compounds that generally determine their dietary and pharmacological properties. Particularly, polyphenols of cranberry and lingonberry leaves play an important role in disease prevention due to their antioxidant and antitumor activity. The aim of this study was to compare phenolics content in cranberry (Oxycoccus palustris Pers.) and lingonberry (Vaccinium vitis-idaea L.) leaves during the periods of flowering (June) and fruiting (September). Plant material was collected in Arzamassky region (Nizhegorodskaya oblast, Russia). Quantitative composition of total soluble phenolic compounds (TSPC), flavonols, catechins and anthocyanins was determined by spectrophotometric method (Shimadzu UV-1700); qualitative composition of polyphenols was determined by high-performance liquid chromatography (HPLC) method (Shimadzu). The content of TSPC (milligrams per 1 g of fresh weight, mg/g) in cranberry and lingonberry leaves in June was 28 and 96, respectively, and in September – 95 and 131, i.e. it increased 3.4 and 1.4 times. The percentage of flavonols in TSPC had risen by September, too: from 32% to 64% (cranberry) and from 41% to 71% (lingonberry). Similarly to this, the content of catechins had increased by the period of fruiting: 6.9 times in case of cranberry and 1.7 in case of lingonberry; moreover, in June in lingonberry leaves there were catechins 2.8 times more than in cranberry leaves, but in September in cranberry leaves there were catechins 1.5 times more than in lingonberry leaves. The presence of anthocyanins was observed in cranberry autumn leaves only (0.03 mg/g). So, leaves of the investigated plants have more polyphenols during fruiting, that is why during this period of vegetation there was also conducted a quantitative analysis of phenolic compounds by HPLC-method. Among the explored phenolic acids in cranberry and lingonberry leaves vanillic, gallic and salicylic (latter in cranberry only) acids were present; among hydroxycinnamic acids – ferulic, chlorogenic and caffeic acids; among coumarins – esculin and among flavonols – rutin (in lingonberry only). Leaves of these plants didn’t contain o-coumaric, p- coumaric acids, coumarin, umbelliferon and quercetin. Thus, cranberry and lingonberry leaves are characterized with considerable increase of TSPC and flavonols, catechins and anthocyanins (in case of cranberry) in particular by the period of fruiting; it means that this plant material is better to be collected in autumn. Most of phenolic compounds serve as growth inhibitors that prepare plants for dormancy period. Besides, polyphenols possess antioxidant and photoprotective properties, that is why high levels of their content may also be a response of vegetable organisms towards summer-2010 anomalous weather conditions, when because of heat and drought in Arzamassky region there was declared a state of emergency.

27 PERSPECTIVES FOR RECEIVING OF BIOLOGICAL ACTIVITY SUBSTANCES AND ATTENDANT PRODUCTS FROM TALL OIL PITCH

T.G. Bezborodova Saint-Petersburg State Forest Technical Academy, Faculty of chemical technology of wood, Saint-Petersburg, Russia [email protected]

Wood of various breeds contains biologically active substances in the structure. As the contents such in tree species of a moderate climatic zone is insignificant (about 2-4 %), to take them directly from wood is not profitable. During chemical processing of wood biologically active substances pass in a solution and concentrate in sulphatic soap and further in a tall pitch. In accordance with the offered technology, allocation of the given substances both from a sulphatic soap, and from a pitch is possible. Used reagents are recycled and come back to manufacturing. After extraction the soap and the pitch are used in manufacture of the by-products finding the application in manufacturing.

MOLECULAR CHARACTERISTICS OF ARABINOGALACTANE OBTANED FROM SIBERIAN LARCH

А.М. Bochek1, O.V. Okatova1, N.M. Zabivalova1, L.G. Makhotina2, E.L. Akim2 1 - Institute of Macromolecular Compounds of Russian Academy of Sciences 2 - Saint-Petersburg state technological university of vegetative polymers (SPb STUVG) [email protected]

Arabinogalactan (AG) is a promising and useful polysaccharide with a number of valuable properties. Chemical composition of AG and its molecular characteristics depend sufficiently on the raw material sources and the method of polysaccharide separation. The values of AG molecular mass obtained by different methods and published in scientific literature differ sufficiently (from 3 to 90 кDа). The complex of hydrodynamic methods (velocity sedimentation, translational diffusion and viscosity) is a powerful instrument for studying the molecular properties in a very large scale of molecular weight and polymer architecture. In this work the hydrodynamic methods (velocity sedimentation, translational diffusion and viscosity) was applied to study characteristics of isolated AG molecules. AG sample was obtained from Siberian larch. Water solution of the polysaccharide was precipitated by acetone and dried under vacuum at room temperature until a constant weight was obtained. Purification efficiency was qualitatively estimated by UV- and Fourier IR- spectrometry. The pure water was used as a solvent and no polyelectrolyte effects were observed. The Beckman XLI analytical ultracentrifuge and Sedfit program were used to evaluate the sedimentation parameters, and Tsvetkov polarizing diffusometer was used to study the diffusion process. The set of hydrodynamic values of intrinsic viscosity, diffusion and sedimentation coefficients is the initial matrix of the experimental data, which might be transformed into the matrix of molecular masses and hydrodynamic invariants. Absolute molecular mass of AG sample was determined from the sedimentation-diffusion data. The value of molecular mass was equal to 40 kDa and hydrodynamic invariant calculated from intrinsic viscosity, diffusion and sedimentation data was found to be 3.0x10-10 erg /K mol1/3. This value of hydrodynamic invariant is characteristic for some other polysaccharides, namely for dextran, chitozan, pullulan.

The work was done in frames of project of Ministry of Education and Science Russian Federation “Development of innovation technology for complex conversion of larch wood (with output of new type of cellulose commodity to world market)”.

28 THE STUDY OF FERMENTATION OF SUGAR BEET JUICE

T.V. Bogdanova, S.V. Vostrikov Voronezh State Technological Academy, Fermentation and Winemaking Technology Department, Voronezh , Russia [email protected]

Nowadays, in Russia sugar beet is the main raw material for sugar production. The classical technology provides obtaining mono-product - sugar. The potential of raw materials is not realized: pectin and cellulose are lost on the stages of processing sugar beet or are go wasted. In our view complex treatment for processing sugar beet is the most promising. Schematic diagram of the integrated treatment of sugar beet includes getting beet juice compaction method, followed by its fermentation and production of fuel ethanol, or alcohol. Solid phase after compression can be used to produce pectin, cellulose, or a set of dietary fiber. We investigated the process of fermentation sugar beet juice at the first stage of the study. One of the most important indicators for alcohol production is a quantitative and qualitative content of carbohydrates in the raw material. The analysis of sucrose and invert sugar showed sucrose content 15.5%, invert sugar – 0.2%. The amount of nitrogen was 1.2%, phosphorus - 0.05%. So we have to insert additional sources of nitrogen and phosphorus to ensure full protection for the composition of the growth medium and reproduction of yeast in the wort. Beet juice and beet juice with the addition of diammonium phosphate and ammonium sulphate as a supplementary source of nitrogen and phosphorus nutrition were fermented. As a control, the model solutions: sucrose and sucrose with the addition of diammonium phosphate and ammonium sulfate were fermented. The initial concentration of solids was 16%. The fermentation was carried out with dry alcohol yeast Saccharomyces cerevisiae DY 7221, having included in the specimen «Fermiol» production «DSM Food Specialties Beverage Ingredients» (the Netherlands). The amount of dry yeast was 0.8 g per 1000 g of beet juice and model solutions. The intensity of the fermentation process was assessed by the quantity of carbon dioxide liberated from the wort for a certain time. Maximum liberation of carbon dioxide was observed during the fermentation of sugar beet mash with the addition of diammonium phosphate - 19.0 cm3/min to 6 hours of fermentation. This is explained by the fact that the wort was made of nitrogen and phosphorus nutrition of yeast in the form of a salt solution - diammonium phosphate and ammonium sulfate. Minimum rate of release of carbon dioxide was observed during fermentation of model sucrose solution: 6.0 cm3/min reached by 4 hours of fermentation. The rate of carbon dioxide – 7.0 cm3/min to 4 hours of fermentation was observed during the fermentation of sucrose solution with the addition of ammonium salts. The maximum amount of carbon dioxide 206.2 cm3 was liberated in the fermentation of beet juice with added nutrients, in the fermentation of beet juice -181 cm3, and for fermentation of the model solution of sucrose and sucrose with diammonium phosphate and ammonium sulfate it was 129.8 cm3 and 108.1 cm3 of carbon dioxide, respectively. By the end of fermentation the volume of alcohol for clear beet sugar juice and beet sugar juice with the addition of nutrient salts is the same and amounts to 8% vol. In a model solution of sucrose it was 5,0%, and in sucrose solution with the addition of ammonium salts – 5.5% vol. This fact can be explained by the presence in the beet wort amino nitrogen, minerals, vitamins, necessary for the activity of yeast cells. Thus, to optimize the fermentation of sugar beet juice the introduction of additional nutrients is necessary for the life of yeast.

29 TECHNOLOGICAL PROCESSES OF PLANT BIOMASS COMPLEX PROCESSING USING PHYSICAL, PHYSICAL-CHEMICAL AND BIOCHEMICAL TECHNIQUES

V.S. Boltovskii Belarusian State Technological University, Minsk, Republic of Belarus [email protected]

With the growing scarcity of fossil organic raw materials the use of constantly renewable plant biomass for solving energy and food problems is becoming a basic strategy and one of the most important areas of research. Currently used in industry hydrolytic and biochemical methods of vegetable raw material processing are not sufficiently effective, highly energy-intensive and accompanied by the formation of large amounts of waste products and wastewater. On the basis of the research had been made we developed more efficient, energy-saving and environmentally safe technological processes using microwave energy for carrying out lignocellulose material pretreatment prior to hydrolytic or biochemical processing; for hydrolysis of plant material polysaccharides, pentose dehydration into furfural in homogeneous conditions. The residue after hydrolysis (cellolignin) is suggested to expose to bioconversion using filamentous fungi in the form of insoluble substrate by solid-phase fermentation method in order to enrich it with protein. Cellulose depolymerization process kinetic patterns during microwave heating were established. During cellulose microwave energy treatment the destruction of its low-molecular structure and the degree of polymerization decrease occurs, and as a result the efficiency of the cellulose and lignocellulose subsequent enzyme and acid hydrolysis increases. In particular, bioconversion of treated milled birch wood by filamentous fungi Trichoderma viride gives the 2.9 times increase of true protein yield in comparison to untreated wood, and during the hydrolysis in the presence of 0.5-% solution of sulphuric acid the yield of reducing substances increases on 25%. The hydrolysis of birch wood polysaccharides in the presence of sulphuric acid dilute solution under microwave energy treatment for 8–10 seconds (the temperature is 190°C) allows having sufficiently high yield of reducing substances by single-stage process, which can be compared to those, achieved in similar conditions by process steam heating for 30–35 minutes. Dehydration of pentoses, contained in the received under mild conditions pentose hydrolyzate, using microwave energy, is carried out without application of sharp superheated steam, significantly intensifies the process (duration is 10–60 seconds) and provides a high yield of furfural (not less than 82% of theoretically possible). Whereas, the yield of furfural by vapor-phase hydrolysis is less than 60% of theoretically possible. Cellolignin, remaining after the hydrolysis of pentose-containing vegetable raw material hemicelluloses in the traditional way of hydrolysis or under microwave energy treatment, is a favorable substrate for bioconversion. During cellolignin solid-phase fermentation with fungi pure cultures or their associations the enrichment of protein achieves 10–12% of the completely dry substrate weight. Developed technological and technical solutions of vegetable raw material complex processing using physical, physical-chemical (hydrolytic) and biochemical (fermentation) methods allow intensifying technological processes, reducing their energy consumption and improving environmental safety.

30 INVESTIGATION AND EXTRACTION OF SAPONINS FROM THE CREEPINGIVY IN THE SUBCRITICAL WATER ENVIRONMENT

S.N. Borisenko1, A.V. Lekar2, S.N. Sushkova3, E.V. Vetrova1, M.A. Kazmina1, S.S. Mandzhiyeva3, N.I. Borisenko1 1 - Scientific and research institute of physical and organic chemistry of the Southern Federal Regional University, Rostov-on-Don, Russia 2 - Ecological and analytical center of the Southern Federal University, Rostov-on-Don, Russia 3 - Scientific and research institute of biology of the Southern Federal University, Rostov-on-Don, Russia [email protected]

Saponins of the creeping ivy Hedera helixare a classical object for progressing methods of secretion and analysis of glycosides. Saponins of ivy contain up to 8 carbohydrate residuerelated with α- hydroxyl group during C-3, and with carboxyl group during C-28. Aglycones are hederagenin and oleanolic acid [1]. Interest to the saponins of ivy is based on their pharmacological activity [2]. Alternate classical extraction of saponins with use of toxic organic dissolvent, activated charcoal, mineral acids and bases [3] is a use of subcritical water [4]. Quality and quantity definition of saponins in the mixture received in the subcritical water environment [4] was made by the TLC and the HPLC-UV (HPLC – DAD “Agilent 1200”) methods. Identification of saponins and aglycones was made by the HPLC-MS (HPLC-MS “Bruker Daltonic MicroOTOF-Q”) method with electrospray ionization. It is established that extraction of saponins from leaves of ivy in subcritical water conditions during the 135 up to 150 оС temperature provides more than a triple increase of the saponins extraction respect to the traditional extraction. When the temperature is higher than 160 оС begins a hydrolysis of saponins to aglycones. Through the HPLC-MS method established that aglycones of the creeping ivy are oleanolic acid (MW=456,356 Da), hederagenin (MW=472,357 Da) and 24-OH-hederogenin (MW=486,330 Da) in the 3:4:2 ratio constant during various ways and regimes of extraction. More hard conditions increase the degree of extraction of saponins and concomitant oligo-glucuronides and products of deglycosylation of saponins. Thus, the results of the present work demonstrate practicability of the use of subcritical water, as an extractant for extraction of saponins and aglycones of the creeping ivy.

Acknowledgement The work was made due to the financial support of the CRDF fund (USA) and Ministry of education and science of the Russian Federation on Russian-American program “Fundamental research and higher education, of the “Development of the scientific potential of the high school” program of the Ministry of education and science of the RF (РНП 2.2.2.2/12560(3.8.11), BP4M04, BG1104) and grant of the President of RF МК-4425.2011.3.

List of references 1. J. Connolly, R. Hill, J. Nat. Prod. Rep., 2001, 18, 131-147;B. M. Zuzuk, R. V. Kutsik, L. I. Zuzuk, Zh Pharmacist, 2003, 11 2. S. Danloy, J. Quetin-Leclercq, P. Coucke J: Planta Med, 1994, 60 (1), 45-49; C.A. Minina, I.E. Kaukhova. Chemistry and the technology of phytopreparations, 2004, C. 460-464 3. L.B. Malchukovskiy, N.I. Libizov, Zh. Pharmacy, 1971, 2, 68-71 4. K.S. Tikhomirova, R.N. Borisenko, E.V. Vetrova, S.N. Borisenko E.V. Maksimenko, N.I. Borisenko, V.I. Minkin. Zh. Ultra critical fluids: Theory and practice, 2008, 3, 71-75

31 MASS-SPECTROMETRIC RESEARCH OF THE PROCESS OF COMPLEXATION OF HEDEROGENINS WITH AMINO ACIDS

S.N. Borisenko,1, A.V. Lekar2, S.N. Sushkova3, E.V. Vetrova1, M.A. Kazmina1, S.S. Mandzhiyeva3, N.I. Borisenko1 1 - Scientific and research institute of physical and organic chemistry of the Southern Federal Regional University, Rostov-on-Don, Russia 2 - Ecological and analytical center of the Southern Federal University, Rostov-on-Don, Russia 3 - Scientific and research institute of biology of the Southern Federal University, Rostov-on-Don, Russia [email protected]

As known, molecules of triterpene glycosides of Araliaceous plants (Araliaceae Juss.)which are - hederin glycoside(glycoside 1) and hederakozid C (glycoside 2) have a polar functional groups that determine their ability of association and connection of a huge number of compounds.[1] The interaction of glycosides 1 and 2 with nonpolar amino-acids (tryptophan, phenylalanine ), polar amino-acids (tyrosine, histidine), and amino-producing purines (adenine and guanine) was researched by us. 30 29 O O

20 OH OH 12 NH NH2 28 2 NH 16 COOR OH 1 9 Tryptophan Phenylalanine O O 3 27 O HO O H 24 23 N O OH OH OH NH2 NH HO 2 O N H3C HO HO Tyrosine Histidine OH 1:R=H; 2:R=Glcp-(61)-Glcp-(41)-Rhap

Among the researched amino-acidsauto-association of tyrosine and phenylalanine with a maximum coefficient of association was observed 4. During the presence of saponins the auto-association was not observed. In the order of the researched amino-acids formation of complexes with glycoside 2 is quite weak (intensity of peaks that correspond to the complex did not exceed 2%) except of the polar histidine, where the intensity of peak in the range of negative ions reached 28,2%. In all researched cases for the complexes with glycosides 2, coefficient of association (guest: host) 1:1 was detected. More various interactions were observed for amino-acids and glycoside 1. Thus, in the range of negative ions peaks of single-charged complexes of glycosides 2 with tyrosine respect to the “guest: host” 1:1 (18,96 %), 2:1 (0,83 %), 3:1 (0,03%) was observed. Non-polar amino-acids tryptophan and phenylalanine formed a single and double charged anions in respect to the “host: guest” 1:1 and 4:2 with intensities of 9% and 0.3% respectively. Histidine forms protonated complexes in respect to the 1:1 and 2:1 with a lower intensity of peaks 2,35% and 0,12%. Received regularities indicate that the formation of amino-acids complexes with glycoside 1 implemented via aromatic part of the molecule and the efficiency of the interaction is determined by the presence of substituents. In the mixture of guanine and glycoside 2 except of the interactions “host: guest“weobserved auto-association of the “host” molecules. In the mass-range of positive ions we observed variation of the interactions between glycoside 2 and guanine. The following complexes were detected 1:1 (3,12%), 1:2 (0,33%), 3:1 (2,3%), 5:1 (0,61%). Each associate of the glycoside 1 included one molecule of guanine. In the mass-range peaks of double-charged ions that correspond to the “guest-host” complexes in respect to 2:1(0,5%), 3:1 (1,9%), 4:1 (0,6%) and single-charged ions with 1:1 (6%) association of were detected. The interaction of adenine with hederogenin was impressed in the formation of the complexes in respect 1:1 with the 6.52% and 4,65% intensities for glycoside 1 and 2 respectively. Gained results indicate that triterpene glycosides form complexes not only with pharmaceutical substances, as we previously demonstrated, but with amino-acids that are included to the composition of proteins, and nucleic bases that are included to the composition of nucleic acids (DNA, RNA and etc.), therefore may affect to the activities of bio-molecules.

List of references 1. L.A. Yakovishin, N.I. Borisenko, M.I. Rudnev, E.V. Vetrova, V.I. Grishkovets, // Chemistry of natural compounds.

OBTAINING OF ECOLOGICALLY CLEAN OLIGOMERS OF APPLE PECTIN

N.S. Borisova, O.I. Valieva, Y.S. Zimin, A.G. Mustafin Bashkir State University, Ufa, Russia [email protected]

Natural polysaccharides pectins posses a series of unique feartures (a good solubility in the water, ecological cleanness, physiological activity, a wide distribution in the natural vegetation, a relatively easy way of obtaining), which allow to consider the pectins as a perspective and easily renewable source for medical, food, and cosmetic industry. Herewith the studies aimed on the obtaining the oligomers of pectins with a certain molecular masses with prescribed functional groups have special practical value. The obtaining of such oligomers is possible by the help of such destructive agents as the peroxide of hydrogen and ozone, and the employing of these matters does not lead to an additional contamination of the reactional mixture. In the present work we study the kinetic laws of the oxidation destruction of the apple pectin (P) in the reaction systems «P + H2O2 + О2 + Н2О» и «P + О3 + О2 + Н2О». The studies were performed in a water environment under the temperature 60-90°С. The initial pectin concentrations ranged in the interval 0.2-5.0 % mass., and 0.251.25 mole/l for the hydrogen peroxide. After adding the hydrogen peroxide or ozone-oxygen mixture to the water solution of the pectin we observe a sufficient increasing of the concentration of carboxyl groups that indicates the oxidation of the polysaccharide. We establish that together with the oxidation of the biopolymer the the destruction of its macromolecules progresses. The justification of the destructive processes in the studied reactionary systems is the changing of the characteristic viscousity of the solutions. For both reactionary systems we studied the influence of the initial conditions (the time of the oxidation, the temperature and the concentration of the oxidants) on the process of the oxidative destruction of the initial polysaccharide. We show that the temperatural dependence of the initial rate of the accumulation of the carboxyl groups (VCOOH) in the interval 60-90ºС is described by the following Arrhenius описывается следующими уравнениями Аррениуса (Θ = 2.303 RT kJ/m): lg VСООН = (1.6 ± 0.5) – (38 ± 4)/Θ (system «P + Н2О2 + О2 + Н2О»); lg VСООН = (3 ± 1) – (44 ± 8)/Θ (system «P + О3 + О2 + Н2О»). Thus, the oxidation the apple pectin under the action of the ozone and the hydrogen peroxide is accompanied by the oxidation destruction of its macromolecules. During the destructive transformations of the polysaccharide low-molecular polymer products containing additional carboxyl groups are formed. Varying of the initial conditions of the process allows one to control the extent of the desctruction of the apple pectin and the level of the functionalization of creating polymer products.

The work is financially supported by ADTP “Development of scientific potential of high school” of the Ministry of Education and Science of Russia, No. 1.103.11.

33 PROSPECTS FOR THE APPLICATION OF CIRKON TO ENHANCE CROP PRODUCTIVITY AND STRESS RESISTANCE

N.P. Budykina, T.G. Shibaeva Institute of Biology, Karelian Research Centre of RAS, Petrozavodsk, Russia [email protected]

The aim of the study was to investigate the effects of Cirkon, a representative of a new generation of agricultural chemicals on productivity, cold tolerance and disease resistance of plants in the northwestern Russia (on the example of Karelia). Cirkon is a natural plant immunomodulator, root developer, bloom booster. Active ingredient of Cirkon is a mixture of hydroxycinnamic acids (0.1 g/l) (phenolic compounds) obtained from the plant Echinacea purpurea (L.) (Asteraceae). Cirkon was applied in accordance with recommendations provided by its developer “NEST M”, Nonprofit Research and Production Partnership (Russia). Field trials of Cirkon on cauliflower (Brassica cauliflora L.) and potato (Solanum tuberosum L.) have shown that treatment (soaking) of propagation material had protective and stimulating effect on plants. Thus, Cirkon stimulated potato bud break resulted in an increased number of sprouts on tubers. In potato plants grown under low temperature and excessive soil moisture Cirkon accelerated seedling emergence and the onset of the subsequent developmental stages, increased the number of stems per plant and yield (by 23%). Double application of Cirkon (during budding and flowering) reduced the damage from Phytophthora infestans by 2,5 times. Treatment of seeds and seedlings of cauliflower by Cirkon improved the quality of seedlings grown under high temperature, low soil moisture and root infection. Thus, the output of standard seedlings was 17% higher compared to non-treated plants due to the reduced damping off of seedlings caused by Rhizoctonia spp., Olpidium brassicae Wor., Pythium debaryanum Hesse, decreased number of plants with bent stems and retarded development. Application of Cirkon ensured 100% survival rate of seedlings under low temperature and low soil moisture (83% in non-treated plants). Plants treated by Cirkon had faster growth and development. Thus, harvesting of treated plants took place 5 days earlier and harvest duration was 1.5 times shorter compared to that of non-treated plants. Cirkon treatment increased head weight and total yield of cauliflower plants by 27 and 34%, correspondingly. Similar experiments were conducted on sweet pepper plants (Capsicum annum L.) in plastic film greenhouses. Application of Cirkon increased germination energy and germination percentage not only under optimum temperature conditions, but also under low positive temperature conditions (15°C and lower). It also promoted seedling growth and development and increased cold resistance. Under low air and soil temperature conditions plants treated by Cirkon had higher survival rate. Cirkon reduced ﬂower and ovary abscission, enhanced flowering and fruit formation. Plants treated by Cirkon had 33-50% higher early yield, and 15-55% higher total yield depending on the number of treatments. Thus, the experimental results have proved anti-stress activity of a growth regulator Cirkon when it is used in the outdoor and greenhouse cultures. Cirkon enhances plant resistance to stresses and unfavorable conditions such as low air and soil temperature, low and excess soil moisture, high and low relative air humidity, fungal and bacterial infection. These results can be used in developing techniques of Cirkon applications in order to improve plant immune system and agricultural productivity.

34 COMPARATIVE STUDY OF QUALITATIVE COMPOSITION OF BIOLOGICALLY ACTIVE SUBSTANCE OF THE PLANTS: SOLIDAGO CANADENSIS L. AND SOLIDAGO DAURICA, ASTERACEAE

М.V. Buinov, G.M. Fedoseeva Irkutsk State Medical University, Irkutsk, Russia [email protected]

The problem of preventing and treating diseases of the genitourinary system and kidneys, especially those related to stone formation, is still one of the urgent problems of modern medicine. In scientific medicine, Solidago Canadensis L. is used along with other means for this purpose. The drugs made of Solidago Canadensis L. have an expressed hyponitrogenic and diuretic effect. Its dry extract is part of the complex preparations Marelin and Phytolizin (Poland) as antispasmodic, diuretic and anti-inflammatory drugs for the treatment and prevention of oxalate and phosphate urolithiasis. Solidago Canadensis L. can be found in Russia in feral form and is often bred as an ornamental plant. It is cultivated for medical purposes. Its habitat is America. Solidago daurica grows in Eastern Siberia and in the Far East, where its stocks are practically unlimited. In accordance with the published data the main biologically active substances of Solidago daurica are polyphenolic compounds (tannins, flavonoids: quercetin, kimpferol, izoramnetin and their derivatives, such as glycosides, phenol carbonic acids: caffeic, chlorogenic, oxycinnamic, coumarins, as well as triterpene spaniny, etc.). As for Solidago daurica, from of old it is widely used in folk medicine of Siberia and the Far East as diuretic in diseases of the urinary bladder, chronic kidney disease, often with urolithiasis. However, the chemical composition of this plant is studied insufficiently. The objective of our study was a preliminary study of the quality of the biologically active substances of Solidago daurica to ground its usage in scientific medicine along with Solidago Canadensis L. Comparative analysis of biologically active substances of these plants is carried out by conventional methods using qualitative reactions, preparative, paper, thin layer and column chromatography, as well as ultraviolet and infrared - spectroscopy. This research of Solidago daurica shows that there are condensed tannins, flavonoids, phenol carbonic acids, coumarins, triterpenoid saponins, amino acids, organic acids, etc. in it. The composition of these substances is similar to the composition of Solidago Canadensis L. Comparative pharmacognostic study of the mentioned above plants continue

NO - DONORS ON THE BASIS NEW STARCH DERIVATIVES

N.S. Butrim, T.D. Bildukevich, T.L. Yurkshtovich, S.M. Butrim Belarusian State University, Research Institute for Physical Chemical Problems, Minsk, Belarus [email protected]

Nitric oxide (NO) is produced continuously from the endothelium and plays a pivotal role in the control of vascular tone. Many of the current therapeutic agents that increase blood flow through production of NO have to be taken orally and can produce significant adverse side effects. The aim of our research was synthesis and study of the pharmacologic properties of new polymeric NO - donors on the basis of carboxystarch nitrate ester. Samples with different degree of substitution (DS) were synthesized (DSCOOH = 0.4-0.5, DS = ONO2 1.4-1.8). The synthesis of new drugs consists of some chemical stages: - starch oxidation in the system nitrogen (IV) oxide – chloroform; - esterification of carboxystarch using mixture HNO3 – H3PO4 – P2O5; - synthesis of carboxystarch nitrate ester water-soluble salts (Li+, Na+, Mg2+, L-Arg+). The influence of synthesized polymeric NO - donors on tone of the coronary vessels and contractive activity of the heart was investigated. The endothelium-dependent and endothelium-independent 35 vasodilative reactions of the isolated aorta segments at carrying out of the medico-biologic testing were studied (Table). Kinetic performances of the vasodilative effects of studing samples on the isolated aorta segment

№ Sample endothelium EC50, mg/l Rmax, %

1 Na-CSN (CN = 9,64%, DSCOONa = 0,46) + 8.8+0.4 98.3+2.1 – 7.1+0.1 97.1+1.1

2 Na-CSN (CN = 8,90%, DSCOONa = 0,46) + 4.0+0.2 81.7+1.2 – 4.0+0.4 79.6+1.4

3 L-Arg-CSN (CN = 7,30%, DSCOOArg = 0,46) + 7.4+0.4 80.1+2.0 – 7.1+0.6 77.8+1.9

CSN – carboxystarch nitrate ester; СN – nitrogen (from nitrate ester) content, %; EC50 - concentration, producing 50% response from maximum; Rmax - maximum value of response. These drugs belong to endothelium-independent vasodilators, as degree of segments weakening both with intact endothelium and without endothelium was similar. The vasodilative effects on the coronary vessels were showed by samples №3 (Rmax – 16 %) and №2 (Rmax – 6 %). Both samples increased myocardial contractility (Rmax, accordingly 20 and 9 %). The compounds №3 and №2 decreased coronary stream and myocardial contractility in the NO- synthase L-Name blockade conditions. These effects can be bound up with NO liberation kinetics. Thus sample №1 showed most powerful vasodilative effect on the system vessels. It didnt influence on the functional heart state and coronary vessels practically. The samples №3 and №2 possessed hypotensive and cardiotropic actions.

THE NEW METHOD OF SYNTHESIS OF CATIONIC ETHERS OF STARCH

S.M. Butrim, T.D. Bildukevich, N.S. Butrim, T.L. Yurkshtovich Belarusian State University, Research Institute for Physical Chemical Problems [email protected]

The starch derivatives with low degree of substitution (DS = 0,02 - 0,10) containing cationic groups are the important commercial products widely used as effective additives in the pulp-and-paper, textile and cosmetic industry. In papermaking cationic starches can increase strength, filler and fines retention and drainage rate of the pulp. The depending on degree of substitution and starch natural basis they are differently kept on a fibre. At degree of substitution from 0,030 to 0,040, potato cationic starch is kept more than on 95 %, corn cationic starch - on 60 %, native starch - on 50 %. The cationic starch is kept and fixes on a fibre of a glue particles, but only at degree of substitution above 0,025. The synthesis of cationic starches can be carried out by various ways ("dry", "wet" and extrusion process) and consists in introduction in a starch macromolecule of the functional groups bearing a positive charge. The among enough wide spectrum of reagents most often for these purposes 3- chloro-2-hydroxypropyltrimethylammonium (Quab 188®) or 2,3-epoxypropyltrimethylammonium chloride (Quab 151®) are used. The cationic starches are received by heating (Т = 35-60 0С) suspensions of starch with Quab 188® in the presence of the catalyst (NaOH or CaO) and a reagent (sodium sulphate or sodium chloride), preventing starch gelatinisation during reaction course. We developed a method of synthesis of cationic ethers of starch with use of more accessible and cheap initial reagents (trimethylammonium chloride and epichlorohydrin) at reaction carrying out in suspension without use antigelatinisators.

36 The two types of cationic starches were synthesized. The first cationic starch is soluble in hot water and can be used in a pulp and paper industry. The second cross-linking cationic starch isn,t exposed gelatinisation and can find application as sorbents of dyes and various toxic substances.

FAST PYROLYSIS OIL CATALYTIC UPGRADING OVER NI-BASED CATALYSTS

M.V. Bykova, S.A. Khromova, M.Yu. Lebedev, V.A. Yakovlev Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia [email protected]

Processes of lignocellulosic biomass conversion into hydrocarbon fuels are currently essential for expanding the utilization of woodworking or food industry waste products, reducing dependency on conventional fossil fuel resources. Fast pyrolysis is considered to be an attractive thermo-chemical technology for solid biomass processing into a liquid energy carrier, also referred to as “bio-oil” [1], and further production of heat, electricity, chemicals, or hydrocarbon fuels. Fast pyrolysis oil being a multi-component mixture of different products formed during thermal cracking of cellulose, hemicellulose and lignin attracts much attention as an alternative liquid fuel. Nevertheless it has inevitable disadvantages making it unsuitable for co-refining and direct use, these disadvantages resulting from high oxygen content such as acidity, corrosiveness, thermal and chemical instability, trend to polymerization on storage and transportation, etc. Therefore the bio-oil upgrading is needed. The quality of bio-oil can be improved by the catalytic hydrotreatment, also known as “hydrodeoxygenation” (HDO), by partial or total elimination of oxygen atoms with the production of hydrocarbons and water [2]. The HDO process is carried out at high temperatures and under high hydrogen pressures (200-400 oC, 10-20 MPa). The reactions occurring during HDO are hydrogenation, hydrogenolysis and hydrocracking. Catalytic hydrotreatment has been researched extensively with the crude bio-oil and oxygen-containing model compounds as the feedstocks over conventional sulfided Ni(Mo), Co(Mo) catalysts and supported noble metal catalysts [2,3]. But the catalysts involved showed themselves not suitable for the target HDO process and currently there is a strong need to search for a new catalytic system meeting such requirements as low cost, non- sulfided nature, high activity in the HDO process, stability against coke formation under reaction conditions and ability for multiple regeneration as well. In the present study a series of Ni-based catalysts supported on different materials has been tested in the hydrodeoxygenation of guaiacol positioned as a model of bio-oil. Some catalysts contained copper as a promoter, primarily to facilitate nickel reduction at temperatures lower than 300 oC. Initial screening studies on the supported NiCu catalysts showed their potential for vegetable oil hydrodeoxygenation [4]. Guaicol HDO has been carried out in an autoclave at 320 °C and hydrogen pressure of 17 MPa. The main products were cyclohexane, 1-methylcyclohexane-1,2-diol, cyclohexanone (aromatic ring reduction products) and benzene. Guaiacol conversion scheme explaining the formation of the main products has been suggested. The highest activity was shown by the Ni-based catalysts prepared by the sol–gel method with SiO2 in the catalyst composition acting as a structure-forming agent. According to XRD, XPS and HRTEM data, the high activity of these catalysts is due to the high nickel content and high dispersion of metal particles formed during the reduction of nickel oxide and nickel silicate species constituting the catalyst structure. The catalysts concerned demonstrated their potential in hydrocarbon fuels production during catalytic upgrading of bio-oil. In addition, the guaiacol HDO has been carried out at 280, 320 and 360 oC under hydrogen pressure of 17 MPa. It should be noted that the results obtained for model compounds may be important to provide insight into the reaction pathways under different conditions in the case of crude bio-oil, and thus may be useful for the HDO process optimization to get upgraded products with the desirable characteristics.

1. Bridgwater A.V., Peacocke G.V.C. // Renew. Sustain. Energy Rev. 2000. Vol. 4, No.1. P. 1. 2. Maggi R., Delmon B. // Stud. Surf. Sci. Catal. 1997. Vol. 106. P. 99. 3. Furimsky E. // Appl. Catal. A. 2000. Vol. 199, No. 2. P. 147. 37 4. Yakovlev V.A. et al. // Catal. Today. 2009. Vol. 144, No. 3-4. P. 362.

CHARACTERISTIC OF AJAN SPRUCE GREEN NEEDLES IN RELATION TO THEIR ACID COMPOSITION

O.A. Chernishova, V.I. Roshchin The St.Petersburg Forest Technical Academy, Department of Wood Chemistry and Forest Chemical Products, Saint- Petersburg, Russia [email protected]

At present coniferous green needles are widely used for biologically active substances extraction. Improvement of existing and elaboration of new technologies of green needles processing can be carried out by more intense use of extractives. However lack of knowledge of their chemical composition hinder carrying out these investigations. Green needles of ajan spruce (Picea ajanensis) gathered in Birobijan region in November 2009 were examined . Green needles were separated from shoots, branches and then deneedled shoots were divided into bark and wood. Each component of green needles was examined separately. There was obtained 37.6 %, 28.3 %, 8.9 % of extractives with the help of isopropyl alcohol from needles, bark and wood of shoots correspondingly. From the obtained extractives there were evolved substances soluble in petroleum ether. Their output made up 4.5 %, 6.4 %, 2.5 % correspondingly from needles, bark and wood of shoots. Petroleum extract was divided into free acids and neutral substances by separating the former with water solution NaOH (3 %), while the latter two were separated with ethanol KOH (0,5 n) into “bound” acids and non-saponifiable substances. The acids were methylated with diazomethane and after that analyzed with the help of chromatomass spectrometry.

Table. – Higher fatty acids from different components of green needles in relation to acids mass, % Acids Green needles Bark Wood free bound free bound free bound Lauric - 1.2 - - - - Myristic - 9.0 - - - - Palmitic 18.1 13.2 1.3 4.0 0.7 4.4 Linolenic traces 9.2 - 12.3 20.7 Linoleic traces 19.5 2.3 22.5 5.0 32.0 Oleic traces 29.1 1.6 17.8 4.7 21.3 Stearic - 1.1 - - - 0.5 Arachic - 1.8 - 2.5 - 1.3 Behenic - 1.0 1.1 5.0 - - Lignoceric - 0.8 0.9 4.9 - -

The group of bound acids consists of only higher fatty acids which are typical for woody plants. Free acids of green needles and bark contain mainly resin acids with admixture of fatty acids. Among resin acids the main ones are dehydroabietic acid, isopimaric acid and abietic acid. Green needles and bark contain also 7- oxodehydroabieticac acid and in the wood – levopimaric and neoabietic acids.

38 RESEARCH INTO NATURAL SUBSTANCES TRANSFORMATIONS UNDER THE ACTION OF LOW FREQUENCY VIBRATION

S.M. Chistovalov, A.N. Korenev, A.S. Peregudov, A.B. Uryupin, K.A. Kochetkov INEOS RAS, Moscow,Russia [email protected]

It is the polyfunctional equipement and flexible automatic systems developed from it that should be used as a basis for purposeful processing of home plant raw materials provided the profitability and ecological requirements are taken into consideration. Essentially all types of chemical-engineering processes (dissolution, reacting, crystallization, filtration, flushing, conductive drying in vibration-fluidized bed, extraction , grinding etc.) are made possible in a unified reaction space without loss of sealing and environmental contact through the utilization of vibrational polyfunctional unit, created in INEOS RAS and tested under operating conditions of pharmaceutical facility. A pilot unit manifested itself as more advantageous compared to standard equipment on trials. Micro- and nano-particles could be produced in this apparatus through the utilization of over- critical technologies without application of high-pressure pump unit due to a design of vibrational polyfunctional equipment. The impact of mechanical activation conditions (ball size, vibration frequency, temperature, duration etc.) on natural menthol oxidation procedure during vibrational milling of its mixture with available oxidizer has been estimated. The mixture composition was checked by 1Н and 13С-{1H) NMR spectroscopy with the help of Bruker Avance 600 device. Starting from the elaborated vibrational unit the model of flexible automatic system has been developed to provide a means for: 1/ control and support of technological and temporal parameters for each phase of feasible processes, current information being monitored and printed; 2/ automatic or interactive mode of operation ; 3/prescription of the order and optimal sequence of operator actions for each phase of process; automatic blocking of non-specified activity of operator; 4/ changing to the production of new product over one hour. Versatility of vibrational unit has been demonstrated by its application in practice to form pellets of sowing material with the resulting enhanced germination of maize seeds.

RECREATIONAL DIGRESSION AND SUSTAINABILITY OF URBAN FORESTS IN TOMSK

M.A. Danchenko, A.G. Myasnikov TSU [email protected]

The aim was to examine the state of urban tree plantation forests in Tomsk - a major industrial center. The objectives of the work included: the study of elemental composition and morphometric parameters of woody plants in urban areas, development of recommendations to optimize condition of woody plant urban forests. The objects of study serves as a natural undisturbed and natural disturbances, gray forest soil and tree species: Scots pine (Pinus sylvestris L.), Siberian larch (Larix, sibirica Ledeb.), Siberian spruce (Picea obovata Ledeb.), Fir (Abies sibirica Ledeb. ) silver birch (Betula pendula Roth). Assessment of soil was carried out with respect to parameters of forest litter and upper horizons. In a study of tree species special attention was paid to Scots pine, having indicator value. It is known that the pine has a high sensitivity to air pollution and, unlike other conifers, the degree of external damage in this species corresponds to its physiological condition and accumulation of toxicants in the tissues. The main negative impact on the environment and sanitary-hygienic state of urban forests provide industrial and energy enterprises of cities of Tomsk and Seversk. According to the Tomsk Regional Center for Environmental Monitoring in the atmosphere of the city thrown up to 24,8 thousand tons of pollutants, including solid 3,4 thousand tons / year of carbon monoxide - 9,6 thousand tons / year

39 nitrogen dioxide 7.4 tons, hydrocarbons - 0,7, sulfate anhydride - 1,6 and other pollutants 2.7 tons Developing petrochemical industry pollutes the air of formaldehyde, phenol, carbon black, methanol and ammonia. In addition to the negative impacts of industrial enterprises and transport, urban forests are polluted landfills and construction of residential moves. Marked destruction of forests from violation of the surface and internal drainage, the spread of forest insect pests and fungal diseases. Particularly clear, this is expressed near polluting industries. Health and ecological condition of the forests is estimated by the presence of snags and dead wood, litter and destruction of fungal diseases. When conducting an inventory of forest resources in urban forests revealed the presence of 37.2 m3 of dead wood and 68.9 thousand m3 fallen and fallen trees, representing 7.2% of the total stock of plantations. Plantations with the presence of dead wood and brushwood 48% forest, including plantations of softwood 32% and 56% softwood. Maximum number of shrunken and fallen trees noted in stands of aspen, birch and fir, in which the volume of dead wood and litter often exceeds 30 m 3 / ha. In the pine plantations of the average availability of dead wood is 3,5 m 3 / ha and brushwood - 6,2 m 3 / ha in fir - 8 and 12.8 m 3 / ha, while the average for coniferous 5,5 and 9.3 m 3 / ha . In the stands of cedar and larch, dead wood and snags are not available. In the birch stands average volume of dead wood was 9.5 m3ga, littering 14.6 m3ga in aspen - 11,5 and 24 m 3 / ha in poplar - 74 and 12 m3 per hectare and in willow - 4,0 and 6,6 m3/ha. On the materials inventory urban forests poorly used for recreation. Plantations damaged by recreation until the fifth stage of digression are not available, the fourth stage - up 0.5% and the third - 4,5%. Dominated stands first stage of recreational digression - 71,5%. The average recreational digression on the object 1,3. The main cause of poor recreational use of urban forests is their high clutter and poor sanitary conditions.

INFLUENCE OF ANTHRAQUINONE AND HYDRAZINE ON DELIGNIFICATION OF PINE WOOD IN THE CONDITIONS OF MULTISTAGE POTASH COOKING IN SYSTEM ISOBUTANOL-WATER

K.S. Davlyashin, E.A. Ponomarev, G.A. Pazuhina Forest engineering academy of a name of Kirov St. Petersburg [email protected]

Multistage potash cooking of wood includes chips impregnations with a solution KOH, selection of impregnation solution, its isobutanol replacement and the subsequent cooking with fast rise of temperature to final. For the intensification of delignification wood process and increase of an yield of cellulose anthraquinone and hydrazine were used. As a result of the executed researches it is istablished that the hydrazine in comparison with anthraquinone has a number of essential advantages. It is all witout bound soluble in water, including low temperatures, it is being loaded in impregnation and reacts with wood components simultaneously with the KOH. Unlike antraquinone it is not dissolved isobuthanol and in the course of cooking it is concentrated inside wood chips. In the presence of a hydrazine the expense the KOH on chemical reactions with wood at impregnation has appeared almost 2 times less than at its absence and almost didn't depend on quantity of an loaded hydrazine. In the conditions of multistage potash cooking of pine wood of a pine in system isobutanol-water an yield and rigidity of cellulose has been continuously going down, and the cellulose yield passed a minimum at the expense of a hydrazine on cooking about 3% to the weight of ovendry wood, after that starting to increase. As a whole, multifunctionality of a hydrazine is an important advantage over anthraquinone and is completely used in the conditions of multistage potash cooking.

40 PLANT BIOREFINERY FOR “GREEN” CHEMICALS

X. Deglise1, N. Brosse1, R. El Hage1, L. Ping1, A. Pizzi1, C. Sheng Goh2, H. Teng Tan2, K. Teong Lee2 1 - LERMaB, University Nancy, France 2 - Universiti Sains Malaysia, Pulau Pinang, Malaysia [email protected]

By-products from agro-industrial activities and energy dedicated crops offer a great opportunity for the development of environmentally friendly production of biofuels, green chemicals and biodegradable materials. However, in the plant cell wall the main components (lignin, cellulose hemicelluloses and in some cases tannins) are strongly linked and this association limits the extent by which lignocellulosics can be used in industrial processes. To achieve the effective utilization of biomass it’s necessary to use pretreatment technologies to separate the main components. One of the major goals of optimizing a pretreatment process is the full recovery of the feedstock through optimum utilization of all components as marketable products. In this presentation, we will describe the application of pretreatment process to three different plant resources: Miscanthus x giganteus, empty palm fruit bunches and grape pomace. At first, optimization of the ethanol organosolv pretreatment is applied to Miscanthus. This perennial grass requires little nitrogen fertilizer or herbicide and can grow up to 3 meters high per year to produce from 20 to 25 tons of dry matter per hectare. The optimized conditions allowed a good separation of hemicelluloses in a water soluble fraction and cellulose in the solid residue. A large amount of a high-quality lignin is also produced. It is relatively pure, primarily unaltered and less condensed than other pretreatment lignins. The impact of the treatments performed at different “severities” is studied on the chemical structure of the isolated lignin fragments by spectroscopic and chromatographic techniques. The results are compared to those obtained from milled wood lignin coming from the same feedstock. The results showed that an increase in the severity of the treatment enhanced the dehydration reactions on the side chain and the condensation of lignin, increased the concentration of phenol groups and decreased the molecular weight of lignin fragments. The resulting cellulose-rich material was evaluated by enzymatic hydrolysis and fermentation for the production of ethanol and the organosolv lignin was used as lignin-based wood adhesives satisfying the requirements of relevant international standards for the manufacture of wood particleboard. The pretreatment of empty palm fruit bunches with ethanol organosolv process was investigated and optimized for the production of glucose, organosolv lignin and xylans. We have used the response surface methodology based on three-variable central composite design (CCD) and the Combined Severity (CS) parameters. Very good predictions were obtained with CS parameters, concerning xylan and lignin extraction whereas CCD is the best model for glucose production. The experimental values concerning glucose and lignin recovery were in excellent agreement with the CCD prediction. The extraction of condensed tannins from grape pomace was performed in water solvent to produce tannin adhesives. The tannin fractions reactivity towards formaldehyde was studied by gel time analysis and thermomechanical analysis in bending and it was demonstrated that despite of their lower phenolic contents, some of these extracts displayed promising properties for adhesive applications. A resin formulation in which the total content of tannin is 75% of the total resin solids content gave good results and was employed for the elaboration of the first grape pomace based- wood particleboard which passed relevant international standard specifications for interior-grade panels.

41 NANODISPERSED AU AND PDAU CATALYSTS FOR SELECTIVE OXIDATION OF GLUCOSE

I.V. Delidovich, O.P. Taran, N.V. Gromov, L.G. Matvienko, P.A. Pirjaev, B.L. Moroz, V.I. Buhtiyarov, V.N. Parmon Boreskov Instiute of Catalysis, Novosibirsk, Russia [email protected]

Gluconic acid is the important compound used in pharmaceutical, food and chemical industry. Biotechnology processes for its production being the dominant commercial procedures have a lot of disadvantages. There is an urgent need to establish new catalytic methods of gluconic acid synthesis [1]. Nanodispersed gold catalysts are active in a variety of reactions [2,3]. The aim of this work is the development of active and stable supported gold and palladium-gold catalysts for selective oxidation of glucose into gluconic acid. The Au/C and Au/Al2O3 catalysts were prepared as described earlier [4,5]. The PdAu/С catalysts were synthesized by deposition of Pd(NO3)2 onto the Au/C precursor followed by reduction in a H2 flow at 300C [6], whereas the AuPd/Al2O3 catalysts were obtained by “a direct redox method”, which involves reductive deposition of gold onto pre-reduced Pd particles [7]. They were characterized by TEM, XRD, XPS and tested for oxidation of glucose by molecular oxygen at 60C, atmospheric pressure, pH = 8.8-9.2. Table shows the selected results of catalytic tests. The Au/Al2O3 catalysts exhibit higher activities as compared to the Au/C ones. The Au/Al2O3 catalysts show high stability during a test run, whereas the Au/C catalysts were deactivated possibly due to enlargement of gold nanoparticles under reaction conditions. Promotion of Au catalysts with moderate amounts of Pd (Pd:Au  0.2 mol/mol) leads to about double increase in the catalytic activity (Nos 2 and 6, 3 and 7). An increase in the Pd:Au ratio results in a decrease in the catalytic activity and selectivity (Nos 5 and 6, 7 and 8). Also, stability of the PdAu catalysts under the reaction conditions will be discussed in the report. Acknowledgements. This work was supported by RFBR (Grant No. 11-03-01022), Russian Federal Innovation and Science Agency (program “Scientific and Educational Cadres”).

Table. Catalytic performance of Au and PdAu catalysts in selective glucose oxidation No Catalyst dl, nm Glucose Gluconic acid Catalytic activity, -1 -1 (TEM) conversion, % selectivity, % molGluconic acid*gM *h 1 Au/C 1.60.4 94 96 3.3 2 Au/C 3.21.8 100 97 1.5 3 Au/Al2O3 2.40.5 100 97 9.6 4 Au/Al2O3 3.00.6 97 96 8.2 5 Pd0.7Au0.3/C 3.11.0 35 40 0.4 6 Pd0.2Au0.8/C 3.00.8 81 87 3.4 7 Au0.9Pd0.1/Al2O3 1.90.6 100 95 22.1 8 Au0.5Pd0.5/Al2O3 2.70.7 100 93 8.3

References. 1. O.V. Singh, R. Kumar, Appl. Microbiol. Biotechnol., 75, 713 (2007). 2. L. Prati, G. Martra, Gold Bull., 32, 96 (1999). 3. Y. Onal, S. Schimpf and P. Claus, J. Catal., 223, 122 (2004). 4. B. Moroz, P. Pyrjaev, V. Zaikovskii and V. Bukhtiyarov, Catal. Today, 144, 292 (2009). 5. P.A. Pyrjaev, B.L. Moroz et. al., Kinet Catal, 51, 885 (2010). 6. P.A. Pyrjaev, B.L. Moroz, A.N. Simonov, V.I. Bukhtiyarov and V.N. Parmon, Russian Patent Application No.2010113899, assigned to BIC (2010). 7. M. Bonarowska, J. Pielaszek, W. Juszczyk and Z. Karpinski, J. Catal., 195, 304 (2000).

42 HYDRODEOXYGENATION OF METHYL PALMITATE OVER SULFIDED COMO/Г-AL2O3 AND NIMO/Г-AL2O3 CATALYSTS

I.V. Deliy, E.N. Vlasova, G.A. Bukhtiyarova Boreskov Institute of Catalysis [email protected]

The blending of biofuels in the diesel pool has become more and more important in the past years due to several reasons: depletion of crude oil resources, environmental protection, possibility of rural supportive policies, utilization of the uncultivated lands, smaller CO2-emission in the total life cycle, etc. One of the problem arising is to introduce a large quantity of renewable fuel into the diesel fuel market with no negative impact on fuel properties, affecting engine performance and pollutant emissions. The bio-oils represent a mixture of oxygenated compounds with various chemical functional groups, and water. The overall oxygen content of bio-oils is about 35-40 wt% [1]. Promising strategies of upgrading these bio-oils could be the direct hydrodeoxygenation (HDO) to produce hydrocarbons [2] or the co-hydrotreatment with petroleum fractions, such as gas oil [3], to achieve the technical and environmental fuel standards. The bio-oil co-hydrotreating process has been approached by applying typical hydrodesulfurization catalysts, such as sulfidied CoMo/γ-Al2O3 and o NiMo/γ-Al2O3 at temperature range 300-600 C and hydrogen pressure within 28-200 bars [4]. The object of the present work is a comparative study of hydrodeoxygenation methyl palmitate as the representative model component over commercial sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts. The catalytic HDO of methyl palmitate was performed in a batch reactor at temperature 300-350oC and hydrogen pressure 35 bars over CoMo/γ-Al2O3 and NiMo/γ-Al2O3, using n-tetradecane, m- xylene or hydrotreated diesel fuel as a solvent. Dimethyl disulfide (0.6 wt%) was added in the reaction mixture as a precursor of H2S. Prior to use, the catalysts were activated by a standard o presulfidation procedure at 400 C under a mixture of a 5 vol.% H2S/95 vol.%H2. The sampling was carried out in the course of reaction in definite intervals. The reaction products were identified by GC-MS and quantified by gas chromatography system equipped with DB-1 column and atomic emission detector (GC-AED). The total oxygen content in the reaction mixture was determined using CHNSO elemental analyzer Vario EL Cube as well as spent catalysts. The spent catalysts were characterized also by HRTEM and XPS. In HDO experiments the performances of sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts were compared in terms of conversion of methyl palmitate, oxygen removal, products yield, concentration of normal alkanes in the liquid products. The effect of the different reaction conditions (temperature, concentration of reagents, solvent nature, etc.) on the products yield and distribution have been studied. It was stated that methyl palmitate completely transformed into saturated and unsaturated C15 and C16 hydrocarbons through the formation of oxygen- and sulfur- containing intermediate compounds. The CoMo/γ-Al2O3 catalyst exhibited higher catalytic activity in the methyl palmitate HDO than the NiMo/γ-Al2O3 one under applied conditions. The main product obtained over CoMo/γ-Al2O3 catalyst was hexadecane whereas pentadecane is preferably formed over NiMo/γ-Al2O3 catalyst, pointing to different reaction route of HDO. The tentative reaction scheme of methyl palmitate transformation was considered in comparison with obtained for methyl heptanoate hydrodeoxygenation. The research work was supported by RFBR Grant No. 11-03-00611.

References 1. Bridgwater, T. Biomass Bioenergy 31 (2007) 7-18. 2. Demirbas, A. Prog. Energy Combust. Sci. 33 (2007) 1-18. 3. Elliott, D.C. Energy Fuels 21 (1991) 1792-1815. 4. Furimsky, E. Appl. Catal. A 199 (2000) 147-190.

43 THE NEW APPROACH OF CAMPHENE PRODUCTION VIA ALPHA-PINENE ISOMERIZATION OVER HETEROGENEOUS GOLD CATALYSTS

Yu.S. Demidova1, S.I. Reshetnikov1, M. Estrada2, A.V. Simakov3, D.Yu. Murzin4, I.L. Simakova1 1 - Boreskov Institute of Catalysis, Novosibirsk, Russia 2 - Posgrado de Fisica de Materiales de CICESE-UNAM, Ensenada, B.C., Mexico 3 - Centro de Nanociencias y Nanotecnologia, Universidad Nacional Autonoma de Mexico, Ensenada, B.C., Mexico 4 - Abo Akademi University, PCC, Turku/Abo, Finland [email protected]

A large number of scientific publications on biomass transformation into valuable commercial chemicals has appeared recently. Terpenes, extracted from biomass, such as α-pinene, are inexpensive renewable raw materials that are widely used in the synthesis of fine chemicals. Currently design of the new catalytic routes originated from biorenewables is one of the key issues in sustainable development. Synthesis of camphene is an important step in an industrial process of α-pinene isomerization to camphor which is a valuable substrate for the pharmaceutical and perfumery industry. The conventional way to transform α-pinene to camphene is to perform catalytic conversion in liquid phase over acid-hydrated TiO2 resulting in camphene yield from 35% to 50% [1]. The reaction rate over TiO2 is rather low and industrial interest is in finding a catalyst which possesses much higher activity and selectivity. The Au/-Al2O3 catalyst was demonstrated recently to be rather active in the vapour-phase α-pinene isomerization to camphene with conversion 99 % and very high selectivity of about 60-80 % [2]. The objective of this work is to further develop the approach for camphene production via α-pinene isomerization over Au/γ-Al2O3 catalyst. The isomerization of α-pinene to camphene was carried out in vapour-phase by using a fixed bed glass reactor over the most stable catalyst 2.2 wt. % Au/γ-Al2O3 in temperature range 463-483 K and atmospheric pressure using n-octane as a diluent. The effects of temperature, residence time and initial α-pinene concentration on the α-pinene conversion and the camphene selectivity were studied. Experimental data showed that the main products are formed in parallel ways. The selectivity to products did not depend on the reaction temperature in the range 463-483 K, therefore activation energies of products formation were approximately the same. The reaction rate was close to first-order in α-pinene. The values of rate constants at different temperatures were determined giving a possibility to calculate activation energy (51 kJ/mol), which is comparable with the literature data for TiO2 catalyst [3]. An increase in α-pinene concentration in the initial mixture results in strong catalyst deactivation. TPO and UV-Vis-mass in situ, as well as TEM were applied to elucidate the deposits formation during the reaction. According to the analyses the deactivation was shown to be caused by adsorption of hydrocarbons on the gold species. It was found that the initial catalyst activity can be regenerated completely by the oxygen thermal treatment. In addition, the effects of isomerization temperature, initial α-pinene concentration and gas atmosphere on catalyst deactivation with time-on-stream were investigated experimentally and correlated with the proposed deactivation model. The research work was supported by RFBR Grant № 10-03-01005-а and partly by UNAM project PUNTA (Mexico) and PAPIIT IN224510.

References [1] M.O. Toshiyuki, T. Ryuichiro Kozo, H. Yoshisumi, US Patent 5802826 A, 1990. [2] I.L. Simakova, Yu.S. Solkina, B.L. Moroz, O.A. Simakova, S.I. Reshetnikov, I.P. Prosvirin, V.I. Bukhtiyarov, V.N. Parmon, D.Yu. Murzin, Appl. Catal. A: Gen. 385 (2010) 136-143. [3] F. Ebmeyer, J. Mol. Struct. (Theochem.) 582 (2002) 251-255.

44 HYDROTROPIC CELLULOSE FROM CEREALS PROCESSING RESIDUES

M.N. Denisova Institute for Problems of Chemical and Energetic Technologies, Siberian Branch, Russian Academy of Sciences, Biysk, Russia [email protected]

The present work is a continuation of research towards hydrotropic cellulose production from nonwood plant raw materials [1, 2]. This paper demonstrates a feasibility of processing agricultural residues, particularly oat husks (OHs), to obtain a valuable product. The hydrotropic pulping, being an eco-friendly method, allows cellulose to be produced in a good yield at relatively low power inputs and without chlorine- and sulfur-containing emissions and effluents. The chemical composition of oat husks is as follows: Kürschner cellulose content – 47.1%, hemicelluloses – 19.4%, lignin – 18.6%, ashes – 4.6%, and extractives – 10.3%. Prior to the hydrotropic cooking, oat husks were water hydrolyzed in a digester at 140°C without holding, modulus 1:8, to remove extractives and partially hydrolyze hemicelluloses. Lignocellulose (LC) was derived in 84.3% yield, with cellulose content being 53.4%. The hydrotropic cooking of LC was carried out with a 30% sodium benzoate solution at a temperature ranging from 155 to 165°C for 1 h, modulus 1:8. The pulp (P) yield was 70% with a cellulose content up to 63.4%. The hydrogen peroxide treatment of the pulp in an alkaline medium was found to give bleached cellulose (BC) in 40.4% yield, with 88.0% cellulose percentage therein. When treating oat husks, the mass fractions of lignin and ashes decrease from 18.6% and 4.6% in the original raw material to 6.0% and 3.3% in the bleached cellulose, respectively. Fig.1. Chemical compositions of OHs, LC, P, Figure 1 illustrates the chemical compositions of and OHs-derived BC. oat husks (OHs), lignocellulose (LC), pulp (P), and bleached cellulose (BC). As can be seen in the diagram, the product yield diminishes after each stage of the chemical treatment of OHs, with the cellulose content increasing therein. Thus, the hydrotropic cellulose has been obtained from oat husks. There are no publications on the hydrotropic delignification of cereals processing residues in the literature.

References 1. M.N. Denisova, R.Yu. Mitrofanov. Hydrotropic delignification of Miscanthus sinensis // Proceedings of the VI All-Russian Conference “Chemistry and Technology of Plant Compounds”, Saint-Petergsburg, 14-18 June 2010, Saint-Petersburg: OOO Sborka, 2010, pp. 30-31. 2. M.N. Denisova et al. Hydrotropically produced cellulose and lignin from Miscanthus, Polzunovskiy vestnik, 2010, no.4, pp. 198-206.

45 EFFECT OF CONSUMPTION OF WHITE LIQOUR ON STRUCTURE PARAMETERS OF FIBERS

О.Yu. Derkacheva, D.А. Sukhov St.Petersburg State Technological University of Plant Polymers [email protected]

For discussing an effect of white liqour on structure parameters of fibers during kraft cooking FTIR-spectroscopic analysis of Segezha mill ‘s pulp samples was carried out. In the work there was used the approach, allowing after spectral data to analyse physical structure of fiber carbohydrate complex, residual lignin, bounded water and functional groups [1-3]. The paper presents some results of IR-spectral testing composition and structure of 50 softwood kraft pulps, produced at increased consumption of white liquor. The samples were selected each hour for three days, the consumption of white liquor in the upper part of the boiler of continuous working ranged 690-820 l/min, and its average value was 740 l/min. The investigation showed that higher concentration of white liqour results to formation of the fibers with increased relative content of disordered native cellulose (CIdis) and decreased content of disordered cellulose (CIIdis). Such changed conditions of cooking does not lead to changing content of ordered fraction of native cellulose. The Kappa number values for studyed pulps were in limits 40 – 54 units. Analysis of spectral and chemical data showed that at increased consumption of white liqour the content of residual lignin was lower. There was revealed increasing more than two times intensity of absorbance band of deformation vibration of bounded water in comparing with average value. It testifies about increased content of residual water in these samples. In the IR-spectra there was observed the band of increased content of functional groups. In these cases its intensity was greater than the average value in more than ten times. The results of the work showed that the most significant effect of raised consumption of white liqour during cook was icreasing hydrophylic properties of pulp fibers and content of some functional groups. It promoted to higher quality of the mill production.

1. Sukhov D. A. Analysis of relationship of structure and property of cellulose fibers after their vibrational spectra: dis. ... doct. of chem. sc. / STUPP. SPb., 2002. 34 с. 2. Sukhov D. A., Zilkin N.A., Valov P.M., Terentiev O.A. Cellulose structure in relation to paper properties. Tappi 74(3) 201-204 (1991) 3. Afanasiev N.I., Lichutina T.F., Gusakova M.A., Prokchin G.F., Vichnyakova A.B, Sukhov D.A., Derkacheva O.Yu. Evaluation of content and structural changes of residual lignin and pitch in hardwood kraft cellulose by FTIR-spectroscopy. Journal of applied chemistry (Rus.). 79 (10) 1706-1709 (2006).

EUCALYPTUS BARK RESIDUES AS SOURCE OF HIGH VALUE TRITERPENIC COMPOUNDS. PRELIMINARY EXTRACTIONS WITH SUPERCRITICAL CO2

R.M.A. Domingues1, E. Oliveira1, G.D.A. Sousa2, C.S.R. Freire1, C.M. Silva1, A.J.D. Silvestre1, C. Pascoal Neto1 1 - Department of Chemistry, CICECO, University of Aveiro, Aveiro, Portugal 2 - RAIZ - Forest and Paper Research Institute, Eixo, Portugal [email protected]

Wood exploitation for pulp production generates large amounts of biomass residues and byproducts which can be important renewable raw materials for the production of high value chemicals and materials [1]. Eucalyptus spp. are the most important fiber sources for pulp and paper production in southwestern Europe and South America among other regions. The lipophilic extracts of E. globulus bark are rich in triterpenic acids such as betulinic, ursolic and oleanolic acids [2]. These

46 triterpenic acids show promising nutraceutical and pharmacological properties [e.g. 3]. In the present communication, we show the triterpenic composition of outer barks of several Eucalyptus spp. exploited in large scale by the pulp industry or with potential interest for this sector, namely E. globulus, E. grandis, E. urograndis and E. maidenni. The contents of the main triterpenic acids identified in the four species varied between 4.5 g/Kg in E. urograndis and 21.3 g/Kg in E. globulus. The production potential of this type of compounds and the integration in existing mills is also discussed. It has been observed that the recovery of triterpenoids from bark is reduced by 82% during the typical industrial debarking process of E. globulus logs, due to inefficient recovery of outer bark [4]. In order to develop a successful exploitation process for these valuable compounds, it will be necessary to develop an integrated system allowing to selectively remove the triterpenic rich surface layers of the bark, prior to the fully debarking of logs. The devolvement of environmental friendly technologies for the exploitation of these valuable compounds is an important issue. Supercritical fluid extraction (SFE) using CO2 is a promising alternative to conventional separation techniques requiring organic solvents. The advantages of this approach are the mild temperatures used, the CO2 inertness as well as its solvent power and selectivity which can be tailored by modification of pressure, temperature and/or co-solvent content [5]. In this work one presents preliminary supercritical extraction experiments aiming to evaluate the applicability of this technique to extract and purify triterpenoids from Eucalyptus globulus deciduous bark.

The authors are grateful to BIIPP project (QREN 11551) and to AFORE Project (European Community's Seventh Framework Programme FP7/2007-2013 under grant agreement no CP-IP 228589-2 AFORE)

References: 1. Murzin, D. Y., Maki-Arvela, P., Salmi, T.; Holmbom, B.. Chem. Eng. Technol., 2007. 30(5), 569-576. 2. Freire, C. S. R., Silvestre, A. J. D., Neto, C. P., Cavaleiro, J. A. S., Holzforschung, 2002. 56(4), 372-379. 3. Liu, J., J. Ethnopharmacol., 2005. 100(1-2), 92-94. 4. Domingues, R. M. A., Sousa, G. D. A., Freire, C. S. R., Silvestre, A. J. D., Neto, C. P., Ind. Crop. Prod., 2010. 31(1), 65-70. 5. Bertucco, A. and Vetter, G., High Pressure Process Technology: fundamentals and applications, First ed., Elsevier Science, Amsterdam, 2001.

PERSPECTIVES OF BASIDIOMYCETES AS AN ACTIVE PRODUCERS OF CELLULOLYTIC ENZYMES

K.G. Dreval, M.I. Boyko Donetsk National University, Donetsk, Ukraine [email protected]

Transformation of raw materials, which contain cellulose, is perspective not only from the point of view creation of independent technologies but also from the point of view the decline of ecological danger of some enterprises which process vegetable raw materials (Volova, 1999; Bhat, 2000). However, without regard to all achievements in the cellulases study, still not known what enzymes and in what amount are necessary for the effective cellulose hydrolysis. Industrial introduction of this technology restrains temper absence of active cellulases producers (Skomarovskiy et al., 2006). This work was focused on screening for new perspective producers of cellulases among higher basidiomycetes and optimization of nutrient medium acidity and cultivation temperature for the new strains – active producers of cellulolytic enzymes. 47 Cellulolytic activity of the cultural liquid of 61 strains of Basidiomycetes, which belongs to the genuses Schizophyllum, Trichaptum, Irpex, Fomes, Trametes (=Coriolus), Pleurotus, Daedaleopsis, Lepista, Inonotus, Stereum, Heterobasidion, Auricularia, Chondrostereum, Phellinus, Hirschioporus and Flammulina was analyzed. Optimization of the cultivation conditions of basidiomycetes – active producers of cellulolytic enzymes was conducted along initial acidity of nutrient medium and temperature of cultivation. During screening strains were cultivated at the temperatures optimal for the growth and on nutrient medium with initial acidity 5.0 pH. During the optimization process strains were cultivated at the temperatures from 24°C to 36°C on nutrient medium with initial acidity from 3.0 to 9.0 pH. Cellulolytic activity of the cultural liquids of strains were determined towards filter paper, Na-carboxymethylcellulose, hydroxyethylcellulose and cellobiose solutions. Reducing sugars concentration were determined by the method of Shomogyi and Nelson (Nelson, 1944). Glucose concentration were determined by the glucosooxidase- peroxidase method. Protein concentration were determined spectrophotometrically (Darbre, 1989). All results were analyzed statistically by the variance analysis (Prisedskiy, 1999). As a result of conducted work difference in activity of cellulases and in composition of cellulase complex between different strains of one species of basidiomycetous fungi was established. Basidiomycetes are active producers of cellulases and can be a perspective objects for the biotechnology of cellulolytic enzymes. It was found, that cellulases of strains К-1, А-Дон-02 and Д-1 Irpex lacteus (Fr.) Fr.; Sh-1 Stereum hirsutum (Willd.) Pers.; AnSc-1 Daedaleopsis confragosa f. confragosa (Bolton) J. Schröt. and J-2An Phellinus pomaceus (Pers.) Maire. have the most active cellulases between researched cultures of Basidiomycetes. On the next stage of experiment optimum terms of initial acidity of nutrient medium and temperature of cultivation were set for all strains to produce cellulolytic enzymes. As the result of optimization the values of the total cellulolytic activity increased on 16-159%, and specific – on the 9-143% in dependence of the basidiomycetes strain. It was determined, that optimal initial acidity of the nutrient medium for all strains to produce cellulolytic enzymes is pH 7.0. Optimal cultivation temperature for strains К-1, А-Дон-02 and Д-1 I. lacteus is 34°С, for strain Sh-1 S. hirsutum – 28°С, for strain AnSc-1 D. confragosa f. confragosa - 32°С. During the optimization process haven’t been found ability for hydrolysis of filter paper in all variants of experiment in the study of the strain J-2An P. pomaceus. Based on this high cellulolytic activity of the strain J-2An P. pomaceus at the stage of screening can be regarded as an artifact.

NEW POLYMER-COMPOSITE FIBROUS MATERIALS WITH ANTIMICROBIC PROPERTIES

V.I. Dubkova1, M.Yu. Smirnova2, M.V. Solovskiy2, N.P. Krutko1, N.A. Belyasova1, O.I. Maevskaya1 1 - Institute of General and Inorganic Chemistry of NAS Belarus, Minsk 2 - Institute of Macromolecular Compounds of Russian Academy of Sciences, St-Petersburg [email protected]

Synthesis of the new physiologically active polymers and creation of the polymeric composite materials, including of the medicinal substances, is an actual problem of the present. Such materials find a wide application in medical practice in the capacity of the wounded coverings, dressing materials, implants et cetera. The materials with various complexes of the properties are required for ensuring of the differentiated approach of treatment. Therefore despite of already available their sufficient quantity, the necessity for perfection of the medicinal materials or creation of new one grows constantly. The purpose of the present work is development of new polymer-composite fibrous materials with the biologically active polymeric complexes immobilized on their surfaces. The polymeric complexes on the basis of copolymers of acryl amide with acrylic and metacrylic acids and antibiotic aminoglycoside, namely kanamycin, gentamycin and amikacin were used. The polymeric complexes contained from 20 up to 30 weights % of the connected antibiotics. As a substrate the

48 cellulose (viscose) and the carbon fabrics were chosen. The macromolecule of cellulose, constructed from anhydroglucose links, has no the structural elements which could cause undesirable chemical influences on biological environments, as well as of products of its disintegration in the soft conditions. The carbon fibrous materials are inert in relation to biological tissues and are concerned to the ideal textile mediums. For immobilization of the medical products it is considered the most expedient of using of the substrates with the groups which capacity for reaction with the polymeric complex included, that in turn predetermines of reception of the more effective medicinal forms of prolonged action. Therefore in the work side by side with the cellulose and carbon fabrics unmodified the phosphorus containing cellulose and carbon fabrics have been used. Immobilization of the preparations on a material - substrate was carried out by the method of sorption from 3 weight % of the polymeric complexes solutions. The gain in weight of a polymeric complex on a material - substrate after endurance in a solution and the subsequent drying in vacuum made 4-7 weight %. The data of Infra-red spectroscopy and the differential thermal analysis of the received composite materials give the basis to consider, that in case of use as a material - substrate of the phosphorus containing cellulose and carbon fabrics for immobilization of a preparation physical and chemical interaction between a material of a substrate and a polymeric complex takes place. The tentative estimation of the common toxicity of the received materials on an express train - method with use of sperm of a bull as cellular test - object has shown, that at immobilization of a complex on the basis of the copolymer of acrylamide with acrylic acid and the aminoglycoside antibiotic of amikacin an increase of time of spermatozoa mobility is observed. It is known, that spermatozoa of a bull, being cells of mammalian, possess a high sensitivity to influence of the chemical substances tested and the mixes of complex structure, and their mobility characterizes the fundamental processes of vital functions of a cell. It has been established by diffusion method with using of bacteria strain Escherichia coli, Salmonella sp., Staphylococcus sp., that all received samples of the polymer composite fibrous materials with the immobilized polymeric complexes on their surfaces effectively inhibit of bacteria growth and are characterized by the antibacterial properties expressed.

COMPARATIVE COMPOSITIONAL STUDY OF ESSENTIAL OILS OBTAINED BY MICROWAVE-ASSISTED HYDRODISTILLATION FROM DIFFERENT PARTS OF CARVONE- AND CITRAL-RICH LIPPIA ALBA PLANTS

D.C. Duran, Y. Perez, C.B. Ramirez, M. Llinas, J.R. Martinez, E.E. Stashenko Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Lippia alba (Verbenaceae family) is an aromatic shrub that grows in Central and South America. The carvone- and citral-rich chemotypes of this plant are found in Colombia. Plant development, cultivation conditions, plant part, post-harvest treatment, and extraction time are some factors which affect essential oil composition. Freshly collected or dried young and mature leaves and flowers of both L. alba chemotypes grown in an experimental garden were subjected to microwave-assisted hydrodistillation for 30, 45, 60, and 90 min. GC-MS (Agilent Technologies 6890 Plus/5973/5975, DB-5MS and DB-WAX 60 m x 0.25 mm, D.I columns) analysis of the resultant oils showed large variations in composition. Carvone relative amount varied between 28,9 and 53,9%, while citral relative amount changed from 22,5 to 89,2% in the oils of the 2 chemotypes, respectively. Dried young leaves (3 weeks), afforded the oil with the largest carvone yield after 30 min of hydrodistillation. For the other chemotype, the largest citral yield was obtained from dry young leaves (3 weeks) after 90 minutes of hydrodistillation. These oils are interesting raw materials for carvone and citral isolation, which are extensively used as flavouring agents and as starting materials in fine organic synthesis.

49 RESURSOVEDCHESKY RESEARCH AND PHYTOCHEMICAL PROBE MELILOTUS OFFICINALIS (L.) PALLAS, GROWING IN THE SARATOV REGION

N.A. Durnova, N.V. Polukonova, Yu.V. Romanteeva Saratov State Medical University n.a. V.I.Razumovsky, Saratov, Russia [email protected]

Productivity and stocks of raw materials Melilotus officinalis (L.) Pallas, growing in territory of the Saratov region are defined. The greatest values of the given indicator are established for Lysogorsky and Balakovsky areas. As the best ecological conditions for plant growth serve good light exposure; low humidity of soil and air; loamy soil. The qualitative structure of raw materials M. officinalis is studied. The maintenance of operating substances – coumarins – depends on type of soil and degree of its humidifying. The greatest quantity is revealed at the plants growing on loamy soils with high moistness, the least – on alluvial with smaller degree of humidifying. The plants growing near of tracks, concentrate iron, and in city boundaries – strontium.

STUDY OF THE POROUS STRUCTURE OF LIGNOCELLULOSE MATERIALS

Z.K. Dzhumanova1, G.N. Dalimova2 1 - Intitute Plant substances chemistry of AS of Uzbekistan 2 - Institute of the plant substances chemistry of AS RUz [email protected]

There are determined the values of specific surface area according to the water (Ssp), a summary porous volume (wo), capacity of monolayer (Xm) and sizes of submicroscopic capillaries (rk) of the lignocellulose materials: rice husk, rice straw, stems of sorghum, stems of corn before and after of alkaline hydrolysis (tabl.1).

Table 1. Porous structure of the lignocellulose materials Parameters of Rice straw Rice husk Corn stems Sorghum stems the porous structure A B A B A B A B Xm, g/g 0,0139 0,0120 0,0052 0,0122 0,0170 0,0087 0,0104 0,0104 2 Ssp, m /g 48,87 42,18 18,28 42,88 59,76 30,58 36,56 36,56 3 wo, cm /г 0,111 0,062 0,075 0,072 0,058 0,057 0,056 0,068 rk, Å 45,4 29,4 82,0 33,6 19,4 37,2 36,1 37,2 A - before the alkaline hydrolysis, B - after the alkaline hydrolysis

The isotherms of the absorption of vapors of water of the investigated models have S- descriptive form, which indicates the capillary condensation of the molecules of sorbate and the polymolecular nature of adsorption (fig.1). The isotherms of absorption show that from the porous parameters the investigated models were arranged in the following number: “rice straw < rice husk < corn stems < sorghum stems”, after the alkaline activation: “rice husk < sorghum stems < rice straw < corn stems”;

Rice straw Rice husk Corn s tems Sorghum stems 12 10 Fig.1. The absorption isotherms of the 8 lignocellulose materials 6 4

Sorption, % Sorption, 2 0 020406080100120 Relative humidity, %

This arrangement corresponds to regular reduction in the values of the summary porous volume of samples under investigation (tabl.1). Consequently, with a study of the porous structure of lignocellulose materials the summary porous volume (wo) can serve as the criterion of evaluation of their sorption activity.

CARBOXYMETHYLATION OF PEAT

M.V. Efanov, A.A. Popova Ugra state university, Khanty-Mansiysk, Russia [email protected]

Complex use of peat is one of actual problems of the peat industry. The optimal in this direction is the way of deep chemical processing of all biomass of peat for the purpose of reception directly from it various humic preparations [1]. Process carboxymethylation cellulose and wood — perspective manufacture of surface-active substances for application as regulators of rheological properties of suspensions [2]. The purpose of the present work is process studying carboxymethylation peat monochloracetic acid in propanol-2 environment at presence sodium hydroxide for working out of a way of reception of water-soluble surface-active polymeric materials. The chemical compound initial transitive peat is defined. Humidity and ashes is made by 8,0 and 9,7 % accordingly. It is established that initial peat contains: 16,63 % of bitumens, 32,89 % of humic acids, 9,92 % polysaccharides, 9,38 % of cellulose and 21,5 % of a lignin. The maintenance of the general OH-groups defined on Verlej, has made 13,6 % (0,08 moth ОН/1 g peat). The quantity monochloracetic used in synthesis has made acids 3,5 g (0,25 mol/mol OH-groups of peat). Influence of duration of preliminary alkaline processing of peat is studied at 50 0С on properties of its products carboxymethylation in propanol-2 environment. The product carboxymethylation with maximum solubility in water, a water-alkaline solution and the maintenance carboxymethyl groups (21,2 %) is received after peat processing by an water-alcoholic solution of alkali during 6 h at 50 0С (a stage carboxymethylation 50 0С, 3 h). Influence of temperature of preliminary alkaline processing during 3 ч on properties of its products carboxymethylation in propanol-2 environment is studied. Carboxymethylation peat at various temperature, has shown that with increase in temperature of processing by alkali with 50 0С to 100 0С the maintenance carboxymethyl groups (20,5 %) naturally increases in products. The maximum solubility of the received products in water and 2 % the water solution of alkali is observed at temperature of preliminary alkaline processing in 100 0С. Relative viscosity of water solutions of the received products carboxymethylation of peat changes within 0,91–1,16. The maintenance carboxymethyl groups depends on duration and temperature of preliminary alkaline processing of peat.

51 Thus, changing conditions of preliminary alkaline processing of peat before carboxymethylation, it is possible to synthesize products with the set properties, that is to carry out the directed synthesis carboxymethyl ethers.

References

1. Naumova G.V. Peat in biotechnology. - Minsk, 1987, - 158p. 2. Bazarnova N.G., Katrakov I.B., Markin V.I. // Russian chemical journal, 68, 3, 108 (2004).

Work is executed with financial support of FTSP «Scientific and scientific and pedagogical shots of innovative Russia 2009-2013» (the state contract № P2446).

ANTIBACTERIAL PROPERTIES OF ESSENTIAL OIL OF SIBERIAN FIR AND ITS FRACTIONS IN RELATION TO STAPHYLOCOCCUS AUREUS 209, ESCHERICHIA COLI, KLEBSIELLA PNEUMONIAE

E.A. Efremov, A.A. Efremov Siberian federal university, Krasnoyarsk, Russia [email protected]

In studying the dynamics of the selection of essential oils from native plant materials in Siberia was found that their component composition changes as you get in hydroparodistillation. In this connection it is interesting to investigate the bactericidal activity of variousfractions of the same essential oil. To this end, we have obtained several fractions of essential oil of Siberian fir, the most studied oil, set the component composition of thesefractions and determined their bactericidal activity against the microbial communities of Staphylococcus aureus 209, Escherichia coli, Klebsiella pneumoniae, which are mostrepresentative of biological media and are responsible for many human diseases. It was established that as the selection of essential oils varies its composition andphysico-chemical properties (Table 1):

Table 1- Data on the dynamics of the selection of essential oils from wood green of siberian fir at hydroparodistillation*. № Time of Weight of the Output of Refraction Density, fraction allocation of allocated essence, whole oil, index, at 20 0С gram/centimeter3 fraction, gram % minutes 1 60 5,17 1,4693 0,9140 26,4 2 50 4,24 1,4686 0,9134 21,6 3 90 5.10 1,4690 0,9108 26,0 4 180 3,24 1,4713 0,9065 16,5 5 500 1,62 1,4783 0,9064 8,3 6 380 0,25 1,4787 0,9066 1,3 TOTAL 920 19,62 1,4701 0,9085 100,0 *- raw materials loading – 611 gram of fresh raw materials; output - 5,400,16% in terms of a.s.n

52 From Table 2 follows that the bactericidal activity of separate fractions can differ considerably, and last fractions, as rule, tended to more bactericidal (MIC (mkg/ml) of separate fractions of oil) № Ingredient Staphylococcus Escherichia coli, Klebsiella aureus 209 pneumoniae 1 Fraction 1 10,6 21,3 5,3 2 Fraction 5 1,3 21,3 5,3 3 Whole oil 5,3 21,3 5,3

PHOSPHORYLATED 3-AMINO-2-ALKYL(ARYL)-3H-THIAZOLO[3,2-B][1,2,4]TRIAZOL-7- YLIUM CHLORIDES

E.B. Erkhitueva, A.V. Dogadina, A.V. Khramchihin, B.I. Ionin St. Petersburg State Institute of Technology (Technical University), St. Petersburg, Russia [email protected]

Many condensed heterocyclic compounds containing triazole ring are known to possess diverse pharmacological properties, including painkilling, anti-inflammatory, anticancer, antibacterial and radioprotecting [1,2]. To date, the phosphorus-containing compounds of such structure are unknown, although they are promising ones as they combine condensed heterocycles and phosphonate groups in one molecule that may lead to even greater variety of valuable biological properties. We found that the reaction of dimethyl chloroactylenephosphonate with 4-amino-3-mercapto-5- alkyl(aryl)-1,2,4-triazoles proceeds readily in acetonitrile medium at room temperature at the mixing equivalent amounts of the starting reagents, to form condensed heterocyclic compounds of unusual structures, namely 3-amino-6-(dimethoxyphosphoryl)-2-alkyl(aryl)-3H-thiazolo[3,2- b][1,2,4]triazol-7-ylium chlorides I–V: Cl Cl S S O O H2N O R O P + NH HO P + NH N N N 2 N N 2 O P Cl + HS O OH N N N O N R=H(I),Me(II),Et(III),Pr(IV),Ph(V) I-V Ia-Va δP –8.6 ppm δP ≈ 2.6 ppm δP ≈ –6.5 ppm The compounds I–V are crystalline substances, poorly soluble in organic solvents, well soluble in water. When heated in concentrated hydrochloric acid, they are transformed into the corresponding phosphonic acids Ia–Va. The structure of the compounds I–V, Ia–Va was proved using 1H, 13C, and 31P NMR spectroscopy. For example, in the 1H NMR spectrum of compound II there is a doublet signal of the methoxy groups at the phosphorus, δ 3.94, JHP 11.6 Hz, the methyl group in 2 position induces a singlet δ 13 2.72. Olefinic proton resonates in a weak field, δ 8.53, JHP 4.4 Hz. The C NMR spectrum of the compound contains the following signals (ppm): δC 10.12 (CH3), δC 55.66 (OCH3), δC 119.62, JCP 195.7 Hz (CH=), δC 132.28, JCP17.3 Hz (=CNH), δC 154.92 (=CCH 3), δC 161.39 (SC=N). The X-ray diffraction data prove unambiguously the aromatic structures of compounds I-V, in contrast to the conclusion in [3]:

General view of the molecule of 3-amino-6- dimethoxyphosphoryl-2-methyl-3H-thiazolo[3,2-b] [1,2,4]triazol-7-ylium chloride (II)

References [1] M. M. Ghorab and A. Y. Hassan, Phosphorus, Sulfur, and Silicon, 1998, 141, 251-260. [2] A. R. Rasad, T. Ramalingamat, A. B. Rao, P. W. Diwas, and P. B. Sattur, Indian J. Chem., 1986, 25B, 556. [3] T.E. Glotova, A. Nakhmanovich, and M.V. Sigalov, – Russian Journal of Organic Chemistry, vol. 24, 10, (1988), p. 1941-1945, Zhurnal Organicheskoi Khimii, vol. 24, 10, (1988), p. 2151-2156.

THE TECHNOLOGY DEVELOPMENT OF SPARKLING LOW ALCOHOL BEVERAGES ON THE BASES OF HONEY AND PLANT MATERIALS

N.A. Esaulko, S.V. Vostrikov VGTA, Voronezh, Russia [email protected]

Currently, when creating a new low alcohol beverages a large role is occupied by drinks on the basis of natural raw materials, which to some extent can compensate for a deficiency of vital nutrients in the body. In this aspect the particular interest is represented by working out of fermented beverages based on vegetable raw materials of high biological value - honey. Natural honey is a unique natural product, both in composition and on biological properties. It contains all valuable to the body minerals, microcells, vitamins, enzymes, carbohydrates, and biologically active substances. It is known that in addition to the basic components (honey, sugar, water) for giving the beverage a special flavor and aroma introduced hops, spices, herbs and their extracts, fruit juices at different stages of it is production. In addition, during beverage fermentation are produced a big number of biologically active substances (vitamins, amino acids, organic acids, minerals, etc.), which yields honey beverage with increased biological value, therapeutic and prophylactic properties. Beverages on the basis of honey such as medovukha, has long been considered as traditional Russian drink. Honey, as one as the most readily available kinds of carbohydrate raw materials, used in ancient Rus in large enough quantities. In the twentieth century, mass production of honey beverages stopped, because the technology of manufacture was lost. So the traditions of apiculture fermentation were again revived only in last decades, arousing interest both for manufacturers and consumers. Thanks to the low concentration of alcohol, good organoleptic quality, refreshing properties, the nutritional and biological value the fermented honey beverages can take a worthy place among the low-alcohol beverages. A revival of recipes opens new possibilities for the solution of a problem of expansion assortment of low alcohol natural beverages with the raised food and biological value. In the Voronezh State Technological Academy was developed a new technology for the production of sparkling honey beverage, with low alcohol content of up to 3%. The production of such beverages includes several stages: - the preparation of honey-fruit wort: honey, apple juice concentrate, sugar are used. As for sources of nitrogen a commercial preparations (energizery) is used. In our work we blended honey with apple juice to accelerate fermentation and improve the quality of the drink. Using juice not only

54 enriches the wort by nitrogenous substances, but also allows to increase the level of natural acidity, reducing the consumption of organic acids to achieve the optimal pH values; - membrane filtration with pre-strainer. It provides sterile wort, prevents the development of foreign microflora with simultaneous removal of proteins; - fermenting wort: a prepared cooling wort is introduced a pure culture of yeast in an amount of 5% of the wort volume. Wort fermentation is proceeds at a temperature of 15 º C in a sealed vessel under pressure, to the accumulation of alcohol not exceeding 3%; - followed deep cooling (- 3 - - 5 º C); - filtering on the two stepped filter cartridge; - isobaric drink.bottling. Thus, the presented technology allows to obtain natural sparkling alcoholic drinks with high quality and original sensory assessments. A revival of national formulations significantly expand the narrow assortment of beverage fermentation.

A NEW FLAVONE GLYCOSIDE FROM AREAL PARTS OF SCUTELLARIA SCHACHRISTANICA

K.A. Eshbakova, Z.O. Tashmatov, Kh.M. Bobakulov S.Yu.Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences, Tashkent, Republic of Uzbekistan [email protected]

Scutellaria schachristanica Zuz. - long-term endemic a plant distributed in the Central Asia, grows on a slope the top belt of mountains in Turkestan a ridge (Samarkand). Earlier from Scutellaria schachristanica we have isolated flavonoids chrysin, wogonin, oroxylin, 5,7-dihydroxy-3-methoxyflavone, 3,5-dihydroxy-7-methoxyflavone, hispidulin, apigenin, scutellarin, apigenin-7-О-glucoside, scutellarin-7-О-β-D-glucopyranside, luteolin-7-О-glucuronide, chrysin-7-O-β-D-methylglucuronopyranoside and chrysin-7-O-β-D-glucuronopyranoside. In continuation our studied of the chemical composition of aerial parts Scutellaria schachristanica collected during blossoming time, which grows in the Samarkand region of the Uzbekistan. From this plant we isolated a new flavone glycoside named by us shachristanoside (1), which has the 0 composition C25Н20О15, m.p. ›340 С. Structure shachristanoside have been established on the basis of it is physical and chemical properties and the analysis of it is spectral data IR , UV, 1H, 13C NMR, DEPT. Thus, for shachristanoside we propose the structure chrysin-7-О-[-L-arabinopyranosyl(1→6)]-- D-glucopyranoside

OH O O HO O OH HO O O HO OH

OH O

55 CARBON DIOXIDE EXTRACTION OF WHEAT STRAW

S.N. Evstafyev, E.S. Fomina Irkutsk state technical university, chair of organic chemistry and food technology, Irkutsk, Russia [email protected]

Extraction by organic solvents, many of them are environmentally hazardous, is used to remove obstructed enzymatic hydrolysis compounds. Using for this purpose supercritical fluid extraction by carbon dioxide will make it possible to set up not only an environmentally safe production but also a more economically effective one. Results of study of CO2-extracts yield and theirs composition in the dependence on temperature, pressure and extraction duration are given. The experiment with wheat straw samples was carried out using flow laboratory apparatus in subcritical (20 ºС) and supercritical (60-200 ºС) conditions under pressure 8-13 MPa during 20-180 min. Composition of extracts was characterize using GC-MS Agilent 5820 chromatograph equipped with capillary column HP-5MS. Identification of mass spectra was carried out using NIST 05 mass spectra library. Yield of extract at changing of pressure from 8 to 12 MPa at 20 ºС increase from 0.48 to 0.96 percent of oven-dry weight. More than 70 compounds was found in the extract composition, amount which (in relative percentage): alkanes С12-С26 (42.5), terpens (12.0), saturated and unsaturated aldehydes С7-С18 (0.5), monoalkylcyclohexanes С15-С27 (21.4), monoalkylbenzenes С16-С25 (14.5), 2 – ketones С7-С17 (0.6). Traces of high molecular monatomic alcohols are present. The basic compound of terpenes and theirs derivates is limonene, which level is more than 80 %. O-cymol, isoceniol, terpineols and terpinolen are notable for theirs content. It is observed in supercritical conditions under 10 MPa with increasing of process temperature to 200 ºС, extracts yield increase to 1.2 percent of oven-dry weight. The dependence of extracts yield on temperature is close to linear. In composition of supercritical extracts level of alkanes was increased, first of all, because of high molecular homologues C25-C29 recovery. The most notable changes of extracts yield are observed at increase of pressure and by using of modifier. So, at change of pressure from 8 to 13 MPa (190 ºС) yield of wheat straw extracts increase from 0.39 to 3.0 percent of oven-dry weight. Along with dominate hydrocarbons, methyl-, ethyl-, isopropyl ethers of myristic, palmitic, stearic and docosanoic acid were found in composition of extracts. At temperature 200 ºС and pressure 10 MPa in presence of water as a modifier yield of extractive compounds was 8.4 percent of oven-dry weight. Presence of carboxylic acids and esters is characterized the obtained extract.

LIGNIN SOLUBILITY PARAMETERS

E.I. Evstigneyev Saint-Petersburg State Forest Technical Academy [email protected]

Lignin solubility in aqueous sodium hydroxide depends on the pH of the solution and pKa of acidic groups in lignin, and a process of lignin dissolution in alkali can be considered as fractionation based on differences in acid-base properties of phenolic hydroxyl groups of the dissolving fractions [1]. In this study, we assessed the most important parameters affecting lignin solubility in aqueous alkali based on a study of lignin solubility vs. molecular weight, temperature, hydro-module, and ionic strength. The solubility of lignins extracted under mild (Freudenberg, Bjorkman, Pepper, and dioxane lignins) and industrial (alkaline, alkaline-anthraquinone, kraft, and kraft-anthraquinone lignins)

56 conditions was studied. A new method of quantification of phenolic hydroxyl groups in lignin was developed that combines aminolysis and differential spectroscopy. It is found that solubility of lignin in aqueous alkaline media is determined by the ratio between phenolic hydroxyls and phenylpropane units in the macromolecule, the solubility increasing with the phenolic hydroxyls content. The minimum ratio providing full dissolution of solid lignin is 31 OHphen/100 PPU. A formula is proposed for calculation of lignin samples solubility in aqueous alkali. Based on this formula, the maximum solubility of kraft lignin is estimated as 200 g/l. Lignin solubility increases linearly with temperature, the temperature coefficient being rather low, and lignin dissolves completely at 100 C. High solubility of lignin at the room temperature should be noticed. The effect of ionic strength on lignin solubility was studied in the range of sodium chloride concentrations 0.01-0.4 M. The solubility decreases with the ionic strength slightly. Lignin solubility decreases with the hydro-module stepwise. Such a pattern can be explained by the constant ration between hydroxide anions and phenolic hydroxyls during the experiments. When the hydro-module increases, the volume of water in the system also increases, thus decreasing the concentration of sodium hydroxide. Therefore, the solubility of lignin depends not only on the relative but also on absolute concentration of the base in the solution. The new results confirm the conclusion of our earlier work [1]: dissolution of lignin in alkali is fractionation. [1]. Evstigneyev, E.I. Zhurn. Prikl. Khim., 2010, 83(3), 510-514.

SYNTHESIS OF ISOCAMPHYLPHENOLS

I.V. Fedorova, I.Yu. Chukicheva, A.V. Kutchin Institute of Chemistry of Komi science centre of Ural branch of RAS [email protected]

Terpenophenols are an important and very common class of nature compounds. A wide range of biological properties of natural low-molecular terpenophenols promotes obtaining of their analogues, study of reaction selectivity between phenols and terpenes, as well as to the study of biochemical and synthetic capacity of alkyl phenols. Earlier alkylation phenol, cresols and two-nuclear phenols by camphene at presence organoaluminium catalysts (PhO)3Al and (i-PrO)3Al has been studied. It is shown, that reaction passes with a high yield of orto-terpenophenols containing isobornylic substituent [1-3]. However, organoaluminium catalysts has lacks - homogeneity of the reactionary environment that leads to an additional stage of process - to processing of a reaction mixture and demands use of additional reagents; and also impossibility to recycle the catalyst. It is known that heterogeneous acid catalysts (clays, zeolites and cation exchangers) widely used in phenols alkylation [4,5]. Advantage of use of acid catalysts is ecological compatibility and possibility it recycling. In the presented work montmorillonite KSF (clay from layered silicates group) for alkylation of para-cresol and pyrocatechol by camphene has been used. This catalyst promoted formation of isocamphylphenols. It is shown, that alkylation of pyrocatechol by camphene at KSF presence leads to primary formation of products with isocamphylic substituent. The main alkylation product in this case is the para(meta)-alkylated pyrocatechol with isocamphylic substituent irrespective of a temperature mode (100 °С, 160 °С) and ratio of initial reagents (1:1 or 1:2). Products with isobornylic substituent have been allocated in minimum quantities. It is established, that alkylation of para-cresol by camphene at 100 °С leads to mono- and dialkylated para-cresol formation with isocamphylic structure of terpene substituent with yields of 44 % and 25 % accordingly.

1. Chukicheva I.Y., Kutchin A.V. Ros. Khim. Zhurnal. 2004. XLVIII. №3. P. 21-37. 2. Kheifits L.A., Aul’chenko I.S. “Terpenophenols and their application in synthesis of fragrant substances” in the book Khimiya i tekhnologiya dushistykh veshchestv i efirnykh masel. M. 1968. P. 142-190. 57 3. Chukicheva I.Yu., Timusheva I.V., Spirikhin L.V., Kutchin A.V. Chemistry of Natural Сompounds. 2007. 43. No. 3. 245-249. 4. Pisanenko D.A., Smirnov-Zamkov Y.I. Zh. prikladnoy khim. 1999. 72. 1564-1566. 5. Fomenko V.V., Korchagina D.V., Salakhutdinov N.F., Bagryanskaya I.Y., etc. Zh. Org. Khim. 2000. 36. 564-576.

NEW COMPOUNDS FROM THE PLANTS OF GENUS LIMONIUM MILL

A.V. Gadetskaya1, Zh.A. Kozhamkulova1, G.E. Zhusupova1, Zh.A. Abilov1, S.A. Ross2 1 - Al-Farabi Kazakh National University. Faculty of Chemistry. Department of Organic and Natural Products Chemistry, Almaty, Kazakhstan 2 - National Center for Natural Products Research, School of Pharmacy, The University of Mississippi, USA [email protected]

Plants of genus Limonium Mill (Plumbaginaceae) presented in the world flora by 300 species, and in Kazakhstan by 18 species and could be placed among the number of the most valuable herbs. Most thoroughly studied two species of this genus (L. gmelinii and L. myrianthum) industrial reserves which exceed 54.4 thousand tons in the Republic of Kazakhstan. Also L. gmelinii has been incorporated in State Pharmacopoeia RK. Recently, phytochemical and biological studies of the aerial parts and roots plants industrially significant species from the genus Limomum Mill had resulted in the isolation and identification of different groups of biologically active compounds. From the aerial part of Limomum gmelinii were isolated a new flavonol glycoside - gmelinoside I (1), which chemically characterized as 3,5,7,3',4',5'-hexahydroxy-3-0-a-D-galactopyranosylflavone and compound of alkaloidal nature, which structure was identified as caprolactam or azepane-2-one by UV, IR, ID and 2D NMR and HRESIMS experiments. The antibacterial and antifungal activities of the isolated compounds were evaluated. Compound 1 is a new metabolite, while 6 was isolated for the second time from a natural source. The isolated compounds showed no antibacterial or antileishmanial activity. Compound 1 was isolated as an optically active yellow amorphous powder. Its HRESIMS showed an [M+H] ion peak at mlz 481.09822 corresponding to the molecular formula C21H20O13. The UV spectrum of 1 in MeOH displayed two peaks at max 265 nm (Band I) and 365 nm (Band II) characteristic for a flavonol skeleton. The bathocbromic shift of Band I with the separate addition of NaOAc (6.0 nm) and AlCl3 (14.0 nm) to the methanolic solution of 1 indicated the hydroxylation at 1 C-7 and C-5 The H NMR spectrum of 1 showed four aromatic singlets at H 6.19, 6.37, 7.19, 7.21 nm corresponding to H-6, H-8, H-6', and H-2', respectively. It also showed an anomeric proton at H 5.33 (d, J = 0.8 Hz, H-1") correlated to C 102.1 (C-l") in the HMQC spectrum indicated a monoglycosylation which was confirmed by the presence of four oxymethine (5c 68.0-75.9) and one oxymethylene (C 60.0) carbons The site of glycosylation was determined by the HMBC 13 correlation of H-1" (H 5.33) and C-3 (C 133.7). The C NMR spectroscopic data of the sugar were quite similar to those reported for D-galactosyl moiety but the small coupling constant of the anomeric proton J = 0.8 Hz) indicates its  configuration, thus sugar was identified as -D- galactopyranose and the structure of 1 was elucidated as 3,5,7,3',4',5,-hexahydroxy-3-0-a-D- galactopyranosylflavone or gmelinoside I. Compound 6 was isolated as creamy amorphous powder. It gave an orange color on spraying with Dragendorff’s reagent indicating its alkaloidal nature The IR spectrum showed a characteristic -1 1 amide absorption peaks at max 1633 and 3296 cm . The H NMR spectrum showed five methylenes ( 1.24-2.17 ppm) but the 13C NMR, APT and DEPT spectroscopic data displayed six resonances including five methylene carbons( 26.3, 27.1, 29 7, 36.7, and 39.9) and one amide carbonyl carbon at  175.5 ppm. The absence of the methyl groups indicated the cyclization of the structure. The COSY, HMQC and HMBC confirmed the structure of 6 as caprolactam. Comparing the physical data of 6 with those reported for the synthetic caprolactam, was found that they are

58 identical. This is the second time to be isolated from a natural source and the first time from family Plumbaginaceae. The isolated compounds were tested for antileishmanial, antimicrobial activity against Candida albicans, Escherichia coli, Pseudomonas aemginosa, Oyptococcus neoformans, Methicillin Resistant Staphylococcus aerus, hfycobactenum intracellulare, and Asperglhts fiimigatus but they were inactive.

THE SYNTHESIS OF 1,2,4-OXADIAZOLINES ON THE BASIS OF TRITERPENIC 2,3- SECOACETYLHYDRAZONES

N.V. Galayko1, A.V. Pereslavceva2, I.А. Tolmacheva1, V.V. Grishko1 1 - Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia 2 - Perm State University, Perm, Russia [email protected]

To develop our research in the field of modification of 2,3-secotriterpenoids [1-3] it was considered the possibility of using these compounds as a platform for the construction of heterocyclic systems, in particular, 1,3,4-oxadiazolines. It is established that substituted 1,3,4-oxadiazolines 3, 4 are produced by heating of lupane and 19β,28-epoxy-18α-oleanane 2,3-secoacetylhydrazones 1, 2 [3, 4] in acetic anhydride. N’,N'- Diacetilgidrazones 5, 6 are formed by the reaction carrying out in a boiling pyridine in the presence of triethylamine and the surplus of acetic anhydride. The structures of 1,3,4-oxadiazolines 3, 4 were confirmed by signals in PMR spectrum of protons of methyl and acetyl substituents of the oxadiazoline cycle in the field of 2.07-2.08 and 2.24-2.26 ppm, respectively. NC CH3 NC R (CH3CO)2O O R

CH3CONHN HC N N 1, 2 3, 4 COCH3 (CH3CO)2O C6H5N, NC R (C2H5)3N (CH3CO)2NN HC

5, 6

O R = (1, 3, 5) or (2, 4, 6) COOCH3

This work was performed by financial support of the Target Program of interdisciplinary projects carried out in collaboration by scientists of the Ural and Siberian of the RAS and by the RFBR Grant No. 09-03-00642а.

References 1. I.А. Tolmacheva, А.V. Nazarov, О.А. Maiorova, V.V Grishko. // Chemistry of Natural Compounds. 2008, 5, 39.

59 2. I.А. Tolmacheva, V.V Grishko, Е.I. Boreko, О.V. Savinova, N.I. Pavlova. // Chemistry of Natural Compounds. 2009, 5, 566. 3. I.А. Tolmacheva, N.V. Galayko, V.V Grishko. // Chemistry of Natural Compounds. 2010, 1, 37. 4. N. V. Galayko, I. A. Tolmacheva, V. V. Grishko, L. V. Volkova and E. N. Perevozchikova, S. А. Pestereva. // Russian Journal of Bioorganic Chemistry. 2010, 36, 4, 516.

POLYMERS FROM RENEWABLE RESOURCES. MACROMOLECULAR MATERIALS FOR THE FUTURE?

A. Gandini University of Aveiro, CICECO-Chemistry Department, Aveiro, Portugal [email protected]

The purpose of this lecture is to provide an overview of the state of the art in the realm of Polymers from Renewable Resources.The topics covered include: - Natural polymers used as such or after appropriate chemical modifications: cellulose, hemicelluloses, starch, chitin, lignin, suberin. - Natural macromonomers and their chemical modifications: vegetable oils, tannins. - Natural monomers: terpenes, sugars - Monomers from renewable resources: furans, polycarboxylic acids, glycerol. Emphasis will be placed on recent advances and on a critical assessment of the potential applications of these novel materials.

CHIRAL CYCLOHEXENE BLOCKS FROM D-CARVONE

F.A. Gimalova1, G.M. Khalikova2, V.A. Egorov1, D.Z. Akhmetshina2, Kh.F. Sagitdinova2 1 - Institute of Organic Chemistry, Ufa Scientific Center of RAS, Ufa, Russia 2 - Bashkir State University, Ufa, Russia [email protected]

In recent few years available and inexpensive R-(-)-carvone is intensively used in directed synthesis of complex structures as chirale matrix. In the given work we describe chemorational ways of synthesizing d-carvone-based cyclohexene blocks 5 and 6. Bicyclic iodide 2 obtained in intramolecular iodine-induced cyclisation of (-)-cis-carveol 1 was used as initial product [1]. Oxidation of Me-group of iodide 2 has proceeded smoothly when boiled in toluene with SeO2. Thus produced aldehyde 3 and primary alcohol 4 are readily separated by SiO2 column chromatography. Aldehyde 3 acted on by KCH-MnO2-AcOH-MeOH – system has been converted to methyl ether 5 and then by boiling in ethanol with activated Zn into the end product 6. Oxidizing alcohol 4 with Jones’ reagent and methylation of produced CH2N2 acid has given ether 5.

60 HO CO2Me NaBH4-CeCl3, I2, NaHCO3 d-carvone MeOH, 0oC MeCN O

I O

1 2 I SeO 2 5 PhMe,  O OH CO2Me 1) H2CrO4, Me2CO HO 2) CH2N2 1) KCN, MnO2, AcOH, MeOH + O O 2) Zn, EtOH, D

I I 6 3 ~2 : 1 4

References: 1. Valeev R.F., Khasanova L.S., Miftakhov M.S. // Zh.Org. Chim., 2010, 46, 643.

ENZYME ACTIVITY OF CELLULASE AFFECTED BY LIGNIN

O.V. Golyazimova1, A.A. Politov2 1 - Institute of Solid State Chemistry and Mechanochemistry SB RAS, Laboratory of Solid State Chemistry, Novosibirsk, Russia 2 - Institute of Solid State Chemistry and Mechanochemistry SB RAS, Group of Reactivity of Solids, Novosibirsk, Russia [email protected]

Enzyme hydrolysis of cellulose can be applied for chemicals and biofuels production. Such products as carbohydrates, proteins and different extractives can be produced with sustainable enzyme technology. Renewable plant materials contain different substances including cellulose, hemicellulose and lignin molecules. Low rate of reaction and high consumption of enzyme prevent enzymatic processing of plant materials in industrial scale. One of the factors that slow down enzyme reaction of polysaccharide is presence of lignin in plant materials. It is considered that enzyme molecules can be irreversibly fixed by lignin molecules and inactivated. To prevent negative influence of lignin on enzymatic reaction it may be removed with special preliminary treatment of plant material with chemicals. Low reaction rate of enzyme hydrolysis restrict its application in industrial scale so researches in this field are very important. In this work influence of lignin samples on cellulase enzyme activity was studied. Samples of lignin were extracted from different kind of plant materials, including mechanical treated materials. Sorption of cellulose enzyme by lignins molecules also was investigated. Enzyme hydrolysis was carried out on cellulose samples (The Dao chemical Co, USA) with cellulase enzyme complex Trichoderma veride («Sibbiofarm», Russia).

This work was supported by Non-commercial partnership on development of the international researches and projects in the field of energetic «Global Energy», grant MG-2011/04/6.

MECHANICAL ACTIVATION OF BIOMASS ENZYME HYDROLYSIS FOR DEVELOPMENT OF BIOETHANOL PRODUCTION TECHNOLOGY

Bioethanol is the ethanol, produced from plant raw materials. The process of bioethanol production consists of the stage of the plant polysaccharides hydrolyses: cellulose and gemicallulose and the stage of gexose and pentose fermentation to ethanol. Hydrolysis of polysaccharides can be realized by acid hydrolysis of carbohydrates at 180 -200 ºC or by enzymatic hydrolysis at 50 ºC and pH 5. The last method is more ecologically safety and so more perspective. For enhancement of enzyme hydrolyses of the plant polysaccharide deferent methods are suggested. There are physical methods of preliminary treatment, e.g. a stem pretreatment of plant materials or chemicals methods, e.g. the treatment of plant materials with acid, alkali and organic solutions. Some time the combination of different methods is used. Also a mechanical treatment of reagents may be used for intensification of these processes. The advantage of this method is its environmental sustainability in comparing with other ones. Also the chemical composition of plant material isn’t changed by this treatment so toxic by-products aren’t formed. And the main advantage of these methods is possibility to use mechanical treatment of reagent during enzyme hydrolysis of plant materials as simultaneous treatment and thereby to enhance chemical reaction even more. In the same time when enzymes are exposed by mechanical treatment its can be denatured as enzymes are protein catalysts. So it is important to research influence of mechanical treatment of reagents on enzyme hydrolysis of plant raw materials. In our experiments enzyme hydrolysis was carried out with cellulose enzyme complex Cellolux –A, Trichoderma veride («Sibbiofarm», Russia).

This work was supported by Non-commercial partnership on development of the international researches and projects in the field of energetic «Global Energy», grant MG-2011/04/6.

EFFECT OF ELECTRIC FIELD APPLICATION DURING CHAGA EXTRACTION ON CHROMOGENES OUTPUT

N.V. Gracheva, A.B. Golovanchikov Volgograd State Technical University, Volgograd, Russia [email protected]

Various successes of domestic and foreign mycological medicine show promise in the area of higher and lower fungi being objects for development of various medicinal and healthcare products [1,2]. According to Pharmacopoeia [3], the main active substance, which content carries out the standardization of chaga raw materials and products, is chromogen (polyphenol hydroxycarboxylic complex - PHC), whose content is about 50% of the extractives. The existing technology does not allow full extraction of PHC. For example, during repercolation of PHC, the output is 9-10%, with remaceration it is 9,6-11,8%, and by mechanical stirring - 6-8% [4].

62 The effect of applying of an electric field on the yield of PHC had been studied. It is shown that the chaga extraction in presence of an electric field of direct current leads to 1.5 – 2 times PHC output increase. It has been revealed that the highest efficiency is achieved during the process at temperatures 40-50C in an electric field in the range of 4-6 V/cm.

Bibliography 1. Gorbunova I.A. Medicinal mushrooms of the south of Western Siberia / I.A. Gorbunova, N.V. Perova, T. Teplyakova, Achievements of Medical Mycology. - 2005. - v.5. - Pages 259 -262. 2. Bisko N.A. Immunological status accessment of patients at using Mikosvit dietary supplements series / N.A. Bisko, E.U. Shevchuk, N.J. Mitropolskaya, V.T. Bilai// Achievements of Medical Mycology. - 2006. - v.7. - Pages 180 -182. 3. State Pharmacopoeia of the USSR. Edition 11, additional. 1987. 389 pages. 4. Sysoeva, M.A. Investigation of sol of aqueous extracts chaga. III. Effect of raw material composition on the yield of extractives in chaga water extractions / M.A. Sysoeva, O. Kuznetsova, V.S. Gamayurova, P.P. Sukhanov, G.K. Ziyatdinova, G.K. Budnikov // Chemistry of plant materials. - 2004. - 4. – Pages 29-34.

CENTERS OF INNOVATION OF ST PETERSBURG STATE FOREST TECHNICAL ACADEMY AS NEW WAY OF INTERNATIONAL COOPERATION

I.V. Gribkov, M.M. Ravizkiy, I.V. Sumersky, S.M. Krutov, M.J. Zarubin St.Petersburg State Forest Technical Academy [email protected]

This year two Centers of Innovation were established in St. Petersburg State Forest Technical Academy by Order of Rector of St. Petersburg State Forest Technical Academy (Academy) in according with Federal Statue №217. The activity of the centers is pointed to help the scientist of Academy to establish the contacts with business society, to promote their invitations in the market and to transfer of the inventions from the author to the industry. The Centers were organized as Limited Liability Company: Open Innovation LLC and Helianthus LLC. Open Innovation FTA LLC was put in charge to serve the inventors of Department of Chemical and Biochemical transformation of wood of St. Petersburg State Forest Technical Academy. The procedure of transaction of intelligent property by means of The Centers of Innovation became more simple and easy. Some actual projects of Open Innovation FTA LLC are followed:  Technology of synthesis of new insulations from industrial lignin (lignin’s polyurethans, authors: Prof. H.Hatakayama, Prof. J. Matsumoto, Prof. M. Zarubin, Prof. S. Krutov, Dr. I. Gribkov, Dr. I. Sumersky);  Technology of utilization of acid hydrolytic lignin with production of high effective sorbate material for chemical and medical usage (authors: Prof. S. Krutov, Prof. m. Zarubin);  Effective organic fertilizer with durable action from industrial by-products of the bark (authors: Prof. I. Deineko);  Etc. ( others upon request). Open Innovation FTA LLC investigates markets of Russian Federation and elaborate the strategy for success presentation of the inventions. Other important role of The Centers of Innovation of Academy is employment of the most success students, graduating student, PhD students, young Doctors and creating new job position in Academy. The positive experience from cooperation with Open Innovation LLC has evaluated by Chemical Plants of Wood Industry (Acid Hydrolytic Plants, Plants of Eurochem Corp., Pigment JSC, Plants of Pulp and Pulping Industry and others).

63 Distribution of goods of the plants in North-West Region of Russia is additional way to obtain financial support for Open Innovation FTA LLC.

SECONDARY PROCESSING OF MULTILAYERED FOOD PACKINGS AS THE WAY OF PRESERVING WOOD RESOURCES

Yu.A. Grigoriev1, M.A. Meshchaninov2, S.B. Strashnova3, E.V. Kushnereva3 1 - Institute of Synthetic Polymeric Materials RAS, Moscow, Russia 2 - LLC «ORION» 3 - Peoples Friendship University of Russia, Moscow Russia [email protected]

Multilayered food packings (MFP) for storage and transportation of liquid foodstuff are made all over the world in the quantity exceeding 150 billion pieces a year. As a rule the share of two-layer cardboard in them is 75-77 %, of low density polyethylene (LDPE) - about 20 % and of aluminium foil – up to 5 %. MFP secondary processing with the subsequent use of its products (instead of usual burning) will allow not only to keep wood resources but also to preserve ecology in towns and cities. The plants separating paper-cardboard fractions by flotation with its secondary use are known. An additional metallic layer in MFP does not make these plants effective. A new experimental plant mounted in the Moscow Region is based on oxygen-free pyrolysis of MFP without preliminary separation of raw materials on fractions. The plant scheme consistently includes a drying chamber supplied with water steams tapping, a pyrolysis reactor of uninterrupted action and a system of pyrolysis products tapping, equipped with condensers and a separator. Useful products for the full cycle are: gas, water, aluminum and coal fractions as well as the main product of pyrolysis – liquid fast hardening fraction – the so-called «artificial solar oil». The obvious advantage of the plant is accurate fractiousness of products, i.e. aluminum and coal fractions can be delivered at once for secondary processing without additional clearing. To optimize the process, thermogravimetric analysis from 50 to 700°С with speed of heating 10 degrees/minute has been carried out. The samples were 1) two-layer packings (cardboard + LDPE); 2) three-layer packings (cardboard+ LDPE +Al) and 3) their mixture. On all the thermograms two bright peaks of weight loss between 200 and 500°С (after loss of residual water at 110-115°С) are observed. It is shown that the cellulose layer is analyzed at lower temperature than polyethylene. The first peak DTG is between 210 and 370°С with the maximum peak temperature 340°С, showing sharp reduction of weight in 45,3 %. The second peak lies in an interval 360-510°С, loss of weight is 39,47 %. The first peak is a result of decomposition of the cardboard layer, while the second - of polyethylene decomposition. Presence or absence of aluminium in the samples had no effect on MFP decomposition. Results TG–DTG have shown that MFP decomposition ends at 550°С. The structure of pyrolysis products has been investigated. The gas fraction consists of carbonic gas, hydrogen and combustible hydrocarbons С1-С5 with advantage (more than 50%) of carbonic gas. It testifies that the gas fraction is formed mainly at the temperature of cellulose decomposition and is in good conformity with the literary data. To increase the share of combustible gases (for their subsequent use for heating) it is necessary to raise the temperature in the gas tapping compartment. Fast hardening fractions include mainly paraffins and some quantity of aromatic hydrocarbons. The plant updating, in particular variation of temperature modes, should reduce power consumption of the plant and improve its parameters.

64 INFLUENCE OF WATER ON PHYSICAL-CHEMICAL PROPERTIES OF SOME NUTRITION BIOCORRECTORS MADE OF PLANT RAW MATERIALS

A.E. Gruzdeva1, V.F. Uryash2, N.Yu. Kokurina2, L.A. Faminskaya2 1 - ”Grande” Ltd., Nizhny Novgorod, Russia 2 - Research Institute of Chemistry, Nizhny Novgorod State University, Nizhny Novgorod, Russia [email protected]

For the purpose of increasing of body resistance to environmental exposure nutrition biocorrectors (NBC) can be used. For NBC application problem handling a complex approach should be followed. NBC process optimization is impossible without knowledge of main physical-chemical properties of NBC as well as influence of water on these properties. Physical state diagrams of systems NBCwater can be used as scientific basis for NBC process optimization. Currently NBC made of plant raw materials are in preference. These NBC include cryo-powders produced by “Grande” Ltd. by way of cryogenic grinding of pre-dried plant products. Cryo-powders are characterized by high biological activity due to full retention of biologically active substances and increased assimilability in the organism. The following cryo-powders were chosen as targets of research: apple powder (I), topinambur powder (II) and black currant powder (III). The samples in air-dried state contained water, mass%: I  4.1; II  5.9 and III  5.3. They represented fine powders with particle size 50-600 m. The research has been carried out on the basis of adiabatic calorimetry method in the range of 80-320 K and differential thermal analysis in the range of 80- 400 K. The thermogramms of totally dehydrated samples showed some relaxation transitions (Tg1, Tg2, Tg3, Tg4, Tβ, Tγ) apparently determined by the fact that apple contained starch and pectin (5.57 and 9.96 g/100 g respectively), topinambur contained inuline (58.6 g/100 g) and black currant  1.5 g/100 g of pectin. Physical-chemical and thermodynamic properties of the specified polysaccharides were analyzed by us earlier. At increase of water concentration in mixtures NBCH2O glass transition temperature in samples (Tg1, Tg2, Tg3, Tg4) decreased which means that water produces a plasticization effect on NBC. Water has almost no effect on temperature of secondary relaxation transitions (Tβ, Tγ). For mixtures containing water ≥25 mass %, except for the indicated relaxation transitions, endothermic melting peak of non-dissolved «free» water in the sample was observed. At such concentrations of liquid component the system becomes two-phase and in fact the «free» water phase stops influencing glass-transition temperature of saturated water solution in NBC. For adequate calorimeter test of water solubility limit in NBC cryo-powders, the mixtures have been prepared using water quantity exceeding its solubility limit in the product evaluated on the basis of thermogramms. Concentration of saturated at 273 K water solution in NBC is, mass%: I  21.7 ±0.8; II  19.3 ±1.0 and III  24.15±0.05. On the basis of data received on physical transitions temperature and water solubility in cryo-powder, physical state diagrams of the system cryo-powder (I)water were made. Such diagrams make it possible to determine temperature and concentration ranges of glass and rubbery state of NBCwater mixtures, their homogeneous and heterogeneous states in the broad temperature range and in the entire range of components concentration. With the help of these the NBC process can be optimized.

65 HARVEST OF MOUNTAIN ASH (SORBUS AUCUPARIA L.) ON THE AREA OF CLEAR CUTTING

A.V. Gryazkin, N.V. Belyaeva, N.V. Kovalev, А.S. Khodachek, A.A. Fetisova The Saint-Petersburg State Forest Technical Academy of S.M.Kirova [email protected]

Significant impact on yields and stocks of non-timber resources of wild fruit plants has uncontrolled recreation and economic activities. In this paper, the results of studies on the yield of mountain ash in felling 13 years ago and under a canopy of trees. Studies conducted in Roshchinsky experienced forestry (Forestry), the Leningrad region in 1997. As objects of study were chosen bilberry spruce forest type (before felling) with tree crown to 0.82, the relative completeness of the stands - 0,8. Clear-cutting done in winter 1998/1999 years. Accounting fruiting rowan was held in 2010. On model trees take into was accounted the number of branches, the branches and bunches of berries in clusters. Then we selected sample of berries for the subsequent determination of their mass and yield of mountain ash in these conditions. Our observations showed that the selected objects give abundant crop of berries of mountain ash it once in 5-7 years (13 year period was noted two fertile years - 2005 and 2010). Number of bunches on a single tree in the good year varies considerably chapels from 4-6 to 30-45. We noted as well and a large variability in the numbers of berries per bunch. Number of berries in one cluster can range from 27 and 72. The average weight of one berry varies widely. The scope of variation of this value is between 0.364 and 0.761 to gr. The proportion of damaged fruit can be, depending on growing conditions from 9 to 16%. The obtained data show that on the harvest of berries of Mountain ash improved after clear cutting.

WATER VAPOUR SORPTION – THE PARALLEL EXPONENTIAL KINETICS MODEL AND CELL WALL VISCOELASTICITY

C.A.S. Hill Edinburgh Napier University [email protected]

It has been recently demonstrated that the water vapour sorption kinetics of the plant cell wall can be accurately described by the so-called parallel exponential kinetics (PEK) model, which has the mathematical form:

MC = MC0 + MC1[1 – exp(-t/t1)] + MC2[1 – e(-t/t2)] (1)

Where MC is the moisture content after infinite time of exposure of the sample to a constant relative humidity (RH), MC0 is the moisture content of the sample at time zero. The sorption kinetic curve is composed of two exponential terms which represent a fast and slow process having characteristic times of t1 and t2 respectively. The terms MC1 and MC2 are the moisture contents at infinite time associated with the fast and slow processes respectively. There has been speculation as to what physical phenomena the two processes represent and there is no clear view on this at the present time. Using such a function, it is possible to obtain highly accurate curve fits.

The fast and slow components of the PEK equation have a mathematical form that is identical with that describing the dynamic response of a Kelvin-Voigt element when subjected to an instantaneous stress increase (σ0):

(2) ε = (σ0 /E)[1 – exp(-t/φ)]

Where ε is the strain at time t, E is the elastic modulus and φ is a time constant which is defined as the ratio η/E, where η is the viscosity [5]. In the case of a plant fibre subjected to a change in

66 relative humidity (RH), there is a change in the swelling pressure (Π –equivalent to σ0) exerted within the cell wall when the atmospheric water vapour pressure is raised from an initial value pi to a final value pf given by Equation 3:

Π = - (ρ/M)RT.ln(pi/pf) (3)

Where ρ is the density and M is the molecular weight of water, R is the gas constant and T is the isotherm temperature in kelvin. In the model described herein, the strain of the system is assumed to be equivalent to the volume change of the cell wall as a result of water vapour adsorption or desorption. This volume change is further assumed to be linearly related to the change in the mass fraction of the water present in the cell wall. The appropriate mechanical analogue comprises two Kelvin-Voigt elements arranged in series. Using such a model, the sorption kinetics data of various wood species and plant fibres has been analysed. The results will be presented and an extension of the PEK model and its consequences discussed.

INSIGHTS ABOUT ENZYMATIC HYDROLYSIS BY USING BICOMPONENT LIGNOCELLULOSIC SENSORS

I.C. Hoeger1, I. Filpponen2, M. Osterberg2, J. Laine2, S. Kelley1, O.J. Rojas1 1 - Department of Forest Biomaterials, North Carolina State University, Raleigh, USA 2 - Department of Forest Products Technology, School of Science and Technology, Aalto University, Finland [email protected]

The concept of biofuels from lignocellulosic material is advancing at a very rapid pace. However, there are still several fundamental questions holding back its commercial development. Importantly, the conditions for optimal rate and extent of cellulose hydrolysis need to be understood. However, this has been a difficult task since these properties are influenced not only by the effectiveness of the enzymes but by the chemical and morphological characteristics of the substrate. For example, lignin has been shown to have a detrimental effect on the hydrolytic degradation of biomass. Most studies in this area have focused on the enzymatic hydrolysis in bulk materials, but direct monitoring of enzymatic hydrolysis on lignocellulosic surfaces has not been reported. Therefore, in this work we used model thin films as a suitable platform to study associated interfacial behavior. To that effect, bicomponent thin films with different ratios of cellulose and lignin were prepared by the spin coating technique. The obtained ultrathin films were used as sensors that were characterized via atomic force microscopy, x-ray photoelectron spectroscopy and contact angle. The activity of cellulolytic enzymes was monitored with quartz crystal microbalance and the results were used to explain some of the complex roles of lignin in enzymatic processes.

HEALTH-PROMOTING PRODUCTS FROM WOOD, BARK AND KNOTS

B.R. Holmbom1, C. Eckerman1, J. Hemming1, T.R. Holmbom2, S. Willfor1 1 - Aabo Akademi University, Process Chemistry Centre, Turku/Aabo, Finland 2 - Separation Research Oy Ab, Turku/Aabo, Finland [email protected]

Today, there is a request for replacing synthetic oil-based chemicals and materials with natural bio- based alternatives from renewable resources. At the same time, there is a growing interest in natural health-promoting compounds. Trees have through millions of years of evolution developed very efficient chemical defense systems enabling them to survive for hundreds of years. Therefore, trees are a rich source of various natural bioactive compounds. Many tree-derived compounds are already on the markets world-wide as active compounds in dietary supplements and health-promoting, functional foods, with xylitol and sitosterol/sitostanol as examples. Research at Åbo Akademi University nhas revealed that knots inside tree stems contain extraordinarily high concentrations of polyphenols, typically 5-15%. Spruce knots contain

67 exceptionally high concentrations of the lignan hydroxymatairesinol (HMR). This HMR lignan has been documented to be a strong antioxidant, and furthermore to inhibit the growth of breast and prostate cancer. ietary supplement. Spruce knot extract is now added also as a bioactive ingredient to cosmetic creams and shampoos. These polyphenols from knots are potent natural antioxidants and biocides which could find also technochemical applications. Resin scraped off from the surface of spruce trees (partly callus resin) has been used traditionally as a chewing gum and for wound healing. Recently it has been developed in Finland to a modern wound-healing salve. Taxol, the best-selling anti-cancer drug, is extracted from needles or bark of yew (Taxus) trees. A pine bark extract, Pycnogenol, has been on the market for more than ten years, stated to be a powerful anti-oxidant and natural anti-inflammatory agent. Spruce bark contains high concentration of potentially very valuable stilbenes, which are currently of large interest because of their possible life-extending (anti-ageing) properties. In summary, trees in northern boreal forests can provide several platforms for production of natural health-promoting substances which can be of exceptionally high value. Development of new products demands fruitful trans-disciplinary research between chemists and biomedical scientists, and furthermore requires engaged entrepreneurs who can formulate the products and bring them to the markets through ever stricter regulations regarding safety testing and health claims, be it dietary supplements, functional food ingredients or pharmaceuticals.

PICEA WOOD GREENERY EMULSION EXTRACT: ISOLATION, RESEARCH, APPLICATION

T.V. Hurshkainen, N.N. Skripova, E.E. Zonova Institute of chemistry of Komi science centre of Ural branch of RAS, Syktyvkar [email protected]

Research of a chemical composition of Pecea wood greenery extractive compounds, technological schemes of its processing and possibility of obtained products application in different branches of a national economy is an actual problem. Comparative studying of emulsion method of Picea wood greenery processing [1] spent with use of laboratory 1L extractor with the mechanical mixing device, rotary-cavitive apparatus (delta- rotor) and pulsation-filtrational device is carried out. Extractive compounds yields at different extraction solvent concentration, liquor ratio, temperature and time of processing are determined. Extraction compounds are divided by acid-base method and adsorption chromatographic method. Analysis of Individual compounds is carried out by means GLC, HPLC, IR-and NMR - spectroscopy. Research of Picea wood greenery extract on content of phenolic components spent with use of pK-spectroscopy method. The content of extractive compounds in emulsion solution is 6,2 - 6,7 %, of them acid components - up to 5,5 % from weight of raw material. From the sum of non-polar sour components p- hydroxyacetophenone is isolated with yield of 0.1 % from weight of raw material. It is found that content of oleic acids is 12.5 %, linoleic acid - 17 %, linolenic - 9 % is certain in the sum of non- polar acids (2 % from weight of raw material) according to GLC. Polar-acid fraction (2,5 % from weight of raw material) contains dehydroabietic acid derivatives and phenolic compounds. Phenolic compounds of Picea possess high activity against to a number of viruses, gram-positive and gram-negative microorganisms, pathogenic mushrooms and ability to adjust growth of plants [2]. On the basis of Kirov State Medical Academy pharmacology faculty a toxicological estimation of Picea wood greenery emulsion extract and fraction of phenolic compounds in experiments on small warm-blooded animals is lead. It is established, that Picea extractive compounds do not possess toxic action. As a result of the lead researches it is offered for practical application fungicidal preparation from Picea wood greenery obtained by emulsion extraction method. Biological tests of a new preparation on protection of cereals crops against illnesses are spent.

68 Work is executed at financial support of the program of basic researches of branch of chemistry and sciences about materials of the RAS «Creation of new kinds of production from mineral both organic raw material» and the State contract № 02.740.11.0081 of Ministry of Education and Sciences of Russian Federation.

LITERATURE 1. Hurshkainen T.V., Skripova N.N., Kutchin A.V. Highly effective technology of complex processing of plant raw material and obtaining of preparations for an agriculture // Theoretical and applied ecology. 2007. №1. P. 74-77. 2. Artemkina N.A., Roschin V.I. Polar extractive compounds of needles and runaways of Picea abies (L.) Karst // Vegetative resources. 2004. Т. 40. No. 3. P. 77-86.

RECEPTION NITROINULIN FROM TUBERS HELIANTHUS TUBEROSUS

A.Sh. Husenov, O.Sh. Kadirov, G.R. Rakhmanberdiev Tashkent Chemical Technology Institute [email protected]

Nitroinulin (Inulin nitrate) – a difficult ether of mineral acids of polysaccharide inulin, containing a little – ONO2 radicals with molecular weight 8500 – 10500, a representing crystal powder, insoluble in water, in acetone, easily soluble in hot water in the alkaline environment, and also in difficult ethers. As, nitoinulin it is received by us for the first time have considered it necessary in more details stand still on reaction nitration of inulin. For studying of reactionary ability of inulin and workings out of modes of reaction nitration have been put a number of experiments. The nitrate mix was following structure: HNО3 - 21, 0 %; Н2SО4 – 70, 0 %; Н2О – 9, 0 % which is usually used for nitration of processes of hydrolysis and oxidation of inulin, time nitration – 10 minutes. polysaccharide cellulose. The module nitration has made 1:20, the reaction temperature was supported in the range of 10 – 20о С as reaction carrying out above 20о С is undesirable because of acceleration Process spent in a following order: 10 g inulin (humidity of 2, 8-3, 0 %), loaded into the device with a reactionary mix. At vigorous hashing in a course nitration was selected every 2 minute by 5 tests (for averaging of results) and placed them in the big surplus of cold water with ice (for the termination of chemical reaction) and defined in them the nitrogen maintenance. Reaction nitration of inulin can be represented schematically as follows:

Reaction nitration is influenced by many factors from which number it is necessary to note the following: concentration of nitric acid and its structure (the maintenance of oxides of nitrogen); relative quantity of sulfuric acid; the water maintenance in nitrate mixes; the bath module;

69 temperature; influences of these factors have been investigated. Received nitroinulin, with maintenances of 10 % of nitrogen has been investigated on display hypoglycemic activity. Researches have shown, that nitroinulin in equal doses on sugar-lowering activity two times is effective, than inulin.

SO2-ETHANOL-WATER (SEW) FRACTIONATION OF SPRUCE: MATERIAL BALANCES

M. Iakovlev1, A. Van Heiningen2 1 - Aalto University, Department of Forest Products Technology, Espoo, Finland 2 - Aalto University, Department of Forest Products Technology, Espoo, Finland and University of Maine, Department of Chemical and Biological Engineering, Orono, USA [email protected]

Two pressing global issues, climate change and limited accessible petroleum reserves, are driving the interest to use lignocellulosic biomass for production of transportation fuels. SO2-ethanol-water (SEW) lignocellulosic fractionation has potential to overcome the present techno-economic barriers which hinder commercial implementation of renewable transportation fuel production. In the present study SEW fractionation of spruce wood chips is examined for its ability to cleanly separate the main components, hemicellulose, lignin and cellulose, and how to recover SO2 and ethanol. Therefore, overall, sulfur and carbohydrate mass balances are established for fractionation at a liquor-to-wood ratio of 6 L/kg, 3.0-12% SO2 in the initial liquor and 10-370 minutes of treatment at 135°C. It was found that the amount of sulfur bound to residual lignin corresponds to only 0.040- 0.090 S/C9 while that bound to dissolved lignin is 0.15-0.26 S/C9. These values correspond to only less than 0.2 and 1.1% sulfur on wood, respectively. Thus the major amount of SO2 remains in the liquid (95-97% of total charged amount) and can be efficiently recovered by distillation. During fractionation hemicelluloses and lignin are effectively dissolved, while cellulose is preserved in the solid phase. Hemicelluloses are hydrolysed producing up to 50% monomeric sugars, whereas dehydration and oxidation of carbohydrates are insignificant. The latter is proven by the closed carbohydrate material balances as well as by the near absence of the corresponding by-products (furfural, HMF and aldonic acids).

ON THE OPTIMIZATION OF ADVANCED OZONATION PROCESSES

A.N. Ignatev, A.N. Pryakhin, V.V. Lunin Department of Chemistry, Moscow State University, Moscow, Russia [email protected]

Ozone is widely used in water treatment, bleaching and paper mill industry. The decomposition of ozone in an aqueous media leads to formation of free radicals. So during ozonation of a dissolved S O products substance S two types of reactions occur: 1) direct molecular ozonation ( 3 ), 2)  indirect radical ozonation (S+ OH products , S+ O products ). Parameter z can be used to indicate a predominant pathway (molecular, radical or mixed). t kdtSO  nt S-O3  3 S-O3  0 z ==tt ntnt+ -  - S-OH S-O kdtkdtSOH+ SO  S-OH  S-O-   00

ntS-O  nt nt-   In the formula above 3 , S-OH and S-O are the amounts of substrate S that have been utilized to the moment t in the reactions of S with O3, OH and O- respectively. If z >> 1, S reacts generally with O3. If z << 1, the indirect ozonation predominates. If z ~ 1, both the radical and the molecular pathways should be taken into account.

70 Parameter z was calculated for wide ranges of pH-values and initial concentrations of the reagents (O3, S and H2O2). Ozonation in batch and semibatch reactors was analyzed. A mathematical modelling based on the kinetic scheme of ozone decay was used. Diagrams of conditions that favor direct and indirect ozonation were plotted (see fig. 1). Increasing of pH and H2O2 concentration and/or decreasing of substrate concentration favor the radical ozonation. Our numerical calculations also showed that there are optimal values of pH and optimal concentrations of H2O2 at which concentration of hydroxyl radical formed during ozone decay reaches the maximum (see figure 2). It should be notes that high concentrations of H2O2 suppress the generation of OH-radical, because hydrogen peroxide starts to play the role of a radical scavenger. Concentrations of other intermediates (HO2, HO3, O3- etc.) were also calculated. The results obtained help planning experiments and could be used to determine optimal conditions of ozonation processes. −3 10

−9 x 10 6

Transition region 0.1< [OH] −4 max 5 10 4 , M 0 , M ] 2 st 3 O 2 [OH] [H 2 −5 Radical 10 Molecular reactions reactions z 1 (direct *<10 (indirect ozonation) ozonation) z z*>10 *<0.1 14 −7 12 −6 10 10 10 8 −5 6 −4 10 pH 4 10 −6 2 −3 ] , M 10 10 O 2 0 [H 2 2 4 6 8 10 12 14 pH Figure 1. Areas of direct and indirect ozonation Figure 2. Dependence of concentration of OH- -4 in presence of H2O2. [O3]0 = [S]0 = 10 M. radical on the pH and initial concentration of -4 H2O2. [O3]0 = 10 M.

THE SYNTHESIS OF COMPLEX ETHERS OF 2,3-SECOTRITERPENOIDS

E.V. Igosheva, I.А. Tolmacheva, V.V. Grishko Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia [email protected]

C-3 Ethers of betulin and betulinic acid on the basis of succinic and glutaric acids exhibited high anti-HIV activity, for example, a drug based on 3-O-(-3', 3'-dimethylsuccinyl)betulinic acid (Bevirimat) is passing the second phase of a clinical trails as the new inhibitor of HIV-1, which is effective in a very low doses [1-3]. A promising as antiviral agents secotriterpene complex monoethers were obtained by interaction of 2,3-secotriterpene alcohols 1, 2 [4] with commercially available anhydrides of succinic, 2,2- dimethylsuccinic, 2,2-dimethylglutaric, 3,3-dimethylglutaric acids in pyridine in the presence of 4- dimethylaminopyridine.

71 Acid anhydrides NC R NC R 1 4-(CH3)2NC5H4N, R COOCH2 HOH2C C5H5N

3, 4 1, 2

O R (2, 4) = R (1, 3) = COOCH3

1 R = HOOCCH2CH2- ; HOOCC(CH3)2CH2- ; HOOCC(CH ) CH CH - ; HOOCCH C(CH ) CH - 3 2 2 2 2 3 2 2

The work was supported financially by the Grant of the Ural of the RAS No. 103-НП-260 and by the RFBR Grant No. 10-03-96044-р_ural_а.

References 1. I-C. Sun, H.-K. Wang, Y. Kashiwada, J.-K. Shen, L. M. Cosentino, C.-H. Chen, L.-M. Yang, K.- H. Lee. // J. Med. Chem. 1998. Vol. 41. P. 4648-4657. 2. K. Qian, R.-Y. Kuo, C.-H. Chen, L. Huang, S. L. Morris-Natschke, K.-H. Lee. // J. Med. Chem. 2010, Vol. 53. P. 3133–3141. 3. J. Xiong, Y. Kashiwada, C.-H. Chen, K. Qian, S.L. Morris-Natschke, K.-H. Lee. // Bioorg. Med. Chem. 2010. Vol. 18. P. 6451-6469. 4 L.V. Anikina, I.A. Tolmacheva, Yu.B. Vikharev, V.V. Grishko. // Russian Journal of Bioorganic Chemistry. 2010. Vol. 36. No. 2. P. 240-244.

THE ASCERTAINMENT OF THE ACTIVITY ANTIFUNGAL OF THE COMPONENTS OF ETHANOLIC EXTRACT OF VEGETATIVE PART OF POPLAR

E.V. Isaeva, T.V. Ryazanova, Yu.A. Litovka Siberian state technological univasity, c.Krasnoyarsk, Russia [email protected]

Fungi of the genus Fusarium produce toxic compounds that represent a threat to human, animals and plants. phytotoxins, suppressing the activity of plant cells in small concentrations, are determinants of many plant diseases, in particular fusariose- producing factors, and Further to soil exhaustion due to accumulation of toxic species. For the control of fusarium you can use plant extracts. It the work it was researched the influence of separate components of ethanolic extract of the vegetative part of populus balsamifera (shoots with the kidneys) on the growth and development of fungi of the genus Fusarium. Fractionation of the substances contained in an alcohol extract, carried out after its clarification, using solvents with different polarities: petroleum ether, ethyl ether, ethyl acetate and butanol. The ascertainment of thet activity antifungal were being carried out with using strains of microscopic fungi T11 Fusarium sporotri-chioides and T13, Fusarium monilifor, being

72 characterized by a high degree of toxicity in relation to seeds, sprouts and seedlings of coniferous and cereals and displaying middle sensitivity to chemical fungicides (fendazol, vial-TT, TMTD,). Practically strains T11 and T13, practically does not differ in the speed of growth between itself, as in control, as well as in the experimental variants. Inoculated the studied strains agar wort was used as a control. As show the results of the research, the smallest increase colonies of both strains was observed in environments containing substances of petroleum and athylacetate extracts in the concentration of 1000 µg/ml and diethyl extract (2000 µg/ml). In the first eight days of cultivation the most constraining growth effect possessed the petroleum extract in wich a high qweta is not containing oxygen of mono- and seskvi-terpenoids, and athylacetate extract, containing predominantly flavanoids and phenolcarbonis acid. Later on more actively restrained growth of fungi were substances taken by diethyl ether (2000 µg/ml), in structure of which there are sesquiterpene alcohol, in particular bisabolol, possessing, antitumour activity. The lowest activity was noted in butanol soluble substances (phenolic glycosides compounds) Investigations of the influence of components ethanolic extract on the radial growth rate of phytopathogenic fungi of the genus Fusarium have shown, that with lower rate they grow on media containing the substance petroleum extract (1000 µg/ml) and the total ethanolic extract (4000 µg/ml). The greatest activity antifungal was installed in relation to both strains of the substances petroleum extract. Thus components of ethanolic extract of the kidneys and shoots populus balsamifera display activity antifungal against phytopathogenic strains of fungi of the genus Fusarium, that is displaying in decreasing the speed of the growth and change in the morphological features of the mycelium, and also diminishing of indexes of konidiegeneza. The investigated compounds of plant origin may be perspective antimicotiks.

EVALUATION OF THE CONTRIBUTION OF VARIOUS TOXIC SUBSTANCES IN THE INTEGRAL TOXICITY OF SOIL IN MOSCOW

O.V. Ischenko, A.A. Ageeva, E.V. Karelina, V.N. Mochna, A.V. Garabadjiu, G.V. Kozlov Saint-Petersburg state institute of technology (technical university), St-Petersburg [email protected]

Based on published data on the content of organic and inorganic contaminants in soils of Moscow and the data on their toxicity we have compiled a chart presented in Fig.

The diagram illustrates the contribution of various pollutants in the integral toxicity of soil.

DECONTAMINATION OF CONTAMINATED SOIL AND TOXIC WASTE, USING COMPOST FROM MSW

O.V. Ischenko1, D.S. Yakshilov1, A.V. Musatov2, A.A. Ageeva1, E.V. Karelina1, V.N. Mochna1, A.V. Garabadjiu1, G.V. Kozlov1 1 - Saint-Petersburg state institute of technology (technical university), St-Petersburg 2 - Branch of the Federal State Unitary Enterprise, St. Petersburg [email protected]

Compost from municipal solid waste heavily polluted with heavy metals. Use it for gardening is impossible. Compost is landfilled. We offer two options for the rational use of compost: The first option - the toxic waste (organic chemicals) are mixed with compost and placed in a stack. Compost is a source of heat and microorganisms - destructors. Value of 1 / 10 to 1 / 100. Compost temperature 50-60oC. The term of 7-8 months of composting. The second option - the use of compost as a biofuel for heating the processed biologics plot of soil. For these purposes, use the compost produced in the winter and having optimal for biological product temperature - 26-34OC. Compost - only heat source. For the destruction of pollutants in the soil make the association of bacteria - degraders. Processing time - the cold season (up to 6 months). We have studied the biodegradation of polycyclic aromatic hydrocarbons (PAHs) and petroleum products. In both cases there was a decrease of concentration of pollution in more than 20 times the original.

74 SYNTHESIS AND WATER SWELLING CAPACITY OF HIGH-SUBSTITUTED CELLULOSE PHOSPHATES

A.V. Ivaniutsina, N.K. Yurkshtovich, V.A. Ramashka Institution of General and Inorganic Chemistry of the National Academy of Sciences of Belarus [email protected]

Modified natural polysaccharides possessing high water-swelling capacity find an application in pharmaceutical chemistry and medicine as drugs mediums. Highly-substituted cellulose phosphates obtained by the methods described in [1-3] are known to be used as promoters of bone regeneration process and as additives in preparation of hydroxyapatite composites. In this work the of study cellulose phosphorylation was carried out as well as the dependence of water swelling capacity of cellulose derivatives on the phosphorylation reaction conditions was investigated. The parent polymer was cellulose regenerated by the viscose process in the form of viscose fibres. The cellulose etherification reaction was carried out at 20-40°С during 1-48 h in waterless systems, containing H3PO4, (C4H9O)3OP, P2O5 at a ratio of (0,12-0,18), (0,01-0,03), (0,06-0,08) respectively. The products of the reaction were washed with ethanol using Soxhlet apparatus for at least 24 h and then dried to air-dry condition. Their characterization has been done by elemental analysis, in terms of their water swelling and their structure was studied by FTIR. In consequence of modification cellulose phosphate samples with degree of substitution DSP ranging from 0,05 to 2,00 and water swelling capacity ranging from 120 to 15000 % were obtained. By means of FTIR spectroscopy – by the noticing of appearing in modified samples IR spectra new bands corresponding to P-containing structures bonds it was demonstrated that during the reaction of etherification phosphorous-containing structures were lead-in the macromolecule of cellulose. The intensive accumulation of phosphate groups in polymer was shown to appear during 6 h, since the time of reaction increased up to 24-48 h the rate of reaction decreased. Such a dependence of the rate of the reaction on time is specific feature of heterogeneous reactions involving polysaccharides, that can be either the result of different reactive capacity of hydroxyl groups of initial polymer or of the influence of the reaction products on cellulose derivatives yield [4]. The containing of phosphate groups in macromolecule of cellulose was supposed to rely linearly on temperature. The investigation of water swelling capacity of cellulose phosphates showed that either watersoluble or gelling phosphorylated polysaccharides can be obtained depending on the conditions of the etherification reaction. The ability of gelling to realize due to appearance of additional cross-linking in the structure of polysaccharide is distinctive for highly-substituted phosphorous-containing samples. The investigation showed the possibility of hydrogels based on highly-substituted cellulose phosphates with high water swelling capacity to obtain. This property in connection with biocompatibility and lack of toxicity of the parent polymer are promising for the use of cellulose phosphates as mediums for controlled-release of drugs due to either ion-exchange interaction with the physiologically active compound or distribution of substances in dimensional polymer network. References 1. Granja, P.L.; Pouysegu, L.; Petraud, M; De Jeso, B; Baquey, C.; Barbosa, M.A. J. of Appl. Pol. Sc. 2001, 82, 3341. 2. Granja, P.L.; Barbosa, M.A.; Pouysegu, L.; De Jeso, B; Rouais, F.; Baquey, C. J. of Mat. Sc. 2001, 36, 2136. 3. Suflet, D.M.; Chitanu, G.C.; Popa, V.I. Reactive and Funct. Pol. 2006, 66, 1240. 4. Azarov, V.I.; Burov, A.V., Obolenskaya, A.V. Chemistry of Wood and Synthetic Polymers 1999, p. 546-552.

75 GLUCOSE ANOMERS AS INDICES OF HONEY THERMAL TREATMENT

I.K. Ivanova1, V.V. Koryakina1, E.Yu. Shitz1, A.I. Fedorova2 1 - Institute of Oil and Gas Problems, Siberian Branch of RAS 2 - Yakut State Technical Institute [email protected]

The authors carried out the NMR analysis of water solutions of several sorts of honey differing by their geobotanical nature, year of collection and thermal effect to which they were subjected. On the basis of the results obtained during experiments it is established that fructose diastereoisomers in honey are in equilibrium concentrations, so their distribution does not change at heating. The influence of temperature on the ratio α-/β - forms of glucose is revealed, which is confirmed by calculating the difference between free conformational energies of anomer forms of glucose. It is established that in the unheated honey the value of the ratio α-/β - glucose >1, thus differences of their energies are characterized by negative values. At honey heating glucose anomerization occurs and due to this the ratio value becomes <1 and energy differences between anomers become positive. Therefore, the ratio of glucose anomers in honey can be considered as an index of its thermal transformation and can be used as an additional technique at examining the honey quality.

SYNTHESIS OF CHIRAL THIOSULFINATES, SULFINYL AMIDES AND SULFINYL IMINES BASED ON THIOLS WITH MENTHANE STRUCTURE

E.S. Izmestev, D.V. Sudarikov, S.A. Rubtsova, A.V. Kuchin Institute of Chemistry, Komi science center, Ural division of the Russian Academy of Sciences [email protected]

The terpene sulfur containing chemistry develops rapidly now. This connects with a large-scale prevalence of terpenes in the nature, their relative cheapness and biologic activity. Sulfur containing terpene derivatives possess valued physiological properties. High antiparasitic, antibacterial and nematocidal activities as well as moderate antitumoral effect in combination with low toxicity for homoitherms are detected for some terpenic sulfinyl containing matters. Some of these drugs can prevent an platelet aggregation and use for a therapy of cardiovascular diseases and arthritises. Based on neomenthyl thiol, various compounds with sulfinyl group coupled in direct contact with sulfur or nitrogen atoms were obtained. The oxidation of neomenthyl thiol by soft oxidants gave dineomenthyl disulfide (3), on basis of which diastereomeric thiosulfynates (5) with de up to 45% were formed.

S S NH S S S 2

2 O 5 O R2 SH 8 HO S S S S N SH S C R1 3 O 6 O H R 1 9 1 H S S N S S S C R2 H H O 10 OH 4 7 O 1. R1=R2=H; 2. R1=Cl, R2=H; 3. R1=R2=Br

76 We obtained the single neomenthyl sulfinyl amide (8) (its absolute configuration was not identified) out of thiosulfinates (5) via the nucleophilic substitution by potassium amide. The condensation of 8 with salicyl aldehyde and its derivatives gave the respective sulfinyl aldimines (9). The compounds 9 were reduced by LiAlH4 to N-substituted sulfinyl amides (10). All diastereomeric sulfides (2, 3, 4) were formed by the oxidation of thiol 1 in the mixture with menthyl thiol. The further oxidation of these disulfides led to three pair diastereomeric thiosulfinates (5, 6, 7).

The work was supported by the Russian foundation for basic research (grant 10-03-00969).

PHYSICAL-CHEMICAL PROPERTIES OF BIOADSORBENTS ON THE BASE OF LEMNA MINOR

Z. Ch. Kadirova1, D.S. Rahmonova1, N.A. Parpiev1, Kh.T. Sharipov2, O.V. Stoyko2, S.A. Chepulsky1 1 - Uzbekistan National University 2 - Tashkent Chemical Technological Institute [email protected]

At present time, the water plants used successfully in developed and developing countries for removal of pollutants from water. The application of local raw plants like biological sorbent is an actual scientific-technical task, which solution in future would rationalize the process of purification of the industrial and domestic wastewaters. The plants possessing to the sorption and accumulation of different pollutants were chosen among the higher water plants of Chirchik and Zarafshan rivers. Many types of functional groups are responsible for the biosorption of metal ions by water plants. Some intensive character vibration bands in IR-spectra of duckweed (Lemna minor) can be assigned to the functional groups observed for proteins and polysaccharides. Because the bands in region of 1657, 1419 sm-1 are determined by different vibrations of carboxylate groups (free and chelate C=O groups, assymetric and symmetric vibrations of C=O and C-O, respectively), the bands of the polysaccharides ester and OH-groups are observed in region about 1160 and 1090 sm-1, respectively. From another hand, the NH vibration bands of proteins are observed in region about 1558 sm-1. The band intensity and frequency changement after metal complex formation are used for confirmation of the metal- biosorbent bond formation. To elucidate the nature of the interaction of copper ions with the biomass functional groups, the infrared spectra of the initial biomass and the samples treated with alkaline solutions were studied. The observed changes in the spectra of the samples treated with KOH, indicate changes in the structure of the substrate, which is caused by destruction of inter-and intramolecular bonds of the duckweed biopolymers. The method of scanning electron microscopy (SEM / EDX) was used to investigate the sorption of metal ions on the surface of the plant and provide a qualitative assessment of surface structure. The surface of the biomass before and after the sorption of metal ions from solution has a surface roughness and the microstructure with the presence of the calcium and other salts of crystalline type deposits. The EDX analysis shows that the calcium is the main inorganic component of the duckweed surface, both before and after sorption of the metal. In this case, morphological contraction and changes of layers in the cell wall were observed. The changes in surface morphology are usually associated with the destruction of cross-linking between the metal ions and the negatively charged chemical groups such as carboxyl groups contained in the polysaccharides cell wall. When the plant is placed in a solution of metal such as cadmium, the cadmium cations replace some calcium and magnesium ions, thus changing the nature of binding on the surface, which leads to morphological changes. The calcium content increased after chemical activation by NaOH solution (pH 10.5) followed by treatment with aqueous solutions CaCl2/MgCl2/NaCl (2:1:1). In this case, the dried biomass can adsorb ions of some heavy metals such as Pb2 +, Cd2 +, Ni2 + and Zn2 + from aqueous solutions with

77 different concentrations. The activated biomass particles have a higher adsorption capacity towards heavy metal ions in a series of Pb2 + ~ Ni2 +

HYDROLYTIC HYDROGENATION OF CELLULOSE AND HEMICELLULOSES OVER SUPPORTED PT CATALYSTS

M. Kaldstrom1, N. Kumar1, M. Tenho2, M.V. Mokeev3, Yu.E. Moskalenko3, D.Yu. Murzin1 1 - Abo Akademi University, Turku, Finland 2 - University of Turku, Turku, Finland 3 - Institute of Macromolecular Compounds RAS, Saint-Petersburg, Russia [email protected]

Hydrolysis and hydrolytic hydrogenation of microcrystalline cellulose (Aldrich) and bleached birch (betula) kraft pulp from a Finnish pulping mill into sugars and sugar alcohols was carried out in the liquid phase in a batch mode under 20 bar of hydrogen at 458 K over zeolites, mesoporous materials per se as well as containing Pt. Proton forms of different microporous and mesoporous materials, Pt modified MCM-48 mesoporous material as well as Pt on Al2O3 were used in the catalytic experiments. The conversion of cellulose and hemicelluloses varied depending on the type of zeolite structure, strength of active sites, their number and presence of metal. The ratio of formed monomers/dimers varied depending on the pore size of the used catalyst. The yields of the main products, e.g. sugars, sugar alcohols and furfurals (xylose, glucose, xylitol, sorbitol, furfural, furfuryl alcohol and 5-hydroxymethyl furfural), varied depending on the type of substrate as well as on the active sites, acidity, presence of metal and structure of the zeolite and mesoporous material. The reaction network was advanced (Figure 1).

OH OH HO OH

OH Xylitol

O H2 H2 O Xylans O HO OH OH Dehydration Furfural Furfuryl alcohol OOH Decarbonylation

OH O OH Xylose Birch kraft Tar O pulp 5HMF OH HO

O OH Dehydration O OH O Cellulose OH OH Glucose HO OH + O OH OH H3C

HO OH O H 2 Fructose Levulinic acid Formic acid

OH OH OH HO

OH OH Sorbitol Figure 1. Reaction network in hydrolytic hydrogenation of bleached birch kraft pulp.

78 SORPTION ACTIVITY OF CARBOHYDRATE FRACTIONS OF WATER-HYACINTH

E.N. Kalmykova1, S.A. Vuai2, S. Begum2, A.A. Gorbatovskyi3, J.J. Makangara2 1 - Department of Chemistry, Lipetsk State Technical University, Lipetsk, Russia; School of Natural Sciences, The University of Dodoma, Tanzania 2 - School of Natural Sciences, The University of Dodoma, Tanzania 3 - School of Natural Sciences, The University of Dodoma, Tanzania; St. Petersburg State Technical University of Refrigeration and Food Technologies, Saint Petersburg, Russia [email protected]

The water hyacinth (Eichhornia crassipes) is known as the noxious weed in the rivers and lakes. The rapid growth of this plant allows using it as a source of raw material for obtaining forage for cattle, manufacturing paper and pressed boards, isolation of different biologically active substances (fermentable sugars and polysaccharides which can be used as biosorbents). This work is devoted to the investigation of the sorption activity of polysaccharides isolated from the flowers, leaves, roots and stalk of the plant collected in equatorial of Lake Victoria (Tanzania). For obtaining the target polysaccharide the crushed mass of each part of plant was frozen and pretreated by ethanol for removing lipids, pigments and other low-molecular substances. The insoluble residue obtained after filtration was treated by water extragents of different composition (diluted water solutions of sodium chloride and acetic acid). The influence of various conditions (nature and concentration of the water-salt and acidic solutions, temperature and duration of extraction) for effectiveness of isolation, purification procedures and yield of carbohydrate fractions were investigated. Water-soluble proteins were removed after addition of 96% water-ethanol solution to concentrated polysaccharide fraction followed by precipitation. Low-molecular admixtures were removed by dialysis against distilled water. The following fractions of neutral and acidic polysaccharides were obtained: warm and hot sodium chloride-extracts (w-NaCl and h-NaCl), warm and hot water-acetic acid (w-Aс and h-Ac), respectively. The yield of polysaccharide fractions varied in the range from 0.7 up to 2 g (0.7 ÷ 2.1 % to defatted homogenate), maximal yield was estimated for polysaccharides of roots and stalks. Neutral sugars (glucose, galactose, mannose) and acidic sugars (glucuronic, galacturonic acids) were identified by paper chromatography in hydrolyzates of each fraction. All polysaccharides isolated were tested on effectiveness of sorption of Pb+2 ions in water solutions using quartz crystal microbalance sensor by “dip and dry” detection. Resonators of AT – cut, 9 MHz resonance frequency, diameters of silver electrodes are 5 mm; CAS “ETNA”, Russia were used as detectors of measurement of sorption activity of thin films formed of the surface of electrode of resonator. Each polysaccharide investigated was immobilized (as a thin film) on the electrodes using technology cross-linking with water-formaldehyde solution. The process of polysaccharide-film formation was controlled by quartz crystal microbalance method. The influence of concentration of polysaccharide solution was investigated and it was estimated optimal concentration is 1.5 % for both (neutral and acidic) polysaccharides. The sorption activity of polysaccharide fractions was tested using diluted solutions Pb(NO3)2 with the same concentration (0.03 М). It was estimated that all fractions obtained are characterized by high sorption activity of Pb+2 ions in the range 0.5 - 18.5 μg/ml and 0.5 - 25 μg/ml for neutral and acidic polysaccharides respectively. The acidic polysaccharide isolated by using hot acetic acid is characterized by highest activity. The means of maximal specific sorption (m∞) of thin polysaccharide layer corresponds to 5 ±0,5μg per each μg of the film. Thus, it is shown that all polysaccharides can be used as additions in food-stuffs and biosorbents for removing cations of Pb+2 from the organism, and the best conditions for obtaining the most active polysaccharide biosorbents (h-Ac) are acidic extraction of roots and stalks at hot temperature.

79 EXTRACTION OF HYPERICIN FROM A HYPERICUM PERFORATUM L. HERB

H.G. Karankevitch, A.A. Ahabalajeu, O.P. Popova, Z.I. Kuvaeva Institute of physical organic chemistry of the National academy of sciences of Belarus, Minsk, Belarus [email protected]

St. John's wort (Hypericum perforatum L.) – is a perennial plant; a representative of a kind St. John's wort of family Hypericaceae. It was widespread in Eurasia. One of the most valuable components of a St. John's wort herb is derivative of anthracene hypericin. Hypericin improves a functional condition of the central and vegetative nervous system. It has an antidepressive effect, moderately expressed sedative effect, antiviral and antineoplastic activity. OH O OH In this research were studied methods of preparation of extracts by water- alcohol solution from a Hypericum perforatum L., containing the greatest possible quantity of hypericin. H3C OH Research of extraction of hypericin from percentage of ethanol in

H3C OH extractant has shown that the maximum extraction of hypericin from a St. John's wort herb reaches at use of 70 %-s' solutions of ethanol. It is characteristic for extraction many substances from raw materials, and, as

OH O OH a rule, speaks that at increase in concentration of ethanol the target substance has been extractioned better, but at a time at the big Fig.1 Hypericin concentration of alcohol there is a denaturation of proteins from a substratum of raw materials that hinders an increasing of containing of these substances in extract. It is shown that extraction degree of hypericin from time (τ) increases and reach a plateau at τ = 60 minutes. It is established presence of positive correlation between temperature of extractions process and extraction of hypericin, however temperature influence on extraction is insignificant. It is studied influence of microwave radiation on hypericin extraction. It is shown, that influence of microwave radiation on extractions system allows to reach considerable of extraction of hypericin. The microwave extraction becomes a perspective method of extraction of hypericin from a St. John's wort herb due to smaller time expenses (less than 60 seconds). The maximum extraction of hypericin at microwave extraction is also observed at using of 70% solutions of ethanol. However at using more volumes of extractant the difference in extraction of hypericin for aqueous-alcoholic solutions with the various content of ethanol is leveled. Thus, on the basis of the received data it is possible to conclude that on hypericin extraction from a St. John's wort herb influence the ethanol content in exstractant, process temperature, volume of extractant, influence of microwave radiation. Most full hypericin it is taken by 70 % solutions of ethanol. The increasing of temperature influences positively on extraction of hypericin from a St. John's wort herb. The extraction at microwave radiation influence allows to reach higher values of concentration of hypericin and allows to intensify process of extraction essentially.

LEVELS OF SOME TRACE ELEMENTS IN SEA GRASS ZOSTERA MARINA L. LAKE KARAKOL (KAZAKHSTAN)

M. Yu. Karapun Astrakhan State Technical University, Russia [email protected]

Hydrophytes – are plants that have adapted to live completely submerged in water, such as marine eelgrass (Zostera marina). A small family of Zosteraceae, whose representatives are often called "sea grass", belongs to a very interesting biological group of flowering plants adapted to living in salt water oceans and seas.

80 Productive capacity of sea grasses is extremely high, and their communities are among the most productive autotrophic communities of the world, including agricultural. So, for a year Zostera marina forms 0,3 - 0,6 kg/m2 dry weight (excluding production of roots). From the seagrass family of Zosteraceae (Zostera asiatica Miki syn. Z. pacifica auct., Z. marina L., Z. noltii Hormen syn. Z. nana Roth, species of the genus Phyllospadix Hook.) in the present moment is developed the technology of pectin (polysaccharide compounds), known as zosterin (Kiesewetter et al, 1981). Zosterin a unique low-methoxylated pectin. An important feature of pectin is its high adsorptive properties and the possibility of prolonged use. Framework of the zosterina molecule is a linear chain of α-1,4-linked residues of D- galacturonic acid (Miheyskaya et al, 1971). In contrast to pectin, a part of zosterina is a rare monosaccharide D-apiose. The total amount of carbohydrates in the sea grass Zostera marina in April 2010 was in the range 59.71 - 63.08%, they were (for the maximum value): monosaccharide -10.88%, a disaccharide – 9.35% and polysaccharide – 42.85%, respectively. The content of chlorophyll in the sea grass Zostera marina from Lake Karakol was 0,11%. Content in April 2010, nickel in sea grass Zostera marina was 3,20±0,62 mg/kg dry weight, compared with August 2009, where the concentration of this microelement was 30,49± 9,17 mg/kg dry weight, indicating that the decrease in 9,5times. And the content of other less important biophyllic elements such as iron, was 119.97± 4.96 mg/kg dry weight, compared with August 2009, where the concentration was in the range 157.12±7.40 mg/kg, respectively.

120

100

60 mg/kg 40

0 Ni Fe Hg Zn

Fig. 1. Levels of some trace elements in sea grass Zostera marina.

Content of toxic elements such as mercury was at 0.01575±0.00125 mg/kg. In addition, the concentration of important trace elements such as selenium was 427 mg/kg.

Literature:

1. Kiesewetter I.V., Suhoveeva M.V. Shmelkova L.P. Harvesting algae and grasses Far Eastern seas. Moscow: Light and Food Promst. 1981. S. 113. 2. Miheyskaya L.V., Ovodova R.G., Ovodov Y.S. Pectic substances of sea grasses. VI. Investigation of degraded zosterina / / Chemistry of Natural Compounds. 1971. № 3. S. 246-249.

81 PHENOL COMPOUNDS OF WATER-ALKALINE EXTRACT OBTAINED FROM NORWAY SPRUCE GREEN NEEDLES

E.S. Kayan, V.I. Roshchin The St.Petersburg Forest Technical Academy, Department of Wood Chemistry and Forest Chemical Products, Saint- Petersburg, Russia [email protected]

Water-petrol extraction in apparatus of sprinkle-dephlegmation type has received wide acceptance. Despite many advantages of the technology it has a number of serious disadvantages: high power consumption, insufficient degree of extractives output, prices rising for carbon hydride solvents. All mentioned above proves that it is a topical and pressing task to elaborate resources saving technologies with the use of more effective extragents and extraction equipment. One of the possible variants of green needle (GN) processing can be spruce GN processing in rotor- pulsing apparatus (RPA). We examined the composition of extractives (EC) obtained from Norway spruce (Picea abies) with the help of alkaline water solution (1 % NaOH). The obtained water-alkaline extractives were processed in series with petroleum ether (PE) and butyl acetate (BA). The substances obtained with BA were extracted with diethyl ether (DE). Substances soluble in DE were divided into phenol acids (53.9 %, treatment with NaHCO3), phenols (21.2 %, treatment with NaOH) and neutral substances (18.9 %). The group of phenol compounds was chromatographied on a column with silica gel and PE with increasing DE addition was used as an eluent. There were obtained 10 fractions. Individual compounds were released by repeat chromatography of fractions as well as recrystallization method. The extracted compounds were identified with the help of spectral analysis methods and method of chromatomass-spectrometry. As a result there were identified more than 20 compounds. Among the compounds of phenol substances group n-hydroxy-acetophenone is the main one (35.5%). The rest compounds are contained in much smaller quantity: 4-hydroxy-3-methoxyacetophenone (18.7%), vanillin (1.3 %), matairesinol (2.7 %). Besides the compounds mentioned above there was released umbelliferone (0.2 %), (there is one report on its extraction from Norway spruce green needles) as well as raspberry cetone (4-(4- hydroxyphenyl) butane-2-on 0.25 % and 4-(3-hydroxy butyl) phenol (1.1 %) (we found no information on these compounds extraction from Norway spruce in literature).

SYNTHESIS AND IN VITRO STUDY INFLUENCE ON THE PRODUCTION OF NITROGEN MONOXIDE AND ON THE ARGINASE ACTIVITY IN ACTIVATED MACROPHAGES OF CONJUGATES OF LUPANE TRITERPENOIDS WITH CHROMANE ANTIOXIDANTS

R.R. Khalitova1, A.Yu. Spivak1, Yu.P. Belskii2, A.N. Ivanova2, V.N. Odinokov1 1 - Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, Russian Federation 2 - Research Institute for Pharmacology, Siberian Branch of the Russian Academy of Medical Sciences, Tomsk, Russian Federation [email protected]

In the last decade, active research has been undertaken to find medicinal agents based on native substances that can inhibit the production of nitrogen monoxide. In this respect, lupane triterpenoids and some of their synthetic derivatives are very promising. We assumed that synthetic combinations of betulin, betulinic acid, or betulonic acid with antioxidant molecules containing the pharmacophore chromane fragment of -tocopherol will help to discover novel broad-spectrum compounds with NO-modulating and antiradical activities.

82 In the present work, we obtained a number of hybrid compounds of betulin and betulinic and betulonic acids with pharmacologically significant analogs of a-tocopherol (a water-soluble metabolite of α-tocopherol - α-CEHC, the accessible hydrophilic antioxidant - Trolox acid and α- tocopheryloxyacetic acid) via the formation of acyl bond or via the linkers (the residues of succinic acid, hydrazine and tetramethylenediamine) and studied in vitro the influence of the hybrid compounds on the NO production stimulated by lipopolysaccharides (LPS) and on the activity of arginase in mouse peritoneal macrophages. We also estimated their cytotoxic effects.

Molecular fragments Hybrid compounds

O O HO OH C H 16 33 HO O O 30' O 20' 29' O 19' 21' 12' 13 22' I 25' 18' HO O 11' 26' 17' 28' OH 9' 5 14' 16' (CH2) NH2 HO 4a 15' N n 6 4 O 1' O O H 3 2' 10' 8' 7 2 3' 7' 27' 1 O 4' 6' 8a O 5' n = 0, 4 8 O O 23 24 II

HO OH O O NHNH O ()n OH O O O O n = 1, 2 III O OH NHNH OH O O O R 2 O 1 IV R HO

OH R1+R2=O; R1=H, R2=OH; R1=H, R2=OAc O O H O HO O O

OH C H O O 16 33 V

Showing low cytotoxicity, some of them suppress nitrogen monoxide production without affecting the activity of arginase, which suggests their antiinflammatory and immunomodulating properties that is effective to cure various autoimmune diseases. This work was financially supported by the Russian Foundation for Basic Research (Project No. 10- 03-00105), the Division of Chemistry and and President of Bashkortostan Republic of Russia (grant No 28 (10.03.2011)).

DITERPENIC RESIN ACIDS IN THE SYNTHESIS OF CHIRAL LIGANDS FOR CATALYSTS OF ASYMMETRIC REACTIONS

T.B. Khlebnikova, V.N. Konev, D.Yu. Yushchenko, Z.P. Pai Boreskov Institute of Catalysis [email protected]

The large-tonnage by-products of arboreal plant processing contains numerous constituents of complex structure that can serve as convenient starting materials for production of a whole series of substances with predetermined physicochemical properties and bioactivity. At present the potentialities of utilization of resin acids, which are the main constituent of galipots and colophonies, are far from exhausting. The use of natural terpenes as convenient chiral pools for the synthesis of optically active compounds is the prospective approach to the creation of wide

83 spectrum of available chiral ligands for the catalysts of asymmetric reactions, highly effective drugs and chiral reagents. As a result of our investigation of the resin acids chemistry we have developed the efficient synthetic routes of stereoselective functionalization of optically pure available natural products – levopimaric and abietic acids.

H H NH2 PPh * 2 * NH PPh2 H 2 H CO2H Levopimaric CO Me CH2R acid 2 R = CH2NHBn, NO

H H N X H H C N OH NH OH NHR NH N OH NH OH H H H C NHR CO2CH3 X CO2CH3 CO2CH3 X=O, S

On the basis of stereospecific transformations of levopimaric acid adducts with fumaric acid and maleic anhydride a series of optically pure diastereoisomeric P-, N- containing terpenoids were prepared. Using the dehydroabietic acid a series of nitrogen derivatives was synthesized. The optically pure tricyclic diterpene derivatives – chiral mono- and diamines, azomethines, ureas and thioureas, phosphines and phosphinites were produced. Complexes of the synthesized P-, N- donor chiral ligands with Rh(I), Ru(II) and V(IV) were prepared and used as catalysts of asymmetric reactions.

The work is supported by RAS Program of basic researches, project N 5.7.3

ORGKHIM BIOCHEMICAL HOLDING: LEADING RUSSIAN PINE CHEMICAL MARKET

N. Khodov, A. Kuimov, A. Radbil ORGKHIM Biochemical Holding, Nizhny Novgorod (Russia) [email protected]

Established in 2001, Orgkhim Biochemical Holding is a relatively new, yet already a successful and reputable business with a turnover exceeding RUB 3 bln that ranks it as the leader of Russian pine chemical industry. Over RUB 830 mln were spent on capex during the last two years only. Today ORGKHIM is: – main supplier of pine chemical-based emulsifiers and initiators of polymerization reactions polymerization reactions, selling over 47 000 tons of products per year to Russian synthetic rubber makers;

84 – unique Russian and second worldwide process developer and producer of safe petroleum-based extender oils for rubber and rubber compounds with current annual capacity of 65 000 tons in Russia that are planned for increase up to 145 000 tons per year; – largest producer of resins for Russian tire industry, supplying over 3000 tons per year; – unique Russian producer of pine oil and α-terpineol from turpentine with the existing capacity over 2 000 tons per year for which a ramp up to 4 000 tons per year is planned. Our mission resides in sustainable business growth, dynamic development and release of high- quality, eco-friendly products of ‘green’ chemistry at the world-class level, using renewable natural sources to protect the environment and the community in general. We set a marketing strategy to sell over 70% of products to producers of synthetic rubber and other polymers, yet keeping a balanced mix of petrochemical and pine chemical products. One of the core drivers to our business efficiency is creation and industrialization of innovative science and application developments that respond to modern engineering, business and environmental challenges. This is the reason why we established our Scientific and Research Center with high-qualified experts achieving at the top quality level the goals defined by the market environment. At the same time we proceed with win-win cooperation with various business players and organizations on a whole number of issues and tasks requiring joint efforts. Such comprehensive approach is the only way for us to meet the targets set, remaining the leader of pine chemical industry over the last years. We are open to a meaningful dialogue and cooperation. We strongly believe in potential of basic and applied sciences and are welcoming any contribution to national and global industrial potential.

RADIOLYTIC CONVERSION OF BIOPOLYMERS: LIGNINE, CELLULOSE AND CHITINE

E.M. Kholodkova, P.K. Metreveli, A.K. Metreveli, V.S. Erasov, A.V. Bludenko, V.N. Chulkov, A.V. Ponomarev Frumkin Institute of Physical Chemistry, Moscow, Russia [email protected]

Renewable biopolymers of a vegetative and animal origin are considered as key raw materials for chemistry and fuel energetics of the future. The additional impulse to studying of biopolymers is caused by the initiation of the researches connected with development of third generation biofuels synthesized by live organisms. Cellulose, lignine and chitine belong to the most widespread biopolymers of a natural origin. In the present work an influence of dose rate P (in a range 0.2-4.0 kGy/s) on yields and composition of products of electron-beam distillation of cellulose, lignine and chitine for the first time is investigated. Also comparative studies are carried out at a mode of post-radiation pyrogenic distillation (in a dose range 0-3 MGy). It is shown that effective electron-beam distillation of samples is observed at Р above 1 kGy/s. The maximum yield of destruction and distillation exceeds 15 mol/J, testifying about the chain mechanism of transformations. At Р = 1.5-2.5 kGy/s a yield of liquid organic compounds from cellulose, chitin and lignine reaches 60 %, 45 % and 40 wt %, accordingly. The condensates which are distilled off from lignine and chitine consist of two phases - brown viscous tar and more light water-organic solution. Dose rate decrease is accompanied by reduction of a yield both liquid and gaseous products of radiolysis. The fraction of organic products in condensate is shrinking. At Р  0.5 kGy/s water (both intermolecular, and an intramolecular origin) dominates in condensates. This mode of an irradiation is interesting in respect of selective dehydration of biopolymers. It gives possibility to remove water in advance to receive anhydrous organic mixes at higher dose rates. At post-radiation distillation of chitin the tar yield fell with dose growth. The preliminary irradiation of lignine did not change a yield of distilled off tar but increased the alkoxyphenols fraction in it. It is shown that the mode of post-radiation pyrogenic distillation gives low molecular weight organic products much less than in a mode of electron-beam distillation.

85 REACTIVITY OF POLY-, DI- AND MONOSACCHARIDE IN HYDROLYSIS REACTION IN SUBCRITICAL WATER

A.G. Khudoshin1, V.V. Lunin1, V.I. Bogdan2 1 - Department of Chemistry Lomonosov Moscow State University 2 - N.D.Zelinsky Institute of Organic Chemistry RAS [email protected]

As our fossil raw materials are irrevocably decreasing and as the pressure on our environment is building up, the progressive changeover of chemical industry to renewable feedstocks for their raw materials emerges as an inevitable necessity. Components of biomass such as lignin and cellulose are considered as basic renewable feedstock. Cellulose, the principle structural component of plants, is the most abundant organic compound on earth. It is a biopolymer that consists of glucose units joined by β-(1-4) linkages. This bond, by itself, is not partially strong, as it can be readily hydrolyzed by simple acids such as HCl or by cellulolytic enzymes. Investigation of cellulose hydrolysis reaction is of great interest. The products of the hydrolysis such as oligosaccharides, glucose, fructose, furfural can be used in foodstuff, medical supplies, etc manufacture. Thus far, a great deal of effort has been put toward the degradation of cellulose with enzymes, sulfuric acid, and hydrothermal methods. The enzymatic processes and the sulfuric acid processes have significant drawbacks such as separation of products and catalysts, and severe controls of enzymes and waste fluids. On the other hand, subcritical water (SCW) is environmentally friendly solvent and catalyst for the hydrolysis reaction due to intensification of dissociation of water at high temperatures and pressures. During hydrothermal treatment not only depolymerization of cellulose but isomerization, dehydration and retroaldol condensation of monosaccharides can proceed. The problem of selective production of valuable substances from cellulose should be solved relying on kinetic data of the degradation reactions of poly-, di- and monosaccharide. In present work the subcritical water treatment of compounds modeling cellulose and products of cellulose hydrolysis is investigated. Carboxymethylcellulose sodium salt (CMC) is used as water soluble analogue of cellulose. Glucose, fructose, sucrose represents mono- and disaccharides. Subcritical water treatement is conducted in flow reactor at temperature 120-320°C and pressure up to 90 atm. Study of the kinetics of CMC degradation carried out by measuring of intrinsic viscosity of polymer solution. The viscosity-average molecular weight was determined using the Mark–Houwink equation. Mathematical model describing changes of molecular weight from temperature and reaction time of SCW treatment is proposed. Kinetics of glucose, fructose, sucrose decomposition studied by determine its concentration by HPLC after the reaction. Activation energy of the hydrolysis processes is stated.

PHYSICAL-MECHANICAL PROPERTIES OF NATURAL FIBER FILLED RIGID POLYURETHANE FOAM OBTAINED USING TALL OIL AS AN ENVIRONMENTALLY SOUND RAW MATERIAL

M. Kirpluks, U. Cabulis, U. Stirna, A. Fridrihsone LS IWC, Polymer laboratory, Riga, Latvia [email protected]

Hydroxyl-containing substances are available in nature in great quantities. This makes them a very promising raw material for the polyurethane industry, which looks for incorporating renewable materials into their products. This paper discusses the studies performed by LS IWC in the framework of the EU 7th FP project FORBIOPLAST into the use of tall oil as a renewable resource in rigid polyurethane (PUR) foam production [1].

86 Tall oil is a by-product of cellulose production - so it is a very cheap raw material for developing new materials. A technology of the synthesis of polyols with the hydroxyl value 200-360 mg KOH/g from different grade tall oil by way of esterification or amidization has been developed. Polyols synthesized from tall oil are suitable for developing polyurethane foam systems; these systems can be classified as “green” products containing up to 25% renewable materials. Polymer materials can be filled with different fibers to alter their physical-mechanical properties. Using natural fibers, it is possible to increase the renewable material’s content in the developed materials up to 35%. In the framework of this project, wood, cellulose and flax natural fibers were used. Wood fibers were supplied by the company LaSole, and different cellulose fibers - by the company Rettenmaier. Carbon fibers from TOHO Tenax were used for comparison. PUR foams with three different densities were developed in the framework of this project. PUR foams with the density 30 kg/m3 can be used as a thermal insulation material in refrigerators and freezers, and other types of containers that require a low thermal conductivity. PUR foams with the density 45 kg/m3 can be used as a thermal and sound insulation material in the automotive industry. PUR foams with the density 220 kg/m3 can be used in the automotive industry for manufacturing parts that are not produced in large quantities, thereby saving costs on expensive injection moulds. All three types of PUR foams were filled with the above-mentioned fibers, and physical and mechanical characteristics, as well as closed cell content were tested. PUR foam morphology and fiber dispersion were evaluated by SEM. Because water can influence the polyurethane material’s properties, the moisture of fibers was established and its influence on the developed materials determined. It has been found that, using natural fibers only in high density PUR foams, it is possible to increase compression strength up to 50% from the initial foam composition [2]. This paper describes innovative rigid polyurethane foam systems obtained from tall oil polyols. The obtained foams have an excellent insulation performance, thus helping the appliance and automotive industry meet energy targets, while offering cost effective solutions by providing low raw material cost, adequate physical and mechanical characteristics, and low applied density using environmentally friendly blowing agents [3].

The research leading to these results has received funding from the EC 7th FP project FORBIOPLAST under grant agreement n° KBBE-212239 (www.forbioplast.eu).

References: 1. U.Stirna, U.Cabulis, M.Kirpluks. Influence of resin acid content in tall oil esters on thermal characteristics and flammability of polyurethane foams. Proceedings BPS 2009, Ventspils, Latvia, p. 95. 2. U.Cabulis, M.Kirpluks, A.Lazzeri. Tall oil (liquid rosin) as source for PUR and PIR foams. Bio plastics Magazine, 2011, Vol. 6, p.42-43. 3. V.Parenti, H.Kramer, K.G.Park. Development and application of high energy efficient polyurethane systems for the domestic appliance industry. Int. Conf. UTECH 2009, Maastricht, The Netherlands.

THE APPLICABILITY OF THEORETICAL IDEAS OF ORGANIC CHEMISTRY TO THE ALKALINE WOOD DELIGNIFICATION

M.F. Kiryushina, T.G. Fedulina, M.Ya. Zarubin Saint-Petersburg State Forest Technical Academy, Chemical Technology and Biotechnology Department, Saint Petersburg, Russia [email protected]

The results of investigation of the interactions of wood components with cooking liquors during alkaline pulping are presented. A well-known Clopman principles about electron donor and electron acceptor (acid-base) interactions in electrophilic and nucleophilic reactions were taken as a basis /1, 2/. The pulpings were carried out at the different regimes (time, temperature and pressure) with use

87 of the monomeric and dimeric with β-either bond lignin model compounds, of the isolated from wood samples of lignin and polysaccarides and of wood samples. It is established that the the charge-controlled reactions give the largest contribution to the lignin degradation because the successful delignification is not occurred in the absence of sodium hydroxide. It is shown the appreciable contribution of the orbital-controlled reactions to the cleavage of β-either bonds in lignin. This reflects on the increase of the degree and the rate of wood delignification in the presence of nucleophilic reagents – bases (sulphide, iodide and thiocyanide anions). It is determined also the considerable contribution of solvation interactions during alkaline pulping. This is confirmed by the very rapid rate of the cleavage of β-either bonds in lignin and glycosidic bonds in wood polysaccharides in the presence of high basic organic solvents (dioxane, DMSO), well mixed with water. The rate of the above mentioned reactions may be regulated by the change of cooking regimes and the chemical reactivity of the components of pulping solutions on the addition of organic solvents and certain reagents. The obtained experimental results allow to draw a conclusion that the electron donor and electron acceptor interactions of wood with pulping solutions predominate in the complex process of alkaline delignification.

References 1. Reactivity and ways of reactions. Ed. G. Clopman. Moscow, 1977. 2. J.March. Advanced Organic Chemistry. Reactions, Mechanisms and Structure. 6th Edition. Eds.J.March, M.Smith. M., 2007.

THE DYNAMICS OF FLAVONOIDS ACCUMULATION IN POTENTILLA ALBA L. ONTOGENESIS IN THE CONDITIONS OF THE REPUBLIC OF BELARUS

M.V. Kitaeva Central Botanical Garden of the NAS of Belarus, biochemistry and biotechnology of plant, Minsk, Belarus [email protected]

Potentilla alba L. is a deciduous, medicinal, perennial herb, which is mainly extended in temperate, arctic and Alpine zones of the Northern hemisphere. The greater part of taxon Potentilla L. is characterized by high quantity of flavonoids, in particular flavonols. According to articles the flavonoids content in P. alba L. is no less 1,8%. Flavonoids have numerous important functions. For example they are powerful antioxidant and scanvengers of free radicals. Besides flavonoids are known to reduce risks of cardiovascular diseases. We are analyzed the dynamics of flavonoids accumulation on the main phenophases of ontogenesis. It was determined by the necessity of new remedy and biological active substances sources search in Belarus. Plants of P. alba L. were gathered at the main phenophases of its development, by cultivation in the Сentral Botanical Garden NAS’s experimental field in 2010. All parts of P. alba L. were cleaned, roots were washed and dried by the thin layers protection. Dried plant material was kept in paper containers. Prior to the experiment the material was cut and pulverized to the extent of 100- 250 mkm. The quantitative determination of flavonoids in terms of rutin in the overground and underground parts of in the ontogenesis P. alba L. was measured using the spectrophotometric method (complex flavonoids- AlCl3 (30 g/l). Conditions of flovonoids extraction: extraction agents - 40% C2H5OH, ratio plant raw material: extraction agents 1:30, time extraction 45 min., temperature 85-90◦C. Optical density was measured at 412 nm. All experiments were carried out three independent determinations. Differences were considered to be significant at P < 0.05. The results obtained using method of spectrophotometry assay are shown in Figure 1. The maximum values are illustrated below: 88

Further studies permit to value biosynthesis potential of P.alba L.

EVALUATION OF IMMUNOTROPIC GLUCONATE TRANSITION METALS IN VITRO AND IN VIVO

O.A. Knyazeva1, I.G. Konkina2, A.V. Knyazev3, Yu.I. Murinov2 1 - Bashkir State Medical University, Ufa, Russia 2 - Institute of Organic Chemistry, USC RAS, Ufa, Russia 3 - Institute Biochemistry and Genetics, USC RAS, Ufa, Russia [email protected]

Gluconic acid is a monobasic penta-hydroxy acid, which can be obtained by enzymatic oxidation of glucose with glucose oxydase. Glucose is widely used in medicine as a universal detoxicant. Currently gluconic acid acquires an independent significance with many applications. It is well known that gluconate metals are correctors of a number of pathological states, and also that coordination compounds of transition elements are able to produce both immunomodulatory and cytotoxic effects. In connection with the recorded annual growth of number of cases of various forms of carcinogenesis, it seems very important to search for such compounds, which both produce antitumor activity and have immunotropic properties. According to many authors, this is due to the fact that those anticancer drugs applied inhibit to a certain degree the body's own immune system thus reducing its resistance against the emerging pathological processes, including neoplastic ones. Thus, a vicious circle is formed. In this regard, we have synthesized a series of complex compounds of 3d-elements- Mn (II), Co (II), Fe (II), Cu (II). Zn (II) with gluconic acid [2]. The choice of 3d- elements was determined in particular by the fact that in various pathological conditions, including the tumor process, its pronounced imbalance is observed. The study of these compounds requires careful analysis, as gluconic acid, being a polyhydroxy acid has in its molecule not only a carboxyl group, but also several potential donor centers in the form of the oxygen atoms of five hydroxy- groups. Involvement in the coordination bond of different donor atoms may lead to the formation of compounds of different composition and structure. The study of their cytotoxic activity in vitro (on K562 cells) showed that all compounds in varying degrees, exhibit cytotoxic activity - from mild to severe (8-14% live cells). It should be noted that a distinguishing feature of this cell line is the lack of tumor supressive p 53 protein - the main inducer of apoptosis when DNA is damaged, thus they are relatively resistant to the known anti-tumor agents. The in vivo study of immunomodulatory actions demonstrated a significant increase in the level of IgG for a number of compounds, which is more than 100% as compared with the respective level in the group of untreated animals. The antitumor activity was demonstrated in vivo in BALB/c mice with mouse mielome compared with

89 cytostatic cyclophosphane. Inhibition of ascites growth as well as increased longevity of animals were recorded. In addition, for the first time there was discovered the effect of leveling the conformational forms of C3 (H2O) in the process of spontaneous hydrolysis of C3 complement component under the influence of these compounds in the venous blood of patients diagnosed with breast cancer and diffuse mastopathy in comparison with healthy individuals. And we identified a correlation between the change in the level of C3(H2O) and the content of tumor marker CA-125 [1] made it possible to use the value of this index as an assessment criterion of effectiveness and impact study of the reactants. Thus, on the basis of these results, and given that the reduction of C3 correlates with immune disorders, cancer concurrent diseases, we may confirm the corrective effect of gluconate 3d-metals on the immune system.

Literature 1. Knyazeva, O.A., Sakaeva D.D., Kamilov F.H., Vakhitov V.A. The relationship between the change under the influence of chemotherapy, the level of C3 (H2O) of the complement and tumor- associated antigen Ca-125 in blood plasma of patients with ovarian cancer // Questions of oncology. - 2007. - T. 46, № 6. - S. 696-698. 2. Konkina, I.G., Ivanov S.P., Knyazeva O.A. and all. Physico-chemical properties and pharmacological activity of gluconate Mn (II), Fe (II), Co (II), Cu (II) and Zn (II) // Pharmaceutical Chemistry Journal - 2002. - V.36, № 1. - p.18-21.

BIOCHEMICAL MECHANISMS OF INFLUENCE OF ESSENTIAL OILS OF PLANTS ON TUMOR CELL GROWTH

O.A. Knyazeva1, I.G. Konkina2, A.I. Urazaeva1, A.V. Knyazev3 1 - Bashkir State Medical University, Ufa, Russia 2 - Institute of Organic Chemistry, USC RAS, Ufa, Russia 3 - Institute Biochemistry and Genetics, USC RAS, Ufa, Russia [email protected]

Essential oils of plants are reffered to natural substances which, taken in minimal doses, provide a corrective effect on the immune system. Most of them are terpenoids - linalool (3,7-dimetil-1 ,6- oktadien-3-OL) and linalilatsetat (1,5-dimetil-1-vinil-4-heksenilacetat). Immunomodulating effect and antitumor activity were observed for both plant terpenoids and essential oils. For example, the antitumor effect was observed for limonene (terpenoid - metyl-4-isopropenyl cyclohexene), the essential oils of clove, lavender, sage [2, 4], eucalyptus [3]. However, the mechanisms of their effects are not fully disclosed and require further research. The purpose of this work is to compare and analyze the nervous, endocrine and immune systems with the development of tumor in mice in a state of depression. It was found that mice of BALB/c in the doldrums on the background of aromatherapy (ART) with the use of essential oils of Eucalyptus globules, Lavandula vera and Salvia sclaria showed normalization of the central nervous system, registered in the tests of "open field" and "forced swimming: an increase in horizontal motor activity equaled to 53,5%, vertical - to 43,4% of orienting-exploratory activity - to 28,5%, reduction of emotional reaction to 31%. Simultaneously, the level of the stress hormone cortisol decreased by 40%, and immunoglobulin G, in contrast, rose by 43%. Also we observed the correction of level of the conformational forms of complement component C3 - C3 (H2O), which, as it had been shown previously [1], correlates with the content opuholassotsiirovannogo marker CA-125, which gives grounds for its use as an assessment criterion of effectiveness and impact of drugs. Depression produced a stimulating effect on tumor development reflected in the increase of ascites by 32,4%, which is probably related to the regulation of cortisol gene expression of the susceptibility to cancer. On the background of ART, on the contrary, we observed inhibition of ascites - an average of 54% and an increase in the lifespan of mice by 318,5% (p <0,05). 40% of

90 surviving animals remained healthy for 6 months, and later in the year no pathological abnormalities were observed. Thus, the results indicate that being used in the mode of ART, essential oils by influencing the nervous, endocrine and immune systems, trigger the mechanism of inhibition of tumor cell growth, induced by depression.

Literature 1. Knyazeva O.A., Sakaeva D.D., Kamilov F.H., Vakhitov V.A. The relationship between the change under the influence of chemotherapy, the level of C3 (H2O) of the complement and tumor- associated antigen Ca-125 in blood plasma of patients with ovarian cancer // Questions of oncology. - 2007. - T. 46, № 6. - S. 696-698. 2. Knyazeva O.A., Konkina I.G., Knyazev A.V., Smolihina T.I. Influence of aromatherapy on the antitumor activity and the spontaneous hydrolysis of C3 complement component / Pharmacy. - 2010. - № 7. - S. 42-45. 3. Soldatenko S.S. Essential oils - recommendations for use. [Electronic resource] / SS Soldatenko - 2010. - // Http://pro-krasoty.panweb.com/biblioteka/efirmasla [date accessed: June 15, 2010]. 4. Chiss V.I., Starinskiy V.V., Aleksandrov, L.N. [Etc. The main results of completed in 2003, research conducted by industry program "Development of high-tech methods of prevention, diagnosis and treatment, improve the efficiency of medical and social rehabilitation and quality of life of cancer patients' // Russian Journal of Cancer. - 2004. - № 6. - S. 42-46.

OILSEED PRODUCTION FOR BIODIESEL AND COPPER PHYTOEXTRACTION USING MUTANT LINES OF SUNFLOWER

A.P. Kolbas1, M. Mench1, L. Marchand1, R. Herzig2, E. Nehnevajova3 1 - UMR BIOGECO INRA 1202 Ecology of Communities Bat, Talence, France 2 - Phytotech Foundation Quartiergasse, Berne, Switzerland 3 - Institute of Biology, Applied Genetics Free University of Berlin, Berlin, Germany [email protected]

Two mutant lines and commercial cultivars of sunflower (Helianthus annuus L.) were cultivated in 2008 and 2009 on Cu-contaminated soils in field plots at a former wood preservation site (the BIOGECO phytoremediation platform). Incorporation of compost and dolomitic limestone reduced root exposure to Cu and promoted plant growth. Phenotypic traits and shoot Cu removal depended on sunflower type and Cu exposure. At low total soil Cu (200-400 mg kg-1), shoot Cu mineral mass peaked using commercial cultivars, i.e. Salut, Energic, and Countri. Based on shoot yield (7 Mg DW ha-1) and Cu concentration, the highest removal was 59 g Cu ha-1. At high total soil Cu (700- 1200 mg kg-1), shoot Cu mineral mass peaked for mutants (e.g. 52 g Cu ha-1 for Mutant line 1) and cultivars Energic and Countri. Energic seed yield (3.9 Mg DW ha-1) would be relevant to produce oil. The Cu accumulation in plant parts decreased as follows: roots > leaves > stem > capitulum > seeds. Using Mutant line 1 and the fading technique, the phenotypic responses depended on total soil Cu, and pH and Cu2+ in soil pore water, but not on DOM. Some commercial cultivars and mutant lines can be included in a crop rotation to both produce oilseed and long-term phytomanage Cu-contaminated soils. Based on 295 € Mg-1, the payback from sunflower seed production would range between 220 (high total soil Cu) and 877 (low total soil Cu) € ha-1 with the effective Energic cultivar and 154 € ha-1 with the mutant lines at high total soil Cu. We assumed several negative effects: a cluster effect, i.e. competition and shading affected the morphological traits of mutants in 2008, impact of drought due to the vicinity of poplar roots from adjacent plots in 2009, and decreased Cu-binding properties of the compost-treated soil. Further experiences are needed to determine the influence of these factors as well the role of endophytes in Cu uptake and removal. Plant performances and phytoextraction efficiency are discussed in the perspective of the sustainable phytomanagement of Cu-contaminated soils.

Acknowledgements This work was supported by ADEME, Dept. Polluted Soils and Sites, Angers, France and EU Erasmus mondus lot 6 external window.

ANTHOCYANINS AND ANTIOXIDANT CAPACITY OF BLACKBERRY

N. Kolbas1, M. Monteiro De Araujo silva2, P.-L. Teissedre2 1 - Brest State University named after A.S. Pushkin, Department of Chemistry, Brest, Belarus 2 - Institute of Vine and Wine Sciences of Bordeaux, UMR 1219 OEnology, Bordeaux, France [email protected]

Over the last years considerable interest has been developed in fruits containing high concentrations of anthocyanins due to their potential biological and health-promoting effects, such as reduction of coronary heart disease, improved visual acuity and anticancer activities (1). Their biological effect is determined mainly by their high antioxidant potential (2). Anthocyanins represent one of the most widely distributed classes of flavonoids present in most of fruits of European origin. In addition, anthocyanins are used as natural and safe to human health colorants. Thus, detection and accurate measurement of anthocyanins in plant material is important for their further application. This study is focused on identification of anthocyanins, estimation of their total content in blackberry as well as on the evaluation of fruit antioxidant activity. Berries of three species (Rubus fruticosus L., Rubus caesius L. and Rubus nessensis W.Hall.) were harvested at commercial maturity stage, lyophilized and grounded. Then the total anthocyanins (TA) were multiple extracted with 1% HCl in methanol using Extractor Dionex ASE-350. Identification of anthocyanins of fruits was performed by HPLC-MS analysis. The mobile phase was composed by solvent A (0.1% aqueous formic acid), solvent B (5% formic acid in acetonitrile) and detection was at 520 nm. Analyses utilized the positive ion modes. Samples were analyzed in the mass spectrometer using full-scan data-dependent MS scanning from m/z 100 to 1000. Antioxidant capacity of blackberry fruits have been tested by ABTS radical scavenging capacity assay (3). A total of 15 anthocyanins were detected and identified. The aglycon forms were represented by four anthocyanidins: cyanidin, delphinidin, petunidin and malvidin. The prevalent sugar moieties were glucose, galactose, arabinose, rutinosе and sambubiose. Cyanidin 3-O-galactoside was the major anthocyanin in the fruits R. caesius and R. nessensis (56.65 and 88.32% respectively); сyanidin 3-O-glucoside was the major anthocyanin in the fruits R. fruticosus (85.27%). Significant differences between the qualitative composition of anthocyanins have been detected in examined fruits. Anthocyanins can be used as biomarkers for species identification in the genus Rubus characterized by high polymorphism. TA ranged (in mg сyanidin 3-O-glucoside per 100 g of fresh weight) from 405.76 to 538.48 and decreased in follows: R. caesius R. nessensis R. fruticosus (p<0.001). Mean values of antioxidant capacity varied (in mmol Trolox equivalent per 100 g of fresh weight) between 6.23- 8.17 in following order: R. fruticosus R. nessensis R. caesius (p<0.001). Correlation between TA and antioxidant activity by ABTS method has not been determined. The results are important from the perspective of utilization in species determination and in practice where the treated fruits might be potential sources of higher antioxidant content due to the higher amount of pigments in the food, pharmaceutical and cosmetics industries.

1. De Pascual-Teresa, S.; Sanchez-Ballesta, M. T. Anthocyanins: From plant to health. Phytochemical Reviews, 2008, 7, 281–299. 2. Kähkönen, М.Р.; Heinonen, М. Antioxidant Activity of Anthocyanins and Their Aglycons J. Agric. Food Chem., 2003, 51 (3), 628–633. 3. Re, R.; Pellegrini, N.; Proteggente, A.; Pannala, A.; Yang, M.; Rice-Evans, C. Antioxidant activity applying an improved ABTS radical cation decolorization assay. Free Radical Biol. Med. 1999, 26, 1231–1237.

92 DETERMINATION OF NATURAL POLYPHENOL CONTENT IN PLANT EXTRACTS AND SYNTHESIS DYES FOR TEXTILE FIBERS ON THE THEIRS BASIS

O.A. Kolpachova, K.I. Kobrakov, G.A. Tselikova Moscow State Textile University, Russia [email protected]

Formerly the сhair of organic and dye chemistry conducted experiments to obtain azoic dyes for different fibers based on polyphenols (flavonoids) extracted from plant materials. The results showed that maximum flavonoid mass extraction had been obtained by means of hydro-ethanolic solution in water-bath. Quercetin, being the most wide-spread and cheapest reagent, had been chosen as a dummy compound to test the nitro-linking. Then this method has been applied to the extracts of Urtica Dioica, Rumex crispus and other plants. The method was aimed at complete linking until the results of R-salt test gave positive reply. The resultant dye showed stabile melting temperature and color characteristics. However the suggested method didn't allow carrying out for selective reaction, as the exact flavonoid content in extracts remained unknown. Therefore we present the method of total flavonoid determination. One is based on the spectrophotometric evaluation of a complex with AlCl3 after acid hydrolysis of the glycosides Two grams (exact shot) of dried and reduced material were put into the round-bottom flask. Then 50 ml of 70% ethanol were added and water-boiled for 45 minutes. The extract was then poured into 100 ml measuring cup. Filtration residue press cake was again bathed with 50 ml of ethanol and water-boiled for another 45 min. 2 ml extract of analysis sample was then placed into 50 ml measuring cup, adjoined by 2 ml 2% aluminium chloride solution and 0,5 mi 30% acetic acid and made up to the volume with ethanol. It was sustained for 30 minutes and after that optical density had been measured with the wave-length of 390 nm. Flavonoid sum content was determined by the following formula:

m D 25 50 X  2 1 D2  m1 50 50 

In which D1 is the optical density of the solution in question; m1 is the shot mass of plant material; m2 is the shot mass of standard rutin sample; D2 is the optical density of standard sample complex of rutin aluminium chloride. After the exact content of flavonoids in the solution had been determined, the coupling reaction had been conducted according to this data. The research on the structure and properties of resultant materials is being conducted.

SELECTIVE AEROBIC OXIDATION OF (BIO)ETHANOL OVER SOLID CATALYSTS

K.Yu. Koltunov1, V.I. Sobolev2 1 - Boreskov Institute of Catalysis and Novosibirsk State University, Novosibirsk, Russia 2 - Boreskov Institute of Catalysis, Novosibirsk, Russia [email protected]

Many of the catalytic systems are successfully used in variety of selective oxidative reactions utilizing molecular oxygen (air) as cheap and clean oxidant [1]. In this connection it should be emphasized the growing importance of biomass-derived alcohols and especially bioethanol as a renewable chemical feedstock to produce useful oxidation products, such as aldehydes, carboxylic acids and corresponding co-products (acetales, esters) [2]. In our presentation we report the results on the comparative study of catalytic activity of a variety of solid catalysts (V2O5-TiO2, V-Mo-Te- Ox, V-Mo-Nb-Ox, V-Mo-Te-Nb-Ox, K-Ni-Co-Fe-Bi-P-Mo-Ox/SiO2, Au-TiO2, Au-SiO2, Au-Al2O3) 93 in the gas phase oxidation of ethanol. The efficiency of these catalysts is estimated by means of temperature programmed experiments in a single pass flow reactor system, operating at atmospheric pressure. It is shown that the catalytic performance strongly depends on the reaction conditions, i.e. the nature of catalyst, the temperature of reaction and the contact time. A highly-selective partial oxidation of ethanol into a desirable product, one among 1,1-diethoxyethane (A), acetaldehyde (B, yield>90%), acetic acid (C, yield >90%) and ethyl acetate (D) is achieved.

O2 OEt EtOH H3C CH3CHO CH3COOH CH3COOEt Cat. OEt ABC D

A long-range aim of the work is to disclose general patterns of the reactivity of alcohols on the catalyst surface and to recognize the mechanism of the oxidation and the concurrent reactions. We also hope that from a practical viewpoint our results will prove useful for further expanding the utility of solid catalysts in greener oxidation reactions.

References [1] G. Centi, F. Cavani, F. Trifiro, in Selective Oxidation by Heterogeneous Catalysis, Kluwer Academic/Plenum Publishers, New York, 2001. [2] a) T. Mallat, A. Baiker, Chem. Rev. 2004, 104, 3037–3058; b) B. Jørgensen, S. B. Kristensen, A. J. Kunov-Kruse, R. Fehrmann, C. H. Christensen, A. Riisager, Top Catal., 2009, 52, 253–257, and references cited therein.

INVESTIGATION OF EQUILIBRIUM IN AQUEOUS SOLUTIONS OF 3-METHYL-1,2- CYCLOPENTANEDIONE

I.G. Konkina, Yu.I. Murinov Laboratory of coordination Chemistry Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Russia [email protected]

As is generally known, 3-methyl-1,2-cyclopentanedione (MCPD) was first extracted from wood thermolysis products, but afterwards was found in other herb substances, e.g. in extracts of coffee corns where the quantity of MCPD multiplies with increasing the temperature of frying [1]. At present this compound is a substance claimed by manufacturing food, pharmaceutical, tobacco and cosmetic products. However its physical and chemical properties have not been studied sufficiently. Besides, a number of authors consider MCPD to be a carbocyclic analogue of ascorbic acid, so deeper understanding its properties is of scientific interest for studying mechanisms of biochemical processes. MCPD is a cyclic α-diketon which possesses a potential ability to exist in three tautomeric forms: diketon, mono- and dienol. Most published data confirms the presence of MCPD in aqueous solutions and nonpolar solvents in the form of monoenol, but there is guidance and education dienol. In addition, in aqueous solutions MCPD can occur processes of the ionization. In this research have been investigation the processes of equilibrium in aqueous solutions MCPD spectrophotometrically. There were used MCPD (from Aldrich), NaOH of highest purity, newly refined twice redistillate Н2О released from СО2. The solutions were used in concentrations of мol·l-1. The рН measurement was carried out with the use of рН-meter ОР 264/1 5٠10-3 («Radelkis») with accuracy of 0,01un. рН, a combined glass electrode of ОР 0808 type was used. Constant temperature with accuracy of 0,1°С was kept up by MLW U4 liquid thermostat. Absorption spectra were registered by Specord M40 spectrophotometer («Carl Zeiss Jena»). The absorption band of the monoenol form of MCPD, whose existence was confirmed by 1Н и 13С NMR spectroscopy data was observed at 257 nm (ε=8160). With рН increasing there occurs a batochromic shift of this band. When рН values equals 12, the absorption peak is observed at 292 94 nm. According to NMR spectroscopy MCPD is present as an ionized hydroxyl group monoenol form in this solution. Based on data from the UV spectra obtained at different pH values was carried out determination of equilibrium constants MCPD in water and the thermodynamic characteristics of this process. Calculations were performed using the method described in [2]. Thermodynamic parameters were obtained using the temperature dependence of equilibrium constants. Judging by the values of the constants obtained Ка, the equilibrium is shifted towards the formation of the protonated form of monoenol. As the temperature grows the equilibrium constant lowers,: + + + рКа=8,83 0.41(298 K); 9,07 0.24(323 K); 9,27 0.11(343 K). The coefficient of correlation of -1 dependence рКа versus Т equals to 0,997. The calculated thermodynamic parameters ΔG, ΔH and ΔS have the following values (respectively): 6,05 kJ·мol-1; -3,60 kJ·мol-1, and -32,4 J·мol-1·K-1.

1. I. Flament, Y. Bessiere-Thomson. Coffee flavor Chemistry. U.K: John Wiley & Sons. 2002.410p. 2. A. Albert, E. Sergent. Ionization constants of acids and bases. M,: IL. 1964. 180 p.

THE PROBLEMS OF CHEMISTRY OF NATURAL COMPOUNDS, BIOORGANIC AND BIOMOLECULAR CHEMISTRY, AND MEDICINAL CHEMISTRY IN RUSSIAN CHEMICAL BULLETIN

G.N. Konnova Zelinsky Institute of Organic Chemistry RAS, Editorial office, Moscow, Russia [email protected]

Russian Chemical Bulletin is International Edition of a prominent Russian Journal Izvestiya Akademii Nauk. Seriya Khimicheskaya. It was founded in 1936 and has been published in English since 1952. The year 2011 marks the 75th anniversary of the Journal. During these years, the Journal has become one of the leading Russian periodicals in chemistry. Russian-language version is published by the Russian Academy of Sciences, while the English-language version is published by Springer. The Editorial Board of the journal includes prominent chemical scientists, in particular, thirteen full members and ten corresponding members of the RAS. The foundation in 1995 of the International Advisory Board with participation of renowned chemical scientists from various countries including three Nobel Prize winners in chemistry also contributed to the high scientific level and international prestige of the journal. Since 1993, the journal has published papers presenting the results of original studies as full papers, brief communications, and letters to the Editor, but also analytical reviews, in particular, authors’ reviews and predictive analytical papers on topical issues of the chemical science. During this period, the volume of the journal increased more than 1.5-fold, which considerably shortened the publication time and made it possible to extend the journal coverage, first of all, by including papers in Chemistry of Natural Compounds, Bioorganic and Biomolecular Chemistry, Medicinal Chemistry, Supramolecular Chemistry, Polymer Chemistry, Nanochemistry, Materials Chemistry, and interdisciplinary articles. Besides ordinary issues, containing materials on different areas of chemical science, specialised issues are regularly published (for example, see issues 7, 2002, 1, 12 2010 and 4 2011, containing materials on Bioorganic and Biomolecular Chemistry, and Medicinal Chemistry). In 2010, more than 350 papers from 100 scientific centres of the Russian Federation and 30 scientific centres from the former USSR and other foreign countries were published. In recent years, the Journal has become widely known in Russia and abroad. The journal is abstracted and indexed in the following base dates: RZhKhimiya, Chemical Abstracts, Chemical Titles, Current Contents/Physical, Chemical and Earth Sciences, Reaction Citation Index, Science Citation Index, Science Citation Index Expanded, The ISI Alerting Services, Chemistry Citation Index, and Energy Research Abstracts. Information about the Journal and the publications is available at the websites of the Journal (www.russchembull.ru) and Springer (www.springerlink.com). The electronic versions of the journal are available online for subscribers. Since 2005, all papers published in English starting with the first journal issue, which appeared in 1952, are available in the electronic library of Springer. In terms of the number of downloads of the 95 full texts of online articles, Russian Chemical Bulletin has the highest score among Russian journals, markedly exceeding the average level (more than 1000 downloads per day on average, Information about the journal is available at www.springer.com/11172), which attests to the high need for the Journal. In addition, subscription for the online version markedly increased. Several hundreds of both individual institutions and large consortia combining many institutions have subscribed for the Journal, which made the access to the Journal global.

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UTILIZATION OF BIODIESEL PRODUCTION BYPRODUCT BY NOCARDIA VACINII K-8

A.D. Konon, N.A. Grytsenko, A.P. Sofilkanych, O.O. Borovyk, T.P. Pyrog National University Food Technologies, Kyiv, Ukraine [email protected]

Biofuels, such as ethanol and biodiesel, are among the most promising sources for the substitution of fossil fuels. Biodiesel can replace petroleum diesel, as it is produced from animal fats and vegetable oils, which generate about 10% (w/w) glycerol as the main byproduct. The excess glycerol generated may become an environmental problem, since it cannot be disposed of in the environment. Due to its ample occurrence in nature, many known microorganisms can naturally utilize glycerol as a sole carbon and energy source. These microorganisms have attracted attention to the potential use in bioconversion of abundant glycerol produced from biodiesel. Glycerol may substitute traditional carbohydrates, such as sucrose, glucose and starch, in some industrial fermentation processes. It can be used for production of practically useful metabolites such as microbial surfactants. Biosurfactants can be used in biological remediation, which is economically and politically attractive and has shown promising results in the treatment of soil and water contaminated with organic compounds. In previous researches oil oxidizing bacteria from oil polluted samples of soil and water were isolated and identified as Nocardia vaccinii K-8. It was determined that strain K-8 was able to produce surface-active substances on nutrient media with glycerol. This media was optimized with the help of math methods of experiment planning. The aim of present work is to investigate the possibility of intensification of surfactant synthesis on glycerol, and also the influence of microbial surfactant on the oil biodestruction. At the first we determined that the highest increasing of surfactant synthesis was obtained after addition of citrate (0.3-0.5 %) at the beginning of station growth phase while growing on the media with glycerol (1.5 % w/w). These results are 10-25% higher that on the media without organic acid. The chemical compose of biosurfactants was obtained with the use of method of TLC (thin layer chromatography), and were the complex of neutral, glyco- and aminolipids. That’s why citrate (regulator of lipid synthesis) and fumarate (precursor of gluconeogenesis) were used together (0.2 %) as the biosynthesis precursors and the surfactant concentration increased for 40%. It was shown that surfactant preparations (cultural liquid and supernatant) and cells of N. vacinii K- 8 can be used for oil polluted water remediation. The highest level of oil destruction was obtained after treatment with the Nocardia cells suspension (9.8107 CFU/ml): 95-98 % after 20 days.

96 So presented results show the possibility of effective utilization of glycerol (the byproduct of biodiesel production) with the synthesis of useful metabolites with surface-active properties, that can be used in environmental remediation technologies.

STUDY OF HYDROXYCINNAMIC ACID CONTENT IN FRUITS OF JAPAN QUINCE (CHAENOMELES LINDL.)

E.Yu. Konovalova, T.V. Dzhan, S.V. Klimenko Kyiv Medical University of Ukrainian Association of Folk Medicine [email protected]

Hydroxycinnamic acids in various combinations, in free form or in the form of glycosides, found in all higher plants. The most widespread in nature are caffeic acid and its derivatives (chlorogenic acid and its isomers). Hydroxycinnamic acids exhibit antioxidant and antiradical properties in tests in vitro. It is also described their immunostimulatory, antiviral and anti-inflammatory activity. Chlorogenic acid has been proven in animal studies in vitro to inhibit the hydrolysis of the enzyme glucose-6-phosphatase in an irreversible fashion. This mechanism allows chlorogenic acid to reduce hepatic glycogenolysis (transformation of glycogen into glucose) and to reduce the absorption of new glucose. In addition, in vivo studies on animal subjects have demonstrated that the administration of chlorogenic acid lessens the hyperglycemic peak resulting from the glycogenolysis brought about by the administering of glucagon, a hyperglycemiant hormone. The studies also confirmed a reduction in blood glucose levels and an increase in the intrahepatic concentrations of glucose-6-phosphate and of glycogen. Chlorogenic acid is marketed under the tradename Svetol in Norway and the United Kingdom as a food active ingredient used in coffee, chewing gum, and mints to promote weight reduction. Accumulation of hydroxycinnamic acids in the process of fruits ripening to determine the terms of fruits of Japan quince harvesting has been studied. The object of the study were fruits of Ch. speciosa (Sweet) Nakai, sorts “Nivalis” and “Simoni”, introduced in the M.M.Gryshko National Botanical Garden of the National Academy of Sciences of Ukraine (NBG) and Japan quince sorts bred in the Department of plant acclimation of NBG: Ch. japonica (Thunb.) Lindl. ex Spach. sort "Jan", a hybrid of Ch. japonica (Thunb.) Lindl. ex Spach and Ch. speciosa (Sweet) Nakai sort "Holiday" and Ch. superba (Frahm) Rehd. sort "Amphora". Japan quince fruits were collected in August and September. Study of hydroxycinnamic acids content conducted by high performance liquid chromatography (HPLC) and spectrophotometric method according to procedure described in European and Ukrainian Pharmacopoeia. The percent of total hydroxycinnamic acid content was calculated and expressed as chlorogenic acid. HPLC analysis revealed that the fruits of Japan quince contain chlorogenic acid free and contain no caffeic and p-coumaric acids. The highest content of free chlorogenic acid is defined for Ch. superba (Frahm) Rehd. sort "Amphora" - 0.137%, the lowest - for Ch. speciosa (Sweet) Nakai sort "Nivalis" - 0,008%. At the same time, the fruits of Ch. speciosa (Sweet) Nakai sort "Simoni" contain up to 6 times higher content of free chlorogenic acid than the fruits of “Nivalis” sort. It is obvious that the content of chlorogenic acid does not depend on the type of Japan quince, and depends on the terms of fruits ripening, as "Nivalis" sort refers to sorts with early maturing fruit. The total content of hydroxycinnamic acids in the process of fruit ripening of Japan quince decreases in fruits of all sorts, except of "Simoni" sort fruits, where, obviously, phase of fruits growth is still in September month. The highest total content of hydroxycinnamic acids, as well as free chlorogenic acid is defined for fruits of Ch. superba (Frahm) Rehd. sort "Amphora» - 3.99 ± 0,07% in calculation on chlorogenic acid. It is interesting to note that a similar total content of hydroxycinnamic acids - 3.93 ± 0,08% - is typical for fruits of Ch. speciosa (Sweet) Nakai sort "Nivalis" having the lowest content of free chlorogenic acid. Obviously, in the process of maturation the binding of free chlorogenic acid in esters takes place. 97 Thus, the accumulation of hydroxycinnamic acids in Japan quince fruits depends on the stage of plant vegetation and is maximal in the phase of un-ripe fruits. Therefore, Japan quince fruits harvesting should be conducted at the stage of late growth and early ripening.

THE EXTRACTS OF CONIFERS BARKS AS BASE THE ECOLOGICALLY PURE WOOD ADHESIVES

G.N. Konovalova, I.R. Serdobintseva, L.A. Tamm St. - Petersburg State Technological University of Plant Polymers [email protected]

Wood adhesives from renewable raw materials have been a topic of considerable interest for many years. The extraction of polyphenols (mainly condensed tannin or polyflavonoids) from a waste product of the food industry, such as Pinus Silvestris, Picea abies and Larix sibirica L. bark, was examined with the aim of analyzing the potential of the extracts for the formulation of wood adhesives. In this work, barks of 20, 40 and 80 years old pine together with barks of 40 and 50 years old spruce and bark of an 80 years old larch were extracted by NaOH water solutions within 1 hour at 100oC. The experiments were planned according to a 22 factorial design to analyze the influence of a ratio of bark to liquor and NaOH concentrations on the yield of extractive substances and impact on different extract properties: Stiasny number (tannin/soluble solids ratio), tannins and sugars contents and tannin mass isolated by acid addition. The extractions were performed on various conditions (a ratio of bark to liquor - 7, 10, 13 and NaOH сconcentration - 1, 2, 3%). Within the scope of operating conditions, extraction yields were in the range 36-70% together with extract Stiasny numbers in the range 25-62% depending on the age and the tree species of the bark examples which were used. The bark sample of 20 years old pine gave the highest yield (nearly 70%) followed by barks of a 40 years old pine and an 80 years old larch. On the other hand, the bark samples of an 80 years old pine and 40 and 50 years old spruce provided sufficiently good extractives yields (more 50%). The extracts quality is determined as approximate amounts of polyflavonoids and characterized with Stiasny value. The highest Stiasny values (more 60) refer to the extracts of an 80 years old pine, 40 and 50 years old spruces and an 80 years old larch obtained at mild and highest conditions of processing. These extracts can be use for adhesives formulation. The extracts of barks of the 20 and 40 years old pine have tannin/soluble solids ratio smaller then 0.33. They could not be used directly for the formulation of wood adhesives. In this case the tannin could be isolated by acid addition. The experimental design performed demonstrated the capacity of Pinus Silvestris, Picea abies and Larix sibirica bark extracts for the applications proposed and allowed selecting the optimal extraction conditions to obtain not only high quality extracts but high extraction yields too.

CELLULOSE MATERIALS WITH HYDRAZONE AND AZOHYDRAZONE GROUPS FOR CONCENTRATION OF HEAVY METALS

D.N. Konshina, V.V. Konshin, E.Yu. Artem’eva Kuban State University, Krasnodar, Russia [email protected]

The products of cellulose oxidation, for instance dialdehyde and aldehyde cellulose, can be used as convenient raw materials for creating matters with a number of useful properties. Formazan- celluloses, which are used as reactive indicator papers, were developed on the basis of the oxidation products of cellulose and put into practice. Methods of obtaining a number of derivatives of aldehyde and dialdehyde cellulose containing hydrazone and azohydrazone groups were worked. Appropriate thiosemicarbazones

98 guanilhydrazones of cellulose were obtained by condensation of dialdehyde or aldehyde cellulose with aminoguanidine or thiosemicarbazide. Processing of guanilhydrazones of cellulose by 5-diazo-1,2,3,4-tetrazolyl and 3-diazo-1H-1,2,4- triazolyl chloride allows to receive materials containing the guanazyl and azohydrazone fragments. The structure of obtained materials was confirmed by elemental analysis and infrared spectroscopy. Adoption efficiency of obtained materials in the form of microcrystalline powders or papers for the sorption extraction of some heavy metals was shown. The extraction conditions of Cu2 +, Co2 +, Cd2 + and Hg2 + were optimized in static and dynamic modes. The prospects of using the obtained materials for the concentration of heavy metals were emphasized in a wide pH range. The combined schemes of natural water analysis were developed with using the obtained materials. These schemes include the preconcentration of Co2 +, Cd2 + and Hg2 + with the subsequent registration of the analytical signal in sorbent phase or solution after ashing the solid concentrate.

This work was supported by Grant President RF MK-2665.2011.3

USING NANOCRYSTALLINE CELLULOSE FOR ADHESIVE REINFORCEMENT

S.A. Konstantinova1, A.N. Korotkov2, A.I. Remezov3, L.S. Galbraikh2, I.V. Voskoboinokov1 1 - Federal State Unitary Enterprise «State Scientific Centre of Timberindustry Complex» 2 - Moscow State Textile University named by A.N. Kosigin 3 - Cherepovets Plywood and Furniture Plant [email protected]

Cellulose is the most abundant natural polymer and contains both amorphous and crystalline structure. Nanocrystalline cellulose (NCC) is a typically a rigid rod-shaped monocrystalline domain (whisker) with 1-100 nm in diameter and tens to hundred of nanometers in length. NCC has a highly crystalline structure, a very large aspect ratio (around 70), a high surface area (ca. 150m2/g), very high tensile strength and Young’s modulus therefore can be used for many applications as a reinforcing filler for different kind of compositions. Adhesive bounding is one of the key steps in wood industry. The stability of adhesive bounds is of vital importance to the performance of almost all products. In the present study there was the novel attempt to exploit the reinforcing potential of NCC to improve the mechanical properties of wood adhesive bounds. Since carbamide-formaldehyde (CF) - adhesives are a widely used class of low- prized wood adhesives, this study focused mainly on the reinforcement of CF-adhesive bonds. NCC was obtained in Laboratory of free radical and radiation-chemical processes (prof. Mikhailov A.I.), at Institute of Problems of Chemical Physics, RAS, Chernogolovka city. For the preparation of NCC were used commercial MCC by treated with a 10% H2SO4, 1% H2O2 solution at 90-950C for 1 h under mechanical stirring (MCC content about 20wt %), after radiation- chemical modification (20Mrad, Co60) of the raw material. Then suspension was washed until neutrality by successive centrifugation at 6 000 rpm for 10 min each step and dialyzed against distilled water, in the sequence, whereupon treated MCC was disintegrated mechanically by means of ultrasonic treatment 1,5 kW for 60 min. A field emission scanning electron microscope (FESEM), model LEO SUPRA 25 with accelerating voltage of 13,4kV was used to check nanocrystalls dimension. This procedure leads to the formation of 2 fraction of NCC with the following parameters: 1) narrow size distribution of nanoparticles: diameter ranging about 25-50 nm, length about 100- 300nm; 2) with a broad distribution of nanoparticle diameters ranging from about 25-200nm, length about 100-700nm. Received second fraction of NCC was used for a partial replacement of toxic carbamide- formaldehyde resin, as a binding agent in the plywood manufacture. The mechanical performance of plywood samples at imitation of various environmental influences (dry and wet) was investigated in Cherepovets Plywood and Furniture Plant.

99 Based on the results of testing according to DIN EN 310:1993-08, DIN EN 314-1:2005-03 by using universal machine for testing materials - Z010 it was established that shear strength of plywood specimens, made with CF-bounded adhesive increased about 5%, the Young’s modulus by 10-15% due to incorporation of 2,5% per weight of nanocrystalline cellulose (Figure 1). Obtained data indicate that NCC as a part of widely used a CF-adhesive composition significantly improves the physical-mechanical performance of plywood. Follow-up experiments will focus on the modification of plywood by CF-bounded adhesive with narrow size distribution NCC particles.

ISOLATION OF BETULIN FROM BIRCH BARK WITH THE USE OF ULTRASOUND

E.N. Koptelova, N.A. Kutakova, S.I. Tretyakov Northem (Arctic) Federal University [email protected]

Birch bark is a source of various extractives. The outer bark from various birch species is the richest in extractive substances; in its extracts the dominating substances are pentacyclic triterpenoids with the lupane skeleton , the main representative of which is betulin. The content of betulin in the outer bark is from 10 to 40% by weight on the initial anhydrous substance, depending on the type of birch, place and conditions of its growth, tree age, etc [1]. Betulin has antiviral, antitumor and antiseptic properties, and shows antioxidant activity. Thus, the availability and biological activity of betulin bring it into the line of valuable natural compounds. The generally accepted way of isolation of the betulin from birch bark is its extraction with the organic solvents. Scientists in the Institute of Chemistry and Chemical Technology, SB RAS, B.N. Kuznetsov and others [2] proposed a preliminary process of bark activation by «exploding autohydrolysis», which allows to extract up to 34% of betulin by weight on the initial anhydrous substance. The disadvantage of this method is its technological complexity connected with the use of high pressure and high temperature for producing superheated steam. If the shock-acoustic activation is used, there forms a homogeneous mass intractable to filtration and precipitated betulin is mudded with alkali that is difficult to separate. Information about the commercial application of this method is not available. Ultrasound extraction is the competitive way of bark activation in comparison to the use of «exploding autohydrolysis». Ultrasound exertion creates cavitation and sinuous flows in the extractant, resulting in the rapid inturgescence of the material, increase in the rate of particle flow, turbulent and eddy flows in the conterminal layer. Molecular diffusion within the particles of the material and the conterminal diffusion layer is almost replaced by the convective one which leads to the intensification of mass transfer [3]. We studied the effect of the extraction method on the rate of the recovery of extractives. Betulin extraction with organic solvents was carried out by infusion in the boiling temperatures of the Figure 1. Dependence of the mechanical stress on solvent or deflegmation in a Soxhlet apparatus. the flexural strain. Plywood samples prepared using 86-95% ethanol was used as the solvent. A CF-adhesive composition modified by 2,5% of NCC. technique of rapid determination of botulin concentration in spirits was worked out. Extraction was carried out in a laboratory ultrasonic apparatus. Oscillatory system provided the introduction of 22 kHz ultrasonic vibration to the work media. The electronic generator was characterized by the consumed power of 140 W. After 3 hours the outcome of betulin from birch bark birch Betula pendula Roth (fractions size 3,5-4 mm), using the method of infusion with a batchwise change of the solvent was 25.4% by weight on the initial anhydrous substance, with deflegmation method — 28,3% with infusion and ultrasound 100 — 29,2%. Thus, the use of ultrasound can increase the outcome of betulin. The rate of the substance transition from the solid phase into solution depends on the rate of penetration of liquid into a solid phase, the rate of diffusion in a liquid and the rate of removal of material from the interfacial area. All these stages are intensified by the influence of the ultrasonic field. The research of kinetics of ultrasonic extraction, the search for optimal conditions for carrying out the process and its implementation into production is currently being held.

References 1. Kislitsyn, A.N. Extractives of birch bark: isolation, composition, application — A.N. Kislitsyn, Timber chemistry - № 3, 1994, pp.3 — 28. 2. Levdansky, VA Integrated processing of the bark using extraction and explosive autohydrolysis Levdansky VA — Krasnoyarsk, 2006. 3. Molchanov G.I. Ultrasound in pharmacy. — M., Science 1980.

COMPARATIVE DETERMINATION OF THE CALORIFIC VALUES OF WOOD PYROLISATES BY EXPERIMENTAL AND COMPUTATIONAL METHODS

D.Y. Kormilkina, A.A. Spitsyn, D.A. Ponomarev St.Petersburg State Forest Technical academy, St.Petersburg, Russia [email protected]

There are several ways of using energy from wood such as the various types of pyrolysis, thermal liquefaction and the direct burning. The first two processes are interesting because they allow to obtain a liquid fuel easy both in transportation and storage. Despite the simplicity and the accessibility of the calorimetric determination of calorific value of liquid fuels, in some studies it is still usual to apply the computational methods to determinate the calorific value of substances proposed as a fuel. Therefore, it has become interesting to compare the results of determination of fuel calorific values using the computational and experimental methods. The industrial sample of the tar obtained by pyrolysis of birch wood was taken for the study. The light fraction was preliminary removed from the sample by a rotary evaporator under mild vacuum. Then the residue was subjected to vacuum distillation at pressure less than 1 Torr and heating up to 250°C to take away as much liquid products as possible. The latter then was named as summary oils (Sample 1) and the residue after distillation is called pitch (Sample 2). Then the chemical composition of these samples was determined. Necessary data for other samples were taken from literature sources. Experimentally calorific value of the samples was determined by calorimetric combustion. Determination of calorific values by estimation was based on the chemical composition of the sample, and calculated with empirical formulas of Dulong and Mendeleev. Mendeleev formula: Q = 81 · C + 300 · H - 26 · O, kcal / kg Dulong formula: Q = 81.4 · C + 342 · (H - O / 8) + 25 · S - 6 · (9 · H + W), kcal / kg Where C, H, S, O – amount of carbon, hydrogen, sulfur, oxygen in fuel given in % W - moisture content of fuel, %

101 The calculated and experimental data and the chemical composition of the samples are presented in the Table. Calorific value (HHV) of the experimental and computational methods Chemical composition of the sample, % Calorific value kJ/kg Exp Mendeleev Dulong С H O S N Ash 1. Sample 1 28100 23200 20500 58.4 5.79 35.81 - - - 2. Sample 2 27300 26800 24700 66.75 5.72 27.53 - - - 3. Redwood 29100 27800 26500 75.6 3.3 18.4 0.2 0.2 2.3 charcoal 4. Ensyn 23100 22900 20100 56.4 6.2 37.1 <0.01 0.2 0.1 5. Dynamotive 17800 19100 15300 43.21 7.73 48.8 0.03 0.14 0.09

It is noteworthy that there is a discrepancy between the calculated and experimental data, which achieve in some cases more than 25%. The best calculated values give the Mendeleev formula. The obtained discrepancy can be explained by an incomplete view of product moisture and other factors. Authors gratefully acknowledge the support of Russian Foundation of Basic Research Grant 10-03- 92500 and Civilian Research Development Foundation Grant RUC1-2989-ST-10.

RECEPTION OF A POWDERY POLYMALT EXTRACT WITH APPLICATION OF NONCONVENTIONAL GRAIN RAW MATERIALS

E.A. Korotkikh, S.V. Vostrikov, I.V. Novikova Voronezh State Technological Academy, Fermentation and Winemaking Technology Department, Voronezh, Russia [email protected]

The malt extracts have obtained a world recognition as the dietary products. They are applied in beer, bakery, confectionery, non-alcoholic and others food-processing industries, and also used as independent products of a special purpose for people with the weakened immunity. Food and biological value of the malt extracts directly depends on the raw materials used by their manufacture. The buckwheat malt is one of nonconventional and perspective sources of raw materials for reception of extracts. Buckwheat grain is a dietary product with high biological value, because the malting process increases its functional properties due to the synthesis of antioxidants, in particular routine and ascorbic acid. The work purpose is reception of a powdery polymalt extract (PME) from the undried malts of barley, buckwheat, peas. The basic stages of its manufacture are: malts reception of barley, buckwheat, peas; preparation of the malts for the mashing; the mashing; the filtration of the wort; the concentration of wort in the vacuum-evaporating device; drying in the pulverized dryer; packing in the tight container. The samples of brewing barley "Skarlett" (Standard documentation 5060-86), buckwheats "Dikul" – (Standard documentation 19 092-92), peas "Leader" (Standard documentation 28674 – 90) last year yield which has been grown up in the Voronezh region are used. Malting of barley, peas are spent on schemes accepted in the malting industry. Malting of the buckwheats is carried out according to the technological modes picked up by us earlier. Recommended time of soaking is 30-35 hours, the optimum degree of soaking is 42-44 %, the general duration of malting is 6 days at temperature 16 °С. The maximum of the enzymes amilose activity in the «green» buckwheat malt was 264 units of W-K. The mashing is carried out by the infusion way, with the smooth rise of mash temperature and its keeping at isothermal optimum for the corresponding enzymes. The wort for reception PME is prepared from the mix of specified «green» crushing malts in weight parity 1:1:1 with the hydromodule 1:5. The further process is conducted under the following step schedule: 102 The temperature, oC: 42-45, 52-55, 63, 70-72 Duration, min: 40-45, 40-45, 60, to full saccharification Further the wort was warmed up till 76-78 оС and transferred for filtering. The filtered wort with containing 12-14 % of solids substances (SS) is concentrated up to 30-35 % SS at the temperature 50 оС which provides the maximum preservation of a primary parity of the mash components, and also biologically active substances: vitamins, enzymes, phytohormones and other biostimulators. Drying of concentrated wort in the pulverized dryer to relative humidity 2-2,5 % is carried out. The received product possesses of the raised food and biological value and can be recommended for reception of functional soft drinks.

NEW METHODS FOR THE PRODUCTION AND PURIFICATION OF BIOLOGICALLY ACTIVE COMPOUNDS BASED ON ANTHRAQUINONES

D.Y. Korulkin, N.A. Vereschagin al-Farabi Kazakh National University [email protected]

Recently, the effectiveness of the substances used was reduced, due to the habituation of the organism and the various mutations of viruses and bacteria that become not sensitive to the antiviral and antibacterial priparatam. On this front of us particularly sensitive question arose about the search for new substances with different activity. One of the first objectives of our research is the search for new antiviral drugs based on anthraquinone skeleton. For the starting material was passed alizarin, which has its own nefroliticheskuyu activity. The advantage of this material is the ability to selectively carry out a variety of substitution reactions of the hydroxyl groups. To create a compound having antiviral activity was proposed to replace the hydroxyl groups by different amino acid type. As these amino acids were selected glutamic and aspartic acid. The replacement was in excess amino acids for a disubstituted product. Substitution produced an N-terminal group. The reaction was conducted among 25% of ammonia for the ionization of hydroxyl groups and to achieve complete dissolution of alizarin, the solubility of amino acids while also increasing, putting them in salt form. Used as the catalyst aluminum chloride, which directs the replacement of only the N-terminal group. ОН

ОН + О О О

О О HN ОН О ОН H2N HN ОН ОН ОН

О О ОН О 1,2-dioxianthraquinone Glutamic 1,2-N-diglutamilanthraquinone (alizarin) acid ОН ОН + О О О

О HN ОН О ОН О ОН HN ОН ОН H N 2 О

ОН О О О 1,2-dioxianthraquinone Aspartic 1,2-N-diaspartilanthraquinone (alizarin) acid

103 After the reaction, neutralize the solution with concentrated hydrochloric acid to weak acid. As a result, there was loss of red-brown amorphous residue, which in consequence subjected to filtration and drying. For the purification of the sediment used the difference in the solubility of the source and received by the agents. As you know, alizarin slightly soluble in water. On the contrary, the resulting compound, and the original amino acids are highly soluble. Purification was performed by dissolving a mixture of substances, and further separation of sludge. The filtrate was evaporated and analyzed by infrared spectroscopy. It was found a small amount of impurity precursors. For further deeper purification used the ability of alizarin is dissolved in benzene and the inability to dissolve in it of the product and source of amino acids. After the solid-liquid extraction of insoluble residue was separated and dried. Separation of amino acids was carried out by adsorption chromatography on Sephadex LH-media 20. As the eluent used distilled water, followed by desorption of the target product from the media. The method of obtaining and purification of substances has been repeatedly revised and found to be optimal. After the process, the solution was subjected to boiling to remove ammonia and then neutralized. It is used to remove unwanted impurities from the solution and for a more rational use of mineral acids. After neutralization the precipitate dissolved in water and filtered. The filtrate was poured an equal amount of benzene and highly agitated or mixed by any other methods to intensify the process of interfacial absorption. The benzene layer was subsequently separated and concentrated, thus leveling the loss of starting materials. The method of interfacial absorption accelerates the cleaning process and prevents the passage of the various processes tarring and reduces the loss of time concentrating. The aqueous solution was evaporated to dry. This material was analyzed by the method of infrared spectroscopy.

NEW APPROACHES TO THE MEDICINAL HERBS RESOURCES STUDYING

V.N. Kovalyov, T.A. Krasnikova, T.N. Kryuchkova, N.S. Zhuravlyov National Pharmaceutical University, Kharkiv, Ukraine [email protected]

Medicinal plants are the source of drugs in modern medicine. Herbal preparations belong to more than 85 pharmacological groups of drugs, and often do not have the equivalent of synthetic analogues. Significant fraction of all drugs for the treatment and prevention of diseases of the cardiovascular system, gastrointestinal tract, nervous system, liver, kidneys – are remedies of plant origin. Professional training of pharmacy specialists requires to study of resources of medicinal plants. In the study of medicinal plants the key characteristics are: places of growth , reserves, classification of species as rare or endangered. In the procurement of raw materials are important the phase of vegetation, the rules for collection, primary processing, drying; these factors influence the quality of raw material, which is the subject of pharmacognosy. The elaboration of herbal medicines involves resource studies of wild medicinal herbs while using them as raw materials. In Ukraine, more than half of the needs of medicinal plants is ensured by wild medicinal plants. Thus, reserves of wild medicinal plants are an extremely important source of medicinal plants. They are undoubtedly national treasure of Ukraine. As a result of antropogenic influence on environment from more than 5000 types of vascular plants of Ukrainian flora extincted and 438 kinds are found under threat of disappearance. For different regions of Ukraine the quantity of rare and engaged species is different. In the Kharkov region 255 kinds require an individual guard, from them 57 are plugged in the «Red book of Ukraine». Collection of raw material of these species requires the license. Traditional use of wild plants and medicinal herbs in the manufacture of drugs in recent years, undergoing major changes. Industrial needs are largely borne by the cultivation of numerous species of valuable medicinal plants. Chemo-systematic principles of study of medicinal plants associated with the use of sampling «eydant» species of medicinal plants, allow the use of the most promising «eydant» race of plants for further investigation and possible introduction into the culture.

104 However, we should consider the fact that many species of medicinal plants is almost unsuitable or unprofitable for cultivation, for example, Ledum palustreL., Potentilla erecta (L.) raeusch., Acorus salamus L., Arctostaphylos uva-ursi (L.) Spreng., Helichrysum arenarium (L.) Moench. and many others. Particular attention should be paid to the source studying Medicinal Plant Research phobanthropy: Rhodiola rosea L., Arnica montana L., Glycyrrhiza glabraL., Which are widely used in pharmaceutical and cosmetic products. Changing climatic conditions, political and economic changes have led to the need for a new approach to the study of quantitative assessment of the resources of individual species, their mapping and identification of biological and operational reserves, both on specific thickets and on large areas. GIS technology in Ukraine is not widespread, it is giving information about the arrays of medical plants and most recently are priority in the resourse studying of medicinal plants. Recent legislative acts of the Verkhovna Rada of Ukraine will be directed to forest inventory. A question about optimization of the use and renewal of present source of raw materials is topical and important. Development of this tendency has the state value. Foremost for the solution of this problem we need a deep estimation of the condition and dynamics of natural phytoresourses. In the light of the aforesaid there is the necessity of medical plants resource control with the use of compatible methods in the given research area.

SYNTHESIS OF CHEMICALS FROM RENEWABLE FEEDSTOCKS CATALYZED BY POLYOXOMETALATES

I.V. Kozhevnikov University of Liverpool, Department of Chemistry, Liverpool, UK [email protected]

Among numerous applications of polyoxometalates (POMs), also known as heteropoly compounds, catalysis is by far the most important, offering significant economical and environmental benefits. The aim of this presentation is to discuss recent results of the author’s group on the application of POMs as acid and bifunctional acid-metal catalysts for chemical synthesis using renewable feedstocks such as terpenes and glycerol. Heteropoly acids (HPAs) are demonstrated to be efficient and environmentally friendly catalysts for acid-catalyzed terpene transformations such as hydration, acetoxylation, cyclization and isomerization in homogeneous and heterogeneous systems. These reactions can provide clean routes to valuable ingredients and intermediates for the fragrance and pharmaceutical industries. Recent development of biodiesel production has made a large amount of glycerol available as a renewable feedstock for the synthesis of chemicals. One of the most important directions for the utilisation of glycerol is its dehydration to acrolein. POMs are amongst the most efficient catalysts for this reaction. We have found that the acidic heteropoly salt, Cs2.5H0.5PW12O40 (CsPW), is a very active catalyst for glycerol-to-acrolein dehydraion in the gas phase. Doping CsPW with platinum group metals and co-feeding hydrogen reduces coke deposition thus enhancing catalyst performance. POM-based multifunctional catalysts can effectively carry out multistep reactions in one pot (one catalyst bed) without separating intermediate products. Discussed examples include one-step hydrogenolysis of glycerol to 1,2-propanediol and synthesis of [-]-menthol by hydrocyclization of [+]-citronellal using POMs doped with platinum group metals as catalysts.

105 RECOVERY AND RECYCLING KIESELGUHR – WASTE OIL PRODUCTION

B.E. Krasavtsev, V.B. Simkin, A.S. Tsaturyan Ltd. Kubanmelprodukt [email protected]

Vegetable oils and waste their production, including kieselguhr filter powder (FP), are perspective renewable vegetable resources. Kieselguhr (diatomaceous earth) is a sedimentary rock, which has origin of freshwater and marine. Diatomaceous earth formed from the remains of siliceous valves of different types of diatoms. Kieselguhr has a high porosity and low density, ability to adsorb, poor heat and sound conductivity, infusibility and resistance to acids. Diatomaceous earth, used as a filter powder, is an amorphous silica (88-94% SiO2) and has an average particle size of 30-40 microns. FP is used at the stage of freezing oil by separating high melting waxes. Search for regeneration and recycling of spent diatomaceous earth is an important ecological and economic problem of the industry. We have proposed and implemented 2 ways of disposal at the plant [ 1 ]: 1) advanced regeneration of spent FP for recycling in oil production, 2) processing in the liquid glass. Regeneration of spent FP. There is a method of recycling the FP by its partial degreasing and immediate return to the process of freezing wax. This method has several disadvantages: during degreasing on the filter centrifuge while hot with intense oxidation of the oil is recycled, along with FP; with part-skim powder can not keep any for a long time; the crushed factions are returned to production. The proposed method of regeneration FP does not have these drawbacks. It includes three stages: 1) deep degreasing powder for which the residual oil content does not exceed 5% ; 2) calcining the powder at a temperature of 550-6500С to the complete removal of organic residues and free moisture; 3) fractionation for remove the crushed particles. As a result, the regenerated powder does not contain fat oxidation residue and crushed fractions. It can be stored indefinitely. Its adsorption activity corresponds to the initial fully. Deep processing of diatomite waste in liquid glass (LG). Chemical and grain composition of degreasing diatomite allowed to use it in production conditions as a feedstock for the wet method of production of LG. Mode of cooking LG is soft and fast – the pressure in an autoclave is not greater than 2atm, temperature 1200С, the duration of the process is not more than 2 hours. After removal of soaps ( formed during the saponification of the fat residue in the powder) and evaporation to the required density LG satisfies the requirements of GOST. Soluble liquid glass (sodium) is a colloidal system of sodium silicate Na2SiO3 in water. Plants are usually released soluble glass density 1.38 – 1.50 g/cm3 ; then it is diluted with water to desired concentration in the workplace. Our company has accumulated extensive experience in the disposal of spent filter powder in other industries. Literature: 1.Tsaturyan A.S., Avdeev, A.A., Krasavtsev B.E., Maslikov V.A., Simkin V.B. Method of non- waste recycling used diatomite and perlite filter powder used in the production of vegetable oils Patent № 2347805 RF 27.02.2009g.

PERSPECTIVE SOURCES OF BIOLOGICAL ACTIVE SUBSTANCES AND DRUGS

E.A. Krasnov, Y.V. Gorina, T.V. Kadyrova, I.P. Kaminskiy, E.Y. Avdeeva Siberian State Medical University, Tomsk, Russia [email protected]

Tremendous successes in treatment of numerous diseases are provided by using in medical practice of new drugs made on the basis of screening and fundamental sciences achievements. At the same time screening search doesn’t lose its significance nowadays especially while studying unknown earlier chemical substances of synthetic and natural origin. In particular it concerns plant secondary

106 metabolites which being similar to metabolites of animal and human being, cause undesirable side reactions rarely. Undesirable side reactions are serious problems of modern medicine. Modern drugs for pharmacological correction of liver diseases may cause various complications that restrict their application. We established that water extracts from Stellaria species especially S. media possess hepatoprotective action coupled with antioxidative activity. Hepatoprotective activity was evaluated by their effect on organ-specific enzymes (ALT, AST) and phosphatase alkaline value, POL. Three PS fractions from S. media aerial part were isolated and studied together with the Institute of physiology RAS. Their hydrocarbon chains contain residues of glucuronic acids, rhamnose, arabinose, xylose, mannose, glucose and galactose. PS with various content of uronic acids (13%-85%) were isolated by the method of IEC on DEAE-cellulose. In some cases isolated from the plants substances with simple structure and proved biological activity are advisable to be produced by simple synthesis. For example, phenolic alcohol p-thyrosol is biological active component of Rhodiola species possesses adaptogenic, antioxidative, antihypoxic, antistress, hemorheological activity and can be used during myocardial and cerebral ischemia complicated forms. Parasitic diseases (ophisthorchiasis and lambliosis) are an actual problem in medicine. In this respect Centaurea species are perspective. They contain sesquiterpene lactones (SL) possessing a wide spectrum of biological activity. We studied antiophisthorchiasis activity of C. scabiosa, C. jacea, C. pseudomaculosa that is equal to activity of the synthetic drug biltricide (FRG). In the mentioned species guainolides grosheimin, cynaropicrin and repin were detected by HPLC. SL was isolated from C. scabiosa. The elaboration of anticonvulsive drugs is an important direction of investigations. We showed the perspective of Empetrum species investigations and studied its chemical composition in detail by original method approach. For the first time macrocyclic alcanes and some retrochalcones were isolated from the plants. Also the composition of lipophylic fractions possessing high anticonvulsive activity was established. Phyto-drug “Empetrin” was elaborated. In the last years search of effective nootropic drugs on the basis of plants attracts considerable attention. There drugs have important significance in neurogenic pathologies, normalize teaching and memory processes under conditions of high psycho-emotial effort inintegrative and mnestic brain functions weakening and their violation caused by physical and chemical factors. By chemico-pharmacological investigation it was established that Filipendula species especially F. ulmaria that have big source potential all over Russia have significant perspectives. Plant extrats revealed evident antistress, nootropic and antioxidative activity, conditioned reflex functioning improvement after hypoxic injury and under conditions of brain hypoxia. It was established that the plant contains phenolic compounds complex consisting of simple phenols, phenolcarbonic acids, coumarines, flavonoides and tannins. By CC on SG and PA 14 compounds were isolated and 12 substances of them were identified as oleanolic, ursolic, anisic, salicylic, gallic acids, ethyl gallat, quercetin and its 4 glycosides – avicularin, isoquercitrin, rutin and filimarin (new flavonol glycoside). The results of investigations are protected by RF patents and underlie the projects of PA on officinal herb and PA on dried C. scabiosa extract.

BIOLOGY-PHYTOCHEMICAL INVESTIGATIONS ABOVEGROUND ORGANS SPIRAEA SALICIFOLIA

I.M. Krivosheev, V.M. Mirovich, G.M. Fedoseeva Irkutsk State Medical University, Irkutsk [email protected]

Objective. To conduct biological and phytochemical study spiraea salicifolia, establish the feasibility of its use in medical practice in the gastro-intestinal diseases. Materials and methods. Aboveground organs of spiraea salicifolia were used dried as a material. For a preliminary study of biologically active substances such as tannins, coumarins, flavonoids, 107 ascorbic acid, water-soluble polysaccharides, free sugars were carried out by qualitative analysis of the reaction with the reagents, and used thin-layer and paper chromatography. The determination of the quantitative content of tannins, ascorbic acid, free organic acids was performed by titrimetric methods and flavonoids performed spectrophotometrically. The optical density of the extracts in the analysis of flavonoids was measured at a length of wave of 410 nm on a spectrophotometer SF-46. The determination of the quantitative content of water-soluble polysaccharides, pectins and hemicellulose A and B was carried out gravimetrically. Microscopic studies were performed on the surface preparations and transverse sections on the microscope MBS and MBI. Transverse sections were stained with 0.1% alcoholic solution of floroglyutsina and hydrochloric concentrated acid. Micro preparations were photographed with a digital camera Nikon and analyzed on a computer with the use of software Photoshop 7.0. Results. The precipitations were noted in aqueous extracts, in reactions with 1% solution of gelatin, quinine chloride and bromine water. A mixture of formaldehyde and hydrochloric acid precipitate was formed during boiling and adding solution of alum zhelezoammonievyh a black-green color appeared, which indicates the content of tannins. Extraction of 70% ethyl alcohol was analyzed for the presence of flavonoids (sample Synod - red coloration; 1% alcohol solution of aluminum chloride, 10% ammonia - a yellow coloring and 1% alcoholic solution of sodium hydroxide and 0.5% alcohol solution of iron (III) chloride - dark green staining), which indicates the presence of flavonoids. The composition of phenolic compounds was carried out with upward one-and two- dimensional chromatography alcohol extraction in the systems: n-butanol - glacial acetic acid - water (4:1:2), 15% acetic acid. The results of acidic hydrolysis of the alcohol extract showed that the flavonoids spiraea salicifolia are derivatives of quercetin. Flavonoids - quercetin, hyperoside, rutin, phenol carbonic acids - caffeic acids and ferulic acids were identified with authentic samples. The investigation of the flavonoids and tannins in plant organs and phases of vegetation showed that the greatest number is stored in the leaves which were collected in July. There were 4,28 ± 0,19% of flavonoids, 7,46 ± 0,115% of tannins. A substantial content of polysaccharides were identified in the leaves: water-soluble polysaccharides 2.94% 5.04% pectin, hemicellulose A - 14.6%, hemicellulose B - 3,8%. The leaves consist of 35 mg% of ascorbic acid, 2,17% of free organic acids. Also were found free sugar and coumarins. In cross-section of leaf spiraea salicifolia is dorzoventrale. Papillate epidermis is particularly at the lower side of the sheet. Stomatal apparatus is of anomotsitnic type. Outer and inner cells of the epidermis corolla are multifaceted with rare stomata. The outer epidermis at the base of the corolla is with numerous unicellular hairs. Conclusion. Spiraea salicifolia contains of valuable biologically active substances such as polysaccharides, tannins, flavonoids, ascorbic acid in therapeutically significant quantities, which make this plant perspective for use in medical practice of treatment of gastrointestinal diseases.

HYDROCARBONS SYNTHESIS FROM BIOMASS-DERIVED SYNTHESIS GAS OVER COBALT CATALYSTS

M.V. Kruchkov1, O.L. Eliseev2, A.L. Lapidus1 1 - Gubkin Russian State University of Oil and Gas 2 - N.D. Zelinsky Institute of organic chemistry [email protected]

Russian Federation possesses huge wood and agricultural resources. However, deep processing of these resources is not developed well enough. The main purposes of the wood industry today are decreasing export of round timbers and increasing of secondary processes of wood processing. Secondary operations of resources processing are the most profitable. This also applies to agriculture. Nevertheless, this sector of economy is progressing actively now and it is possible to hope that this problem will be solved soon. Meanwhile wood industry and agronomy waste can be used as a feedstock for other industrial processes which are also important. One of these prospective

108 processes is production of synthetic higher hydrocarbons from this type of raw materials. With the appropriate technological design, this method can be cost-effective even at low power-ups [1]. The way offered to consideration consists of several stages: (1) synthesis gas production from wood industry and agronomy waste; (2) purification of synthesis-gas from undesirable components; (3) Fisher-Tropsch synthesis (FTS). The first stage is the most expensive, with cost depends strongly on the type of oxidizer applied. Oxidizer may be technically pure oxygen or an air. In the last case resulting synthesis gas is diluted with nitrogen (up to 60% vol.) that is hard to be removed. Such dilution of synthesis is usually taken as a drawback of air-based process. On the other hand, diluted synthesis gas possesses a number of advantages in FTS. Namely, applying this feed prevents local overheating in catalyst bed, thus increasing target products selectivity and prolonging catalyst life span. [1]. A number of cobalt-alumina catalysts promoted by rare-earth metal oxides were prepared and tested in low temperature FTS. Feed gas composition simulated synthesis gas produced in air-based gasification of organic waste. Gas composition: 62% N2, 26%H2, 12% CO. The catalysts were tested in temperature interval of 180…230°C and a pressures of 1, 5, 10 and 20 bar. We demonstrated that cobalt catalysts are capable to convert nitrogen diluted synthesis gas into hydrocarbons with high per pass conversion, selectivity to fraction С5+ of 85-90% and methane selectivity of 5-7%. Due to high CO conversion level, gas recycle is not needed, thus reducing operating costs.

Literature 1. A. Jess ;_, R. Popp , K. Hedden, Fischer–Tropsch−Synthesis with nitrogen-rich syngas. Fundamentals and reactor design aspects, Applied Catalysis A: General 186 (1999) 321–342

EQUIPMENT AND PROCESSES OF COMBINED CULTIVATION OF MICROORGANISMS AS A PROMISING TECHNOLOGY BASE FOR BIOCONVERSION OF VEGETABLE RAW MATERIALS

V.K. Kudryashov1, Yu.V. Redikultsev1, M.A. Zinoviev1, R.M. Malyshev2, M.R. Taraskevich1, A.A. Ugraitskiy1, A.N. Shkidchenko1 1 - IBI RAS (Pushchino) 2 - OOO “Obyedinenye IREA-Penzmash” (Moscow) [email protected]

Comprehensive processing of renewable vegetable raw materials assumes the most complete recovery of their components isolated under their native form. Raw material biomass remaining after isolation of soluble components mainly contains lignocelluloses components (more than 50%). These components are considered as the main kind of renewable raw materials to obtain liquid biofuels and other products for chemical industry by biotechnological methods. Processing of vegetable raw materials with the use of microbiological technologies without pretreatment is rather difficult due to high content of biologically active substances in the starting raw materials, that significantly slows down microbiological processes. Extraction methods are used to isolate biologically active substances. In order to intensify the processes of vegetable raw material extraction and to increase reactivity of lignocelluloses components, fast vacuum evacuation and pulsed pressure increase are used to attack the raw materials, which enables to accelerate the extraction processes and provides transferring of raw materials and products to various stages of the technological process. To apply microbiological technologies for processing renewable vegetable raw materials characterized by a high content of insoluble components of lignocelluloses, cellular tissue, starch, it is necessary to provide mass- and gas exchange in viscous culture media having a high content of insoluble components. The need to automate the processes of preliminary preparation of raw materials for implementing said technologies, as well as those of loading substrates and unloading cultivation products require new technical solutions.

109 The use of combined cultivation joining characteristics of liquid- and solid-phase modes of microorganism cultivation represents one of promising directions to use microbiological technologies when utilizing insoluble substrates. The modes of combined cultivation are carried out in bioreactors based on running down films, composed of two hydraulically linked bioreactor vessels, the liquid phase of cultivation medium flowing from one bioreactor vessel to the other and back. In this case, the solid-phase process takes place in the discharged vessel and the liquid-phase cultivation process is activated in the cultivation vessel filled with liquid phase into which the cultivation medium solid phase is immerged. The running down film forms a media phase interface: aerating gas and culture liquid, the larger the running down film surface, the higher aerating power of the process. The culture liquid entering the second bioreactor vessel displaces metabolic gases filling the second vessel to a device for filtering departing gases. Therefore, the first fermentation vessel passes to the solid-phase cultivation mode and the second one, to the liquid-phase cultivation mode. When a third vessel and a device for commutating liquid streams are added to the bioreactor, a continuous (taking off and loading) mode of cultivation is allowed, and the possibility to automate the process of preparing a full valuable nutrient medium under the conditions of a cultivation process as well as the processes of product unloading is provided. Such a way of organizing the physical volume of bioreactors enables to group several uniform bioreactor vessels into a multibioreactor system where multistage and multi-phase processes of obtaining target metabolites of film-like and mycelium cultures as well as various associations of microorganisms become possible.

MICROALGAE PROCESSING FOR 3G BIOFUELS PRODUCTION

R.G. Kukushkin, V.A. Yakovlev, K.N. Sorokina, A.V. Piligaev, S.A. Selishcheva Boreskov Institute of Catalysis SB RAS [email protected]

World energy consumption is supposed to increase over the next few decades as well as transport fuel demands. Renewable biofuels are needed to partially displace petroleum derived transport fuels. Liquid biofuels might help to avoid lack of transport fuels, to decrease fuel prices in future and more over to reduce green house gas emissions. Currently, different types of biofuels (e. g. biodiesel, bioethanol, biobutanol etc.) are derived from different types of biomass. Biodiesel is mainly associated with mono-alkyl esters of long chain fatty acids produced by transesterification process from vegetable oil, animal fats and waste cooking oil. Although, agricultural crops are used for biodiesel production, they have some disadvantages. For example, fuel production from edible crops influence on food prices and agricultural crops do not have enough oil productivity for commercially successful fuel production. Microalgae are believed not to influence on food prices in comparison with edible agricultural crops and most productive oil crops, such as palm oil do not come close to microalgae in their ability to produce so much quantity oil per area [Y. Chisti, 2008]. Nowadays homogeneous catalysts (e. g. NaOH, H2SO4 etc.) are used in transesterification process. The final mixture needs to be separated, neutralized and thoroughly washed, generating a great amount of salt, soaps, and waste water which need to be further purified and treated. It is to be mentioned that the catalyst cannot also be recycled [R. Luque, 2008]. Biodiesel has a number of restrictions due to its higher viscosity and cloud point in comparison with conventional diesel. Therefore oxygen removal by different processes (e. g. hydrodeoxygenation or pyrolysis) is required for production of hydrocarbons suitable for diesel fuel blending [D. Yu. Murzin, 2005]. The aim of our study was the investigation of different catalytic processes for biofuel production using microalgae as a feedstock. The esters (biodiesel) were derived by transeresterification process from lipid fraction of microalgae Botryococcus braunii UTEX 2441. The process was conducted over homogenous catalyst (H2SO4) and heterogeneous catalyst (BaAl12O19) the experiments were carried out in batch reactor. The hydrocracking process was applied for oxygen-containing groups removing (ester functional group in this case). This process was conducted over Ni - based catalysts, having been reported as good catalysts for upgrading biodiesel from rapeseed oil into 110 conventional fuel [V. A. Yakovlev, 2009]. The experiments were performed in a conventional flow reactor with ethyl ester of octanoic acid and methyl ester of hexadecanoic acid used as model compounds. The choice of model compounds was based on experimental data and data available in literature. The maximal conversion of esters has been observed over Ni – Cu/Al2O3 catalyst. The hydrockracking of microalgae’s lipid fraction (Botryococcus braunii UTEX 2441) over Ni – based catalysts has been carried out as well to derive transport fuel compounds in one step process without transesterification reaction.

Chisti Y. Biodiesel from microalgae // Biotechnology Advances. – 2007. – Vol. 25. – P. 294 – 306. Luque R. et al.. Biofuels: a technological perspective // Energy & Environmental Science. – 2008. – Vol. 1. – P. 542 – 564. Murzin D. Yu. et al.. Hydrocarbons for diesel fuel via decarboxylation of vegetable oils // Ctalysis today. – 2005. – Vol. 106. – P. 197 – 200. Yakovlev, V. A. et al.. Development of new catalytic system for upgraded bio-fuels production from bio-crude-oil and biodiesel // Catalysis Today. – 2009. – Vol. 144. – P. 362 – 366.

SYNTHESIS AND RESEARCH OF SURFACE-ACTIVE SUBTANCES ON THE BASIS OF INDUSTRIAL WASTE PRODUCTS

A.E. Kurbanbaeva Institute of General and Inorganic Chemistry, Academy of Sciences, Tashkent, Republic of Uzbekistan [email protected]

Now it is felt lacks of raw material for synthesis and the manufactures, new surface-active substances with a various structure of molecules. The basic raw material at reception of surface- active substances (PAS) is fat acids, spirits and oils of a vegetative and animal origin. In manufacture of cotton oils in a plenty it is formed cotton gossypol, the supreme fat acids representing a mix. Use of waste products of manufacture as raw material for synthesis of PAS solves an environmental problem and provides cheapness of received preparations. In this connection, in the given work for synthesis of PAS as initial raw material fusel oils (waste products of manufacture ethyl spirit) and gossypol pitch (waste products of manufacture Vegetable oil grouped enterprises) have been used. For reception of PAS gossypol pitch sulphonation the concentrated sulfuric acid (95 %, 1,84г/sm3). For acceleration process sulphonation the opportunity of use of catalyst Al2 (SO4)3 is established. Optimum conditions of formation of ethers gossypol pitches are established on the basis of the experiences lead to a series with a variation of temperature, a parity of initial reagents, time and quantity of the catalyst. It is established, that optimum conditions sulphonation gossypol pitches are the following: temperature 75-80С, molal a parity of the concentrated sulfuric acid to gossypol to pitch 1,3-1,4 : 1, duration of reaction 3-3,5ч. Then to the received product of reaction added fusel oils. Optimum conditions of formation alkyl an ether gossypol pitch are the following: temperature 85-1050С, a parity of reagents 1:1,5, duration of reaction of 4, 5-5 hours. From the taught product of reaction drove away unreaction surplus of initial reagents and spirit under the lowered pressure. Results of studying kinetics reactions sulphonation gossypol pitches testifies to natural decrease of speed sulphonation with reduction of concentration of a sulfuric acid. The received results have 20 3 shown, that increase of concentration of a sulfuric acid up to 85 % (d4 =) conducts 1,84г/sm to acceleration of process sulphonation waste products. Then carried out reactions neutralization at constant hashing within 1,0-1,5 hours 25 %-s' water solutions various amino compounds (mono-, di-, triethanolamites). Monoethanolamination, diethanolamination, triethanolamination salts gossypol pitches are received at constant hashing during 15 minutes on drops added mono-, di-, and triethanolaminates. Synthesis of PAS proceeds under rather soft conditions (Т0С=25-35). The received product of reaction represents viscous substance, dark, brown, dark-brown color, with an original smell, well soluble in warm water, ethyl spirit and acetone, not soluble in hexan, benzene.

111 The synthesized connections are identified by methods of ИК-spectroscopy. There is the intensive strip caused by valiant fluctuations of -СООН-group in area 3000-2500sm-1. Strips, characteristic for valiant fluctuations -СООR, are in a range of 1200-1030 sm-1, 1730-1720 sm-1. IT groups -1 concern to deformation fluctuations a strip at 1620-1640 sm . To deformation fluctuations NH2 of group concern a strip 1580 – 2000sm-1. Symmetric and dissymmetric violent fluctuations СОО- group concern a strip 1400-1410sm-1. New surface-active connections with a various structure of molecules which can represent the big interest for various branches of a national economy are synthesized.

THE ACIDS OF CARBON DIOXIDE EXTRACT OF SIBERIAN SILVER FIR

A.K. Kurganov1, V.I. Karpitsky1, V.I. Roshchin2 1 - The Siberian factory of extracts and biotechnologies,Tomsk, Russia 2 - The St.Petersburg Forest Technical Academy, Department of Wood Chemistry and Forest Chemical Products, Saint-Petersburg, Russia [email protected]

The Siberian silver fir green foliage – the residual remaining on the forest floor after timber harvesting - is used to obtain silver fir oil (steam distillation) and preparations «Silk» and «Verva» (ethyl acetate and emulsion way of extraction), CO2-extraction. The component composition of CO2 – extracts hasn’t been enough studied. The acid composition of CO2-extract was studied. The acid fraction was separated from neutral substances of oil fraction by water solution of sodium hydroxide. Higher fatty acids (10.5%), resin acids (76.0) and acids of polar compounds (9.5 %) were separated by the column chromatography method. The extracted fractions were methylated with diazomethane; the composition was determined by the method of chromatomass spectrometry. Higher fatty acids consisted of 68% linolenic, linoleic and oleic acids and 32% of saturated acids with an even number of carbon atoms in a molecule chain С14, С16, С18, С20, С22, С24, The diterpene acids are: isopimaric acid (23%), dehydroabietic acid (48%), abietic acid (19%), nonabiatic acid (10% of resin acids). Triterpene acid of lanostane series (firman acid (4.2% of the sum of acids)) was isolated from the fraction of polar compounds. The fractions of esters of neutral substances (39% here and further of neutral substances) consisted of ethers of higher fatty acids, aliphatic alcohols and sterols (16%), methyl ethers of resin acids (0.4%), triacylglycerols (3%) and monoterpene acetates (20%). The composition of acidic component of esters is close to the composition of higher fatty acids and resin free acids respectively.

COMPARATIVE ANALYSIS OF THE NATURAL PHENOLIC ANTIOXIDANT CONTENT IN EXTRACTS OF MEDICINAL PLANTS

D.V. Kurilov1, N.N. Sazhina2, V.M. Misin2, N.D. Zubareva1, A.V. Strelyaeva3, V.M. Sadykov3, E.B. Kirichenko4, S.S. Zuev3, T.A. Scheglova3 1 - N.D. Zelinsky Institute of Organic Chemistry, RAS 2 - N.M. Emanuel Institute of Biochemical Physics, RAS 3 - I.M. Sechenov First Moscow Medical University 4 - N.V. Tsitsin Main Botanical Garden, RAS [email protected]

Free radical oxidation, being universal and unspecific factor of the damage of cells and tissues, plays the important role in pathogenesis of large number of diseases. Phenol type antioxidants (AO), containing in a significant amount in medicinal herbs, break this process. The purpose of the present work – comparison of the total natural phenolic AO content in extracts of some herbs: a milfoil (Achillea millefolium L.), a sage (Salvia officinales L.) and spearmint (Mentha piperita L., both mentholic and linaloolic chemotypes) depending on their extraction conditions. For this

112 purpose an ammetric method of measurement of the total phenolic AO content, realized in device "TsvetYauzа-01-АА", was used [1]. The essence of the given method consists in registration of the electric current arising at oxidation of investigated substance (or mixes of substances) on a working electrode surface at certain potential (from 0 to 1.3 V) At these potentials there is an oxidation only OH-groups in AO of phenolic types. The electrochemical oxidation, proceeding under the scheme R–ОН → R–О• + e- + H+ (R – AO fragment, that is flavonoids, tanning substances, terpenoids etc.), can be used as modeling process at measurement of the ability of substance molecules to intercept free radicals in biosystem [2]. For carrying out of researches samples of the dried up plants (cultivated on an experimental area of Main Botanical Garden of RAS) were crushed till the particle size 1-2 mm, and 1.0 g of material was flooded by ethanol (conc. 96%), distilled water or their mixture in the volume ratio 70:30. The extracting volume was 100 ml, temperatures - 200С and 950С for water, 200С and 750C for ethanol, 200С and 850C for a ethanol-water mixture. Extraction was carried during 10 minutes without thermostatic process, and then received solutions were quickly filtered through the paper filter «a dark blue tape» [3]. Values of the total phenol type AO content in extracts (in comparison with a gallic acid as a standart) depending on extraction and temperature conditions was found to vary within the range: for a milfoil - from 2.7 to 13.0 mg/g; for a sage – from 4.9 to 19.6 mg/g; for spearmint (linaloolic and mentholic chemotypes) – from 5.4 to 39.5 mg/g and from 8.6 to 45.0 mg/g, accordingly. Thus, the highest values of the total AO content in extracts of the investigated plants were observed in samples of mint (both chemotypes). Optimum conditions for the AO extracting process used in work are the following: extractant – ethanol-water (70:30) mixture at the temperature 85°C.

50 40 C, 30 mg/g 20 10 0 Milfoil Sag Spearmint Spearmint linaloolic mentholic

1 - water, 20С 2 - water, 95С 3 - ethanol, 96%, 20С 4- ethanol, 96%, 75С 5 - ethanol, 70%, 20С 6 - ethanol, 70%, 85С

Literature. 1. Peyrat-Maillard M.N, Bonnely S., Berset C. Determination of the antioxidant activity of phenolic compounds by coulometric detection // Talanta. 2000. V. 51. P. 709. 2. Misin V.M., Sazhina N.N., Zavjalov A.Yu., Yashin Ya.I. Measurement of the phenols content in extracts of medicinal herbs and their mixes by ammetry // Khim. Rastit. Syr’ya. 2009. № 4. P. 127- 132. 3. Yashin A.Ya. Inject-flowing system with ammetric detector for selective definition of antioxidants in foodstuff and drinks // Ross. Khim Zh. 2008. V. L II, № 2. P. 130-135.

113 COMPARATIVE ANALYSIS OF CHEMICAL COMPOSITION OF EXTRACTION FROM DRY AND FRESH SAGE LEAVES

D.V. Kurilov1, N.D. Zubareva1, A.V. Strelyaeva2, T.A. Scheglova2, V.M. Sadykov2 1 - N.D. Zelinsky Institute of Organic Chemistry, RAS 2 - I.M. Sechenov First Moscow Medical University [email protected]

Sage leaves (Folia Salviae (producing plant - Salvia officinalis L.)) as broadly known medi-cinal plant are used for preparation extracts and complex remedies (for instance «Salvin»). It is the leave dry material of the plant that is prescribed for using in academic medicine practice. On the other hand in homeopathic pharmacy just vegetative parts of fresh plant to preparate various dilutions are used. The aim of present investigation was to compare an quantification in etanolic extracts obtained from the dry and fresh material of S. officinalis L., cultivated on an experimental area of N.V. Tsitsin Main Botanical Garden of RAS. The investigation was carried out by gas chromato-mass-spectrometry with a device of «Agilent Technologies» including: 1) gas chromatograph 7890 (column HP-5, 50 m x 320 μm x 1.05 μm) and 2) mass-detector 5975 C (quadrupole type). Software - ChemStation E 02.00. Identification was accomplished according to the mass-spectrum library «NIST-05» and corres-ponding chromatographic Kovach indexes. Quantification was fulfilled by calculating the ratio of chromatographic peaks areas. In composition of the analysed samples the content of volite compounds (more than 40 components) were identified and evaluated its ratio. This list covers the mono-, sesqui- and diterpenoids, derivatives of furane and pyran heterocycles, substituted phenols, unsaturated alcohols as well as esters of various saturated and unsaturated fat acids (%, dry, fresh material accordingly, abbreviation: tr. – trace amount and abs. - absent): α-pinene (0.36, tr.), α-fenchene (0.22, 0.52), α- terpinene (0.13, 0.06), p-cymene (0.21, 0.19), limonene (0.08, 0.31), 1,8-cineole (2.45, 3.91), τ- terpinene (0.48, 0.26), linalool (0.36, 0.33), α-thujones (9.90, 14.39), camphor (4.64, 10.38), borneol (2.21, 1.29), 4-terpineol (0.15, tr.), α-terpineol (0.06, tr.), bornylacetate (0.90, 0.35), 2-(7- hydroxy-3,3-dimethyl-4-oxo-7-vinylbicyclo[3.2.0]hept-1-yl)acetaldehyde (1.56, 1.28), β-caryophyllene (3.86, 1.84), 5-ketobornylacetate (0.67, tr.), α-caryophyllene (3.44, 4.40), valencene (0.35, tr.), δ-cadinene (0.13, abs.), 4,4,7a-trimethyl-5,6,7,7a-tetrahydro-1-benzofuran-2(4H)-one (0.03, abs.), β-caryophyllene epoxide (0.71, 0.60), ledol (8.40, 5.83), 1,5,5,8-tetramethyl-12- oxabicyclo[9.1.0]dodeca-3,7-diene (0.92, 0.64), 2-furaldehyde (0.24, tr.), 2-furylmethanol (0.14, tr.), 2,4-dihydroxy-2,5-dimethyl-3(2H)-furanone (0.24, 0.44), 5-(hydroxymethyl)-2-furaldehyde (1.42, 2.76), 3,5-dihydroxy-6-methyl-2,3-dihydro-4H-pyran-4-one (1.67, 1.25), 2-methoxy- 4- vinylphenol (0.76, 2.26), 4'-hydroxyacetophenone (1.12, 5.00), 4-acetyl-2-methoxyphenol (0.30, tr.), methylsubstituted O-acetyltetradecen-1-ol (0.45, 1.33), succinic acid monoethyl ester (0.72, tr.), ethyl palmitate (5.14, 0.13), labda-8(20),14-dien-13-ol (34.27, 38.43), labd-14-ene-8,13-diol (1.38, 0.38), ethyl linoleate (4.00, 0.88), ethyl linolenate (5.15, 0.35) and ethyl stearate (0.78, 0.19). As it is seen from the data cited above a supermajor component in extracts from both dry and fresh material is a diterpenoid of labdane type - labda-8(20),14-dien-13-ol. It is important to note that the compounds such as α-pinene, 4-terpineol, α-terpineol, 5-ketobornylacetate, valencene, δ-cadinene, 4,4,7a-trimethyl-5,6,7,7a-tetrahydro-1-benzofuran-2(4H)-one, 2-furaldehyde, 2-furyl-methanol, 4- acetyl-2-methoxyphenol, succinic acid monoethyl ester in extract from fresh material are present as its trace amount or absent at all, whereas the extract from dry material contains a great amount of ones. Besides, in the extract from dry material compared with fresh material the amount (%) of some compounds noticeable decreases: limonene (from 0.31 to 0.08), 1,8-cineole (from 3.91 to 2.45), α-thujones (from 14.39 to 9.90), camphor (from 10.38 to 4.64). Thus, the content of the minor volite components in the dry and fresh material extract has some difference, although the content in respect to the major components is quite equal. Seemingly, the fact of decreasing of some extract components indicated above suggests that oxidizing occurs in the course of material drying

114 and preserving. This situation in the event of limonene is clearly displayed: the contain of 4- and α- terpineols as oxidized forms of limonene increases in dry material.

SYNTHESIS AND EFFECT OF THE NEW PHYTOHORMONES ANALOGUES ON THE CUTTING’S ROOTING OF THE JUNIPERUS PLANTS

N.B. Kurmankulov1, K.B. Erzhanov1, M.K. Asemova2, M.Yu. Ishmuratova3, A.T. Klimchuk3 1 - A.B. Bekturov’s Institute of Chemical Sciences, Almaty, Kazakhstan 2 - al-Farabi Kazakh National University, Almaty, Kazakhstan 3 - Zhezkazgan Botanical Garden, Kazakhstan [email protected]

In the practice of forestry and the nursery the various methods of stimulation root’s growth ability of cuttings: physiological, mechanical, physical, chemical are used for improving of the yield and quality of plant materials. Among chemical methods, we note the use of plant growth regulators - synthetic analogs of phytohormones. Their application provides a more complete utilization of biological potential, can increase the yield of seed per unit area and significantly improve the quality of seedlings. Heteroatomic propargyl compounds are important synthons in the synthesis of biologically active compounds. The scheme shows the directions of chemical transformations of aromatic compounds on the example of prop-2-ynyloxybenzene which are studded in the A.B. Bekturov’s Institute of Chemical Sciences.

R O O N R R O O O R R

OH O O R O R H N N N OH O O X O R

Among the synthesized compounds were identified substances with a high root’s growth activity against various species of Juniperus genus. In the experiment we used the water solutions of new regulators of growing KN-2 and AES-17 at concentrations 0,01, 0,001 и 0,0001%%. The green and bed hafts of the different species of Juniperus were been felt concern about in the conditions of the Zhezkazgan region (table).

The factors of ingraining of the green and bed hafts of Juniperus species

Ingraining of cuttings, % Type of Species Control 0,01 % 0,001 % 0,0001 % cuttings (water) КN-2 АЕS-17 КN-2 АЕS-17 КN-2 АЕS-17 Juniperus Green 13 32 30 35 33 33 31 communis Bed 28 41 39 60 57 60 50 Juniperus Green 12 36 31 40 37 38 36 horisontalis Bed 30 60 56 75 70 73 64 Juniperus Green 20 41 36 45 41 40 33 pseudosabina Bed 28 59 54 75 71 70 61 Juniperus Green 17 31 27 35 33 30 28 sargentii Bed 34 72 68 80 80 75 69 Juniperus Green 15 39 35 45 40 42 37 squamata Bed 45 57 50 60 55 56 50

115 Juniperus Green 22 36 39 40 40 37 35 sabina Bed 37 60 54 75 70 74 64 Juniperus Green 25 40 42 45 42 36 31 conferta Bed 50 73 70 90 83 82 80

So, the high efficiency of new growth regulators for ingraining of green and bed cuttings of Juniperus species was revealed. The experiences will be continued.

COMPARISON OF COMPOSITION AND BIOLOGICAL ACTIVITY OF EXTRACTS OF WOOD GREENS (WG) OF PINES AND SPRUCE

N.A. Kutakova, E.V. Minina N(A)FU,The Department Of Forest-Chemical Productions, Arkhangelsk, Russia [email protected]

Preparation VERVA receive by extraction of fir WG. It is a growth factor of the plants. Value of it is caused by presence triterpen acids.It is possible that pines and spruce wood greens extracts contain other components wich have the same properties. The purpose of our work is comparison of composition of water pines and spruce WG extracts and definition of possibility of their use for preseeding processing of seeds. The technoiogy extraction include raw crushing and insisting of it with hot water. The range of temperature is from 60 to 85оС. There were two modes: with simultaneous processing by ultrasound (SPUS) and without it. The experimental data resulted in the table testified that spruce WG extracts 1) active extraction of tannides is note with SPUS; 2) containing of soluble sugars is stable; 3) total containing of solids is lowered with SPUS. The pine WG extract contain more tannides and water- soluble fibers than spruce WG extracts. The containing of ascorbic acid is decrease with high temperatures since this acid is astable. Comparison of extracts, % Water-soluble Kind WG Solids Tannides Soluble sugar Ascorbic acid fibers Without SPUS, t = 85оС spruce 1,98 0,56 0,40 0,64 0,008 pine 1,38 1,20 0,42 0,87 - SPUS, t = 60оС spruce 0,90 1,02 0,49 - 0,064 SPUS, t = 85оС spruce 0,88 5,05 0,40 - 0,0006

The preseeding processing of seeds by the received extracts (with SPUS) spent with aeration for 1 h. Sprouting was carried out in accordance to GOST 13056.6-97 which contain describes of definition germination seeds condition. Water and preparation VERVA were used for comparision with pines and spruce WG extracts. The spruce and acacia seeds were used as germinating samples. Dose of pines and spruce WG extracts was 0,01 g/l and dose of preparation VERVA was 0,05 g/l. While the results of germinating were the same. The pine WG extract was shown the bigger activity, than spruce WG extract and was surpassed preparation VERVA on 14 % with concentration 2 g/l. The 100 % th germinating of seeds was reached using spruce WG extracts with concentration 3 g/l. While 90 % th germinating of seeds was reached using preparation VERVA with the same concentration. The 82%th germinating of seeds was reached using water. Thus, water pines and spruce WG extracts have growth regulation properties by reason of biological active substances complex, which is a part of it. Recommendations about a dosage of extracts at processing of seeds need in specification.

116 SYNTHESIS OF BIOLOGICALLY ACTIVE COMPOUNDS BASED ON NATURAL MONOTERPENOID

A.V. Kutchin, M.A. Torlopov, L.L. Frolova, I.Yu. Chukicheva Institute of Chemistry of Komi science centre of Ural branch of RAS [email protected]

Low-molecular components isolated from plant materials are building blocks for chemical transformations in order to obtain of analogues known nature compounds having physiological activity, as well as new drugs for medicine, veterinary medicine and agriculture. Existing development and proposed technology allows efficient use of available renewable raw material and receive a wide range of new products. Oxygen-containing monoterpenoids of different nature are of great interest for medicine as part of various drugs. Mix monoterpenic hydrocarbons constitute of their main part of the neutral components of extractive substances of coniferous. The main component of the Russian turpentine is α-pinene. As a result of oxidizing modification of α-pinene we obtained a lot of valuable mono- and bifunctional oxygen-containing derivatives. These compounds are used by manufacture of pheromone preparations for the monitoring and control of insect-pests, vitamins, medical products. The introduction of nitrogen-containing functional groups in the molecule of terpenes obtained potential medical substances with antiviral, antibacterial, antiparasitic activity. On a basis of terpadienes we develop a way of selective synthesis ortho-terpenophenols with various structural type of terpenic substitute. Low-toxical terpenophenols and their functional derivatives determines the possibility of using them in obtaining high-performance medical products with multitargetny activity and combination of properties: antioxidant, hemorheology, antiaggregant, antiarrhythmic, antithrombogenic. The combination in one molecule of hydrophilic vegetable polymers, providing water solubility, and prolonged action antiaggregate effect with the terpenophenols, show any significant hemorheological and antioxidant effect, will create a new macromolecular substance has complex pharmacological properties. The sulfate, phosphate polysaccharides of plant origin are obtained for develop new and effective means of anticoagulation deprived of side effects, which have a heparins. Cellulose, due to its high biocompatibility and availability, especially in the form of structural modifications - powdered cellulose is one of the most promising biopolymers for a class of sulfate of polysaccharides and anticoagulants based on them. This will allow get on their basis highly effective medicaments for the treatment of cardiovascular disease and effects of strokes, heart attacks. The work has been carried out with the financial support of Ministry of Education and Science of the Russian Federation (State contract №16.512.11.2012), Russian Academy of Sciences ("Basic Sciences - Medicine" project № 09-II-3-1021).

CATALYSIS IN INTEGRATED BIOREFINARY

B.N. Kuznetsov Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia [email protected]

The US National Renewable Energy Laboratory (NREL) has described a biofinery as a facility that integrates biomass conversion processes and equipment to produce fuel, power, and chemicals from biomass. The biorefinery of the future will be analogous to the petrochemical refinery of the present: the integrated processes that are optimized for energy efficiency and resource utilization. The success of the petrochemical industry can be attributed to an application of the processes of heterogeneous catalysis. Similarly, the future success of biorefineries will require a fundamental understanding of

117 the types of processes best suited for biomass conversions to various chemicals and biofuels and the design of a new generation of catalysts for the selective processing of carbohydrates and lignin. The preliminary fractionation of biomass on individual components opens a new prospects for advanced high-performance biorefinary. The following methods of wood biomass separation were studied by authors: catalytic oxidation by molecular oxygen in water-alkaline medium to cellulose and aromatic aldehydes; catalytic oxidation by hydrogen peroxide in acetic acid-water medium to cellulose and to low molecular mass lignin (LMML); two-step catalytic hydrolysis to xylose, glucose and hydrolytic lignin; exploded autohydrolysis (short-time cracking by overheated steam) to cellulose, LMML, C6-sugars, furfural; catalytic cracking by overheated steam to levulinic acid and condensed lignin. Depending on the used method of wood biomass fractionation and type of further transformations of primary products the biorefinary can be directed on dominant production of liquid biofuels or chemicals. The suggested process of integrated biorefinary of plant biomass (wood and agricultural residues) includes the following steps:

Lignocellulosic biomass

Fractionation by catalytic oxidation or exploded autohydrolysis

Nanoporous Lignin Cellulose carbons

Liquid Binding Modified Levulinic Sorbents Glucose fuels agents cellulose acid

Wood Biodegradable Bioethanol composites polymers

For promotion the key chemical reactions of integrated transformations of biomass (separation on cellulose and low molecular mass lignin, acidic conversions of cellulose to glucose, levulinic acid, levulinic acid ethers and the low molecular mass lignin conversion to aryl ethers, benzol, phenol) the different catalysts were used.

BETULIN COMPOSITES AND THEIR ANTIULCER PROPERTIES

S.A. Kuznetsova1, M.A. Mikhailenko2, T.P. Shakhtshneider2, Yu.N. Malyar1, G.N. Skvortsova1, O.F. Veselova3, V.V. Boldyrev2 1 - Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia 2 - Institute of Solid State Chemistry and Mechanochemistry SB RAS, Novosibirsk 3 - Krasnoyarsk State Medical University, Russia [email protected]

Betulin, (3β, 28-dihydroxy-20 (29) Lupeni) is the pentacyclic triterpene alcohol, derived from birch bark. The wide range of natural tritherpene activities (anti-inflammatory, anti-tumour and immunostimulating, etc.) have prospects to creation on their base of drugs. One of the main barriers for the use of betulin and its derivatives is their low biological availability related to poor solubility. Mechanochemical activation (MA) of pharmaceutical substances in the presence of excipients can be used to improve solubility of drugs to increase their bioavailability.

118 In the present work, the mechanocomposites of betulin with water-soluble polymers were prepared and antiulcer activity of betulin and its MA composites was studied. Betulin was obtained from the bark of birch. Polyvinylpyrrolidone (PVP) (Mr = 12,600 and 360,000) (Sigma-Aldrich) was used without pre-cleaning and drying. Mechanochemical activation of the initial components and the mixtures was carried out in a planetary centrifugal mill AGO-2 (ISSC, Russia). X-ray diffraction analysis was performed on a diffractometer D8 DISCOVER with two-dimensional detector GADDS (Bruker), CuKα-radiation. The concentration of betulin in an alcohol solution was determined by liquid chromatograph Milihrom A-02 (“EcoNova” Ltd., Russia), column ProntoSil C18, mobile phase - water-acetonitrile. Antiulcer activity was studied on 30 male white mongrel rats. The experimental model of ulcer formation was carried out by introducing via metal tube into the stomach by 0.1 HCL 4.5 ml. The test substances were introduced one hour before the introduction of HCL for the implementation protector models or one hour after the introduction of HCL for correction model in experiment. After mechanochemical activation, a disorder of the crystal structure of betulin was observed. Mechanochemical activation of mixtures of betulin with PVP leads to the homogenization of the mixtures by dispersing the components and the formation of composites. With increasing polymer content in the composites, the disordering of the crystal lattice of betulin until complete amorphization was indicated. Solubility of the composites of betulin with PVP in water was improved compared with the original betulin. It may be due to amorphization of betulin, as well as solubilizing action of the polymer and the formation of intermolecular complexes of betulin with PVP. It was established that in the case of MA composites of betulin with PVP, the antiulcer and protective activity in equal doses of introduction was higher than the activity of original betulin. Antiulcer activity of the MA composites of betulin was 3.81 units, while betulin - 2,52 units, taking into account index Pauls.

The work was supported by the RAS Program “Fundamental Sciences for Medicine”.

ANTICANCER PROPERTIES BETULIN AND BIRCH BARK EXTRACT

S.A. Kuznetsova1, I.I. Morgulis2 1 - Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia 2 - International Scientific Centre for Organism Extreme Research attached to the Presidium of the Krasnoyarsk Scientific Center of SB RAS, Krasnoyarsk, Russia [email protected]

The outer layer of birch bark is a unique source of valuable biologically active substances. Betulin is the main of them. Betulin and birch bark extractive have been proposed for use in cosmetics as an additive to shampoo, skin-care, dental-care and hair-care products. For these purposes, however, pure betulin is not usually used, but rather birch bark extract. Fundamental research into the bioactivity of betulin and betulin derivatives are ongoing. Conservative methods (radiotherapy and chemotherapy) play now an impontant role in oncologic patients therapy. The preparates being used in chemotherapy are known not to be selective. They may induce cell death of both tumour and other tissue cells. So current clinical investigations are directed to development of medicinal preparates with specific effects on the tumour cells. The prospects of using betulin and ethanol extracts of birch bark for prevent and treatment of tumors Ehrlich ascites carcinoma was studied in this work. Betulin was obtained and recrystallized from the birch bark. Identification of the betulin was confirmed using physicochemical methods (IR, NMR spectroscopy, gas chromatography and mass spectrometry). Ethanol extracts was obtained from birch bark extraction in the Socsklett´s apparate. The analysis of obtained substances was conducted by using chromato-mass-spectrometry.

119 Experimental mice of the group 1 were injected with substances investigated 9 days before EAA inoculation and during 18 days after. The animals of group 2 were given with our substances during 18 day after inoculation. The mice of group 3 were given only standard food. One of adequate methods for whole organism state evaluation is peripheral blood investigation, so we have measured blood parameters. On days 9 and 18 after EAA inoculation we evaluate total value of tumour cells in ascytic fluid and the fractions of the dead and alive EAA cells. It´s demonstrated that betulin has more pronounced anti-tumour effects than ethanol birch bark extracts. Ethanol extracts induced cell death 3 time more then in the control group 3, but betulin induced 6,6 times more. Dead cells contents was higher in 18th day than in 9th. It can be concluded that bethulin has positive effects on the peripheral blood parameters and leucocyte formula in animals bearing EAA.

This work is supported with the grant of RAS Program “Fundamental sciences – for medicine”

PRODUCTS FROM A BIRCH BARK FOR THERAPY OF DIFFERENT DISEASES

S.A. Kuznetsova1, O.F. Veselova2, Yu.N. Malyar1 1 - Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia 2 - Krasnoyarsk State Medical University, Russia [email protected]

A birch bark contains various extractive substances having biological activity and representing potential interest for production of new products. The birch outer bark is an available source of biologically active triterpenoids primary presented by betulin, causing white colour of a birch bark. The content of betulin in outer birch bark varies from 10 up to 40 %, depending on birch nature, place and conditions of its vegetation, age of a tree and a season. The birch outer bark for a long time was used for production of birch tar, which till now is applied in pharmacology and veterinary, as antiseptic and anti- scab agent. The birch outher bark in national medicine also was used in quality antiseptic at treatment of purulent wounds and various skin diseases. Intensive researches of pharmacological action of betulin and others triterpenoids of a line lupine recently will be spent. Betulin has antiseptik, anti-virus (virus herpes and Epstein-Barr), antiinflammation, hepatoprotective, antioxidative and other useful properties. Betulinic acid and its derivatives can suppress growth of melanоm and virus HIV. Betulin also can be used for synthesis of new classes of biologically active compounds. All specified properties of betulin open new opportunities for their application in medicine, pharmaceutical, parfumerno-cosmetic, food and other branches ofproduction. Pharmacological properties of betulin, extractive substances from outer birch bark and enterosorbent from inner birch bark were investigated. According to the results of toxicological study, accomplished on white mousses the all substensis from outer birch bark belong to the 4th class of low-toxic substances. For the first time it was established, that betulin shows capillaroprotective action. The capillaroprotective properties of betulin are higher, than that of known natural preparation - dihydroquercetin. Obtained data show that betulin and hexane extract of birch outer bark demonstrated the antioxidative, hepatoprotective, antytumor and immuno-modulator actions. It was shown, that enterosorbent produced from the inner birch bark and from all part of birch bark is capable to suppress the development of stomak infections. The results of toxico - farmacologycal study of biologically active substances from birch bark can be used for the development of new preparations with antioxidative, capillaroprotective, hepatoprotective properties and remedy for treatment of stomak infections.

The work was supported by the RAS Program “Fundamental Sciences for Medicine”.

120 FABRICATION OF PECTIN BASED NANOCOMPOSITES FOR BIOMEDICAL APPLICATIONS

K.A. Kydralieva1, N.G. Zakharova2, B.M. Khudaibergenova3, E.M. Khudaibergenova1, N.V. Gorbunova4, Sh.J. Jorobekova1 1 - Institute of Chemistry and Chemical Technology, NAS, Kyrgyz Republic 2 - Moscow Aviation Institute 3 - Institute of Biotechnology, NAS, Kyrgyz Republic 4 - Institute of Applied Biochemistry and Machine-Building, Moscow [email protected]

The objective of research is to produce nanocomposites based on amongst other natural polymers pectins that could lead to novel interesting products for targeting the treatment related to antitumor activity. Both the leaves and the roots of Beta vulgaris were the objects for the isolation of the pectic polysaccharides present in both parts of the plant due to its low gelation capacity owing to the low molecular masses and high content of acetyl groups. Acetylated pectins find application owing to their emulsifying properties, which can be used in drug delivery system as nanobubbles. After removal of low molecular weight and lipofilic material, the plant material was extracted with water. These extracts were purified by dialysis, and separated into neutral and acidic polysaccharides by anion exchange chromatography. Further purification and isolation were performed using gelfiltration. The products obtained were investigated for their bioactivity in the complement system, a system that is well suited for the identification of products that have an influence on the immune system. The monosaccharide composition was determined by the use of gas chromatography as well as by HPAEC-PAD chromatography. The linkage determination was determined using a series of chemical methods in order to obtain the partly methylated alditol acetates. This mixture has been analysed by gas chromatography combined with mass spectrometry in order to show how the different monosaccharides are linked to another monosaccharide. Enzymatic degradation combined with separation by gelfiltration concomitant with determination of the bioactivity will give the information on what part of the pectin that is important for the bioactivity. This fraction will be the part of the molecule that is chosen for further use in the project. Molecular size will also be determined by FPLC.

This research is supported by International Science and Technology Center (ISTC Project KR- 1880).

ANTIRADICAL ACTIVITY OF THE VEGETABLE EXTRACTS, OBTAINED IN THE MEDIUM OF SUBCRITICAL WATER

Yu.O. Lesishina, I.I. Volodchenko, A.F. Dmitruk Donetsk national university of economics and trade named after Mikhail Tugan-Baranovsky [email protected]

The aim of this work was to study qualitative and quantitative composition of the vegetable extracts obtained in the medium of subcritical water (superheated water under pressure at temperatures from 373 to 647 K) and to estimate its antiradical activity. As objects of research were used: leaves and flowers of Crataegus sanquinea Pall., flowers of Tilia cordata Mill., Helichrysum arenarium L., Matricaria recutita L. and grass of Hypericum perforatum L. The extractions in subcritical water were performed as follows: a samples of ground plant raw material were placed in the stainless steel reactor and then bidistilled water were added in the ratio raw material:bidistillate = 1:10. The reactor was tightly closed and exposured at 393 K for 10 minutes. After cooling of the reactor to a room temperature its innage were consistently treated with water, ethanol, ethyl acetate and hexane.

121 Due to subcritical water extraction it can be possible to extract from a plant raw materials about 38 % of the various chemical nature substances, among which there are phenolic compounds. Water- soluble fractions of the obtained extracts had a maximum yield of solid residue (17 – 30 %); solid residue yield of ethanol fractions was 3-6 %; ethyl acetate fractions – 1 – 3 %. Hexane fractions had a minimum yield of solid residue (0,4 – 0,7 %). By methods UV - and IR - spectroscopy it was established that water-soluble fractions of extracts basically contain simple phenols and restored forms of flavonoid compounds (catechins, leukoanthocyanidins, etc.), carbohydrate components; while ethanol-soluble fractions contain flavonoids (flavones, flavonols and its glycosides), phenolcarboxylic acids, methoxylative derivatives of these compounds. Results of qualitative analysis of the content of phenolic compounds in water-soluble and ethanol- soluble fractions of extracts are presented in the table 1. Table 1. extract Total content of phenolic Total content of flavonols*, compounds*, tannin % rutin % water-soluble ethanol- water-soluble ethanol- fraction soluble fraction soluble fraction fraction Crataegus sanquinea Pall. 0,88 1,29 0,41 0,49 Tilia cordata Mill. 3,19 0,49 0,23 0,31 Helichrysum arenarium L. 2,51 0,83 0,29 1,48 Hypericum perforatum L. 2,71 2,35 0,46 1,84 Matricaria recutita L. 5,30 1,45 - 0,80 * In recalculation on air-dry raw material

Antiradical activity (ARA) of water-soluble and ethanol-soluble fractions of extracts was estimated by magnitude of a reaction rate constant (k) of interaction with a free stable radical diphenilpicrylhydrazyl (DPPH). Change of concentration DPPH was defined by spectrophotometric method at the temperature of 290 K. Water-soluble fractions and ethanol-soluble fractions of all vegetable extracts have antiradical activity. The reaction kinetics of observable fractions with DPPH in the range of 0-200 sec is followed to the kinetic equation of the pseudo-first order on DPPH, except for water fraction of an extract of an Helichrysum arenarium L. ARA of water- soluble fractions of different plants´ extracts is practically identical (k≈0,1 sec-1), ARA of ethanol- soluble fractions is changed in range of 0,03-0,44 sec-1.

NEW AROMATIC DERIVATIVES OF BETULIN

M.Y. Lezhneva1, T.A. Mikheyeva1, I.V. Shtrants1, A.S. Us1, A.S. Zozulkina1, V.Y. Nikonov1, O.V. Kaminskaya1, I.I. Bondarenko1, N.M. Volkova1, T.V. Bogdanchikova1, Y.S. Sidorenko1, K.Y. Gavrilova1, S.M. Adekenov2 1 - North Kazakhstan State University named after M. Kozybayev, Chemistry, Petropavlovsk, Kazakhstan 2 - Scientific Production Centre “Phytochemistry”, Karaganda [email protected]

Triterpene alcohol betulin, which is easily and efficiently derived from the birch bark [1], is a potential syntone for various chemical modifications used in order to create new biologically active compounds. The labile lupane structure of betulin is dehydrated in ring A under the influence of sulfuric acid, after which the formed double bond migrates until coupling takes place in rings C and D. As a result, a system of coupling ties is formed [2]. While creating the stable conjugated structure, terpene compounds undergo the stage of forming carbcation, which is an active electron-seeking reagent.

122 This fact facilitated the implementation of a series of electrophylic substitution reactions in aromatic compounds in which triterpene compound carbcation acts as an electron-seeking reagent (in particular, betulin-based carbcation). The bulk structure of carbcation contributes to its low stability. As a result, this reagent enters into electrophylic substitution reactions only with active substrates. Aromatic derivatives which were activated with the help of electron-donor substituents, such as: acetanilide, tyrosine, and tryptophan, were used as the substrates. As a result, derivatives (1-3) were formed. H OH H N N NH2

H2N O HOOC HOOC

CH2OH CH2OH CH2OH

HO HO HO 1 2 3 The composition of the derivatives is verified due to the elemental analysis and infrared spectroscopy. The stretching vibrations: O—H – 3396.7 cm-1; C—H of the lupane skeleton – 2876 cm-1; C–C of the aromatic ring – 2448.2 cm-1; C=O – 1691.6 cm-1; stretching vibrations N–H are equal to 3393.7 cm-1. The projected biological activity of the substances was tested with the help of the computer program named PASS. According to PASS, all the betulin-based derivatives possessing the aromatic ring have a marked transferase-stimulator activity and hepatoprotecting activity. Simultaneously, the probability of their toxicity is low. Summing up, this direction of forming betulin-based derivatives has good prospects in the field of getting new biologically active substances.

References 1. Prepatent # 16091 RK, (51)7CO7J63/00. Betulin Getting Method / V.V. Polyakov, M.Y. Lezhneva, E.A. Vergassov. – Published on August 15, 2005; Bulletin № 8. 2. Oganesyan, Eduard. On the mechanism of triterpenoid reactions with sulfuric acid // Natural Compound Chemistry. – 1980. - № 5. – PP. 23-25.

RESEARCHES OF FRUIT BREED ZIZYPHUS JUJUBE AS BIOLOGICALLY ACTIVE RAW MATERIALS IN THE FOOD-PROCESSING INDUSTRY

L. Linda, D. Nicolaeva, M. Podogova, V. Caragia Practical Scientific Institute of Horticulture and Food Technology [email protected]

The Ziziphus fruit breed Jujube Mill concerns to high-value raw materials, having equally both food, and biological value. High food value and a wide spectrum of treatment and prophylactic action of products of processing ziziphus fruits are due to the presence of the biologically active substances necessary for the human health. The generic name is Ziziphus, and the most widespread kind - jujube. The ziziphus is one of most tolerant fruit crops to drought and heat and wild breeds grow in such countries as China, Afghanistan, Syria, Iran, India, Japan, and also in Central Asia, Transcaucasia. It does not require the use of protective chemicals for cultivation. The introduction and selection of the varieties of ziziphus in Moldova was made at the Scientifically-Practical Institute of Horticulture, Viticulture and Food Technologies since 1975. During the period from 1990 till 2005 there were made researches in the Institute for different varieties of ziziphus fruits for the purpose of their use as raw materials for food branch.

123 The basic directions of the use of ziziphus fruits were established by testing raw materials and the products of its processing. Thus, there were defined the physical, chemical and technical characteristics of the raw materials, there were elaborated recipes of products based on ziziphus and were established the organoleptic, physical and chemical indexes (for mashed fruits, compotes, marinades, jam, candied fruits) and also the nutritional value of products. There were performed analysis for functionality of products from ziziphus in medical research establishments (Institute of Pediatrics and Obstetrics АМN of Ukraine, in the Center of Radiating Medicine of Ukraine) using the accepted techniques of making clinical tests. The fruits of ziziphus are high biological value due to vitamins in raw materials . According to the physicians, the natural vitamins from fruits and berries, being in certain natural combinations, are much more effective, than synthetic additives. In the ziziphus fruits, in comparison with other breeds, the content of vitamin C (ascorbic acid) is much more than in fruits of citrus or black currants. The results of researches made in industrial conditions, have shown that fruits of different varieties have different content of vitamin C in pulp (from 327 mg/100g to 533 mg/100g), different content of dry substances – (from 21 % to 37,2 %) and different acidity (from 0,36 % to 1,48 %). It was remarked the tendency of increasing the content of vitamin C in fruits during thermal processing, that could be explained by the liberation of the connected forms of vitamin C and their transition in the active form. Other important biologically active substances of ziziphus fruits are Р - active substances (polyphenols). The content of vitamin Р in ziziphus fruits is 150-750 mg/100g. Considering the complex of biologically active substances the ziziphus is unique among the fruit cultivated in the Asian and European countries. The tests made in the nineties in children’s of younger age clinic and in radiological laboratories (Institute of Pediatrics and Obstetrics АМN of Ukraine, in the Center of Radiating Medicine of Ukraine) on the product of processing of ziziphus fruits - the ziziphus paste - have shown that the application of this product in the food of sick children promotes quickly (within 10-12 days) avitaminosis liquidation, positively influences the indicators of red blood, strengthens nonspecific immunity. At its long consumption essentially decreases the level of radio nuclides in adult’s and children’s organism and fortifies the immunity to various diseases, like catarrh, pneumonia and others. The ziziphus paste is recommended as natural vitamin correcting food additive for baby food. It provides the daily requirement for vitamin C. Products from ziziphus fruits could be considered as food having the role of a natural food additive, without strict restrictions in its use. There was elaborated the technology and the technical documents for the fabrication of canned food from ziziphus (pastes, compotes, marinades, desserts, candied fruits, dried products) which was tested in the food industry.

Literatura: 1. Настас Г. Малораспространенные плодово-ягодные растения //Кишинев, Картя молдовеняскэ», -1987, с.182. 2. Ксенофонтова Д.Научные основы создания промышленных садов унаби в Краснодарском крае//Интеграция науки и производства и развитие субтропического растениеводства: Тезисы докладов научно-технической конференции. Сочи, -2003, с.86-91.

SYNTHESIS OF COVALENT SUPRAMOLECULAR COMPLEXES BASED ON CHLOROPHYLL AND BIOCOMPATIBLE MACROMOLECULES

A.V. Lobanov1, A.N. Shchegolikhin2, G.G. Komissarov1 1 - Semenov Institute of Chemical Physics RAS, Moscow, Russia 2 - Emanuel Institute of Biochemical Physics RAS, Moscow, Russia [email protected]

For development of synthesis of covalent supramolecular complexes of tetrapyrrolic compounds the study of binding of Chl b with a water-soluble polymers - albumin (BSA) and polyvinyl alcohol

124 (PVA) was carried out. Immobilization of Chl b was performed in a two-phase system water / carbon tetrachloride. Conjugation with the polymers was carried out more efficiently in the case of Chl b than for Chl a. Participation of -CH=O group of Chl b in covalent bonding with the N- and O- containing amino acid substituents BSA and the hydroxyl groups of PVA was shown by IR and incomplete internal reflection spectroscopy. The IR spectrum of complex Chl b - BSA contains bands with wavenumbers 2143 and 2182 cm-1 characteristic for the C = N. These bands were absent in the IR spectra of Chl b, BSA and the complex of Chl a - BSA. Consequently, the interaction of Chl b with the BSA results to imine bond (Schiff base) formation:

NH2 + O=CH Chl b N=CH Chl b

BSA BSA

Schiff bases are known to be quite labile. However, restoration of communication imine -N=CH- allows to obtain a stable amine bond -NH-CH2-. In the infrared spectrum of the complex Chl b - BSA, treated with NaBH4, it was discovered the band at a frequency of 1150 cm-1 characteristic for the C-N. Thus, the formation of complex with Chl b protein is caused not only by weak interactions (ionic, ion-dipole, dipole-dipole, van der Waals, hydrogen bonds), but the covalent bond. The IR spectrum of complex Chl b - PVA a band at 1390 cm-1 was observed, which is absent in the IR spectra of Chl b, Chl a - PVA and PVA. This band is typical for dioxolan cycle, which proves the formation of a covalent bond between the formyl group of Chl b and PVS hydroxyl:

OH OH

OH O + O=CH Chl b CH Chl b OH O ПВС ПВС

Thus, Chl b is capable to form covalent bonds with functional groups of some water-soluble polymers. On the one hand, it indicates the possibility of covalent binding of Chl b in vivo, and, on the other hand, it makes such structures suitable objects for the biophysical and pharmacological studies. This work was supported by the Grant of President of Russian Federation for the state support of young Russian scientists - candidates No MK-227.2011.3, Program of Presidium of RAS No 3, No 25, and Leading scientific school (grant NSh-65059.2010.3).

SYNTHESIS OF DIISOBORNYLQUINON

I.V. Loginova, I.Yu. Chukicheva Institute of Chemistry, Komi Science Center, Ural Branch of RAS, 48, Pervomaiskaya st., Syktyvkar, Russia [email protected]

Interest in terpenophenols explained not only by the possibility of using them as reagents for the synthesis, modifiers and stabilizers of polymer, antioxidants of organic materials, but also as potentially physiologically active substances. The benzoquinones with isoprenoid side chains are play a crucial role at all levels of the organization of cellular life forms. They are indispensable components of the biochemical mechanisms of photosynthesis and respiration.

125 Quinones are among the medicines for the treatment of coronary heart disease, muscular dystrophy, in cases of poisoning with heart poison, as antibiotics, anticancer agents. Development of methods for quinones of sterically hindered phenols is of practical interest. This paper presents the results of the synthesis of 2,6-diisobornylbenzoquinon by the reaction of chlorine dioxide oxidation of 2,6-diisobornylphenol and 3,5-diisobornyl-4-hydroxybenzaldehyde containing chiral terpene fragments.

OH O ClO2

R O

R= H, HCO

The synthesized compound is yellow crystals with a melting point of 223-225 ° C. The structure of the first obtained compound was proved by IR and NMR spectroscopy.

RECOVERY OF ANTHOCYANINS FROM GRAPE POMACE EXTRACTS (PINOT NOIR) USING MAGNETIC MICROPARTICLES BASED ON POLYVINYLALCOHOL

T.S. Lozovskaya1, M. Franzreb2, M. Nusser2, G. Brenner-Weiss2 1 - Voronezh State Technological Academy Organic Chemistry Voronezh Russia 2 - Karlsruhe Institute of Technology Institute of Functional Interfaces Karlsruhe Germany [email protected]

In order to make food optically more attractive food dyes, both synthetic and extracted from plant materials, are widely used. In comparison, from the standpoint of healthy eating, the use of natural dyes is preferable. In addition, finding ways to stabilize the color pigments, expanding the color palette, as well as recovery of pigments from plant materials will expand the use of natural pigments. The first natural red dye «enocyanin» was obtained from the pomace of red grapes and produced in Italy since 1879. Despite the significantly expanded resource base, the waste of wine production remains one of the economically attractive sources of anthocyanins. In addition, recent studies have shown that the pigment composition of dark skin grapes presented the most resistant to temperature and pH molecules. The paper considers the possibility of obtaining a concentrate of anthocyanin pigments from grape pomace extract (Pinot noir) using magnetic microparticles on the basis of polyvinyl alcohol (M-PVA) having an average size of only approx 2 μm. The used polymer matrix provides a number of advantages, such as hydrophilicity, availability and cost efficiency. When using magnetic microparticles the sorption step is conducted in a well mixed vessel within a few minutes, followed by a simple solid/liquid separation step applying magnet technology. To obtain an extract the grape seeds were separated from the skin, using a sieve. Plant material was crushed and immersed in 0.1% HCl at a ratio (w/w) of raw material to solvent of 1:2.5. Extraction was carried out at 50 0C for 2 hours. The extract was rapidly separated from the feedstock by coarse filtration applying a sieve (100 mesh). The concentration of total monomeric forms of anthocyanin, determined by the pH-differential method, in the resulting solution was 13 mg/L, pH = 3.2. Analysis of the extract by high performance liquid chromatography showed that the main pigment is Malvidin-3-0-β-glucopyranoside. In a comparison of different surface functionalisations plain polyvinylalcohol beads with OH- groups showed to be the most efficient in the recovery of anthocyanins. Applying a particle concentration of 10 g/l 40% of the pigments present in the extract were absorbed. Desorption carried out with ethanol (99%) containing 0.1% HCl eluted up to 85% of the adsorbed pigments.

126 Judging these numbers one have to keep in mind, that the base material is available at practically no costs in huge amounts, and that in this case simplicity and speed of the process are more important than high percental yields. The comparison of the sorption capacities of M-PVA and nonionic sorbents (Amberlite XAD-16 and XAD-4, Stirosorb MHDS-100) commonly used for extraction of polyphenols showed that after 10 minutes adsorption of pigments from an aqueous solution the efficiency of the magnetic microsorbents was always higher than the ones of the larger polymer sorbents. For example, the adsorbate concentration per unit of weight of M-PVA at pH=4.4 is seven times higher than the one of Amberlit XAD-16 and reaches the value 1,05±0,08 mg/g. In addition, the results showed the effectiveness of magnetic microsorbents in the recovery of anthocyanins from cloudy solutions. Finally, the possibility of the repeated reuse of the microsorbents without special treatment for cleaning was demonstrated over 7 cycles. Future work will concentrate on an improvement of the sorbent capacity and on the scale-up of this simple and fast pigment isolation process.

PROCESSING OF ARTISAN RICE HULLS BY COMBINING DILUTE-ACID HYDROLYSIS AND NMMO TREATMENT

Y. Lуpez1, K. Karimi2, M.J. Taherzadeh3, C. Martin1 1 - Department of Chemistry and Chemical Engineering, University of Matanzas, Cuba 2 - Department of Chemical Engineering, Isfahan University of Technology, Isfahan, Iran 3 - School of Engineering, University of Borеs, Sweden [email protected]

Because of their particular composition, artisan rice hulls, which are produced in small-scale mills that are common in rural areas, are a promising raw material for ethanol production in Cuba. In addition to cellulose and hemicelluloses, artisan rice hulls contain up to 15% (DM) starch, which can be hydrolysed and converted to ethanol. However, starch is a challenge to the hydrolytic process, since the glucose resulting from its hydrolysis is sensitive to be destroyed under the standard pretreatment conditions. In the current work, the optimization of dilute-acid hydrolysis of starch was performed using a central composite experimental design. The investigated factors were temperature (70 – 150ºC), biomass load (5 – 15 %), acid concentration (0 – 2%) and reaction time (30 – 90 min). The maximum hydrolytic conversion (97.02%) was reached at 125ºC, 1.36% (v/v) sulphuric acid, 8.04% of solids, and during 74 min of reaction time. Under those conditions, the recovery of xylose from hemicelluloses’ hydrolysis was also high (82.3%), and the formation of furfural and hydroxymethylfurfural was low. The resulting cellulignin was either delignified with NaOH or submitted to treatment with N-methyl-morpholine-N-oxide (NMMO), and then hydrolysed with commercial cellulases. The highest enzymatic convertibility (84.0%) was achieved in the NMMO-treated cellulignin. On the other hand, direct NMMO pretreatment was not effective for improving the enzymatic hydrolysability of artisan rice hulls.

ROLE OF L-CARNITINE AND SILYAMRIN IN THE PREVENTION OF ACUTE LIVER DAMAGE INDUCED BY CARBON TETRACHLORIDE IN MALE RATS

H.I. Mahmoud, E.S. Shaker, H.S. Abdel-Salam, A.G. Darwish Minia University, Agricultural biochemistry Department, Minia, Egypt [email protected]

Background and Aim: Lipid peroxidation appears to be the most important mechanism in the pathogenesis of acute liver damage caused by CCl4. the present work aimed to study the protective role of L-carnitine against the acute dose of CCl4 liver intoxication comparing to Hepaticum, which contains sylimarin the standard hepatoprotective drug for treatment of liver diseases. Material and methods: Twenty four male rats allocated to four equaled groups; (1) Control group; (2) CCl4 group: injected with intraperitoneal CCl4 single administration 2 ml/kg body weight; (3)

127 Silyamrin + CCl4 group: the same as CCl4 group and oral administration with hepatoprotective standard drug Hepaticum (100 mg silymarin/kg b.w. daily); (4) L-carnitine + CCl4 group: the same as CCl4 group and oral administration with 100 mg L-carnitine/kg b.w. daily. Liver enzymes activities, lipid peroxidation (MDA), reduced glutathione (GSH), the tumor marker α-L-fucosidase and lipid profile was studied beside the Histopathological investigation of the liver. Results: L- carnitine followed by silymarin significantly ameliorated daily body weight gain and feed efficiency with decreasing the liver weight after CCl4-induced damage. Obvious significant decrease (P<0.01) in liver enzymes activities has been noticed for L-carnitine followed by silymarin especially for AST activity. Silymarin showed significant decrease in lipid peroxidation (MDA) than L-carnitine treatment did. The standard hepatoprotective drug silymarin significantly increased GHS followed by L-carnitine after CCl4-induced damage. Silymarin was significantly better than L- carnitine effect in decreasing total cholesterol with HDL-c increasing and lowering the risk factor comparing with CCl4 group. Few improvements for L-carnitine and silymarin have been shown in Histopathological investigation compared with CCl4 group. Conclusion: L-carnitine showed obvious amelioration in the most studied biochemical and histopatholigical measurements. That indicated the potential use of L-carnitine as protective and treatment for liver diseases comparing to hepatoprotective standard drug silymarin.

THE INFLUENCE OF MECHANOACTIVATION ON THE BIOLOGICAL ACTIVITY OF PEAT LIPIDS

E.V. Maltseva, K.V. Miheev, N.V. Yudina, V.N. Burkova Institute of Petroleum Chemistry RAS SB, Tomsk, Russia [email protected]

The basic tendency of development of the industry at modern level is engineering of wasteless and low-waste technologies of ecologically pure products from natural raw materials. One of such kinds of materials is a high-moor peat, where lipids are one of the major components, possessing high biological activity. However high-molecular compounds of peat are bound in the difficult organic complexes forming micro-and macrostructures with strong bonds in it that complicates their extraction. One of methods of increase of product yield from natural materials is mechanoactivation of the peat, causing changes in porous supramolecular structure, a physical condition and properties of peat and raising efficiency in the process of extraction. As object of research was taken high-moor sphagnous peat of Tomsk area which had degree of decomposition is 5 %. Mechanoactivation of peat was fulfilled in a mill of planetary type АGO-2С with frequency of rotation of drums 1820 about/mines-1 and centrifugal acceleration - 600 m/s2. Grinding bodies were steel spheres in diameter 8 - 10 mm, processing time made 2 minutes. Lipids were extracted with double spirit-chloroformic extraction from peat. Research of cardio protective properties of lipids липидов was made in laboratory of expert cardiology of scientific research institute of cardiology of the Tomsk scientific centre. In this work the influence of mechanoactivation of high-moor peat on lipid yield, a content of resinous and wax parts, neutral and acid fractions, the content of carotinoids and chlorophylls was researched. The estimation of antioxidative activity of initial lipids and extracted from of peat after mechanoactivation was made. It is established, that mechanoactivation of peat promotes increase lipid yield in 1,5 – 2,0 times depending on conditions. Thus, the part of acid fractions, content of carotinoids and chlorophylls increase in lipids that is explained with the destruction of intra- and intermolecular bonds in associate complexes formed by active oxygen-containing groups. Lipids of mechanoactivative peat show antioxidative activity which twice exceeds at initial lipids in a range of concentration 0,2 - 1,0 mg/ml. The inhibition degree of peroxide oxidation in lipids is detected in relation to preparation “Essentiale” at concentration in 10 times less. Mechanoactivation of peat allows to regulate qualitative content of antioxidative functional groups in lipids. The increase of antioxidative groups is explained with the structure change of lipids, in particular, the destruction of bonds between 128 hydrophilic part and hydrocarbon residues in macromolecules and enhancement of quantity -ОН, - NH2, -SH2 and other functional groups with labile hydrogen atom. Therapy of acute aseptic inflammation by peat lipids showed that oppression degree of carageenen- induced edema reaches 40 % as compared with the control.

CELLULOSE PRODUCING BY OZONATION OF WOOD

N.A. Mamleeva1, S.A. Autlov2, N.G. Bazarnova2, V.V. Lunin1 1 - Lomonosov Noscow State University,Chemistry Department 2 - Altai State university Chemistry Department [email protected]

The development of raw vegetable materials processing is connected to new oxidative delignification technologies. Ozone has been known as a strong oxidant of a lot of organic compounds. In general, ozone reacts with organic substrates by ozonolysis, i.e. ionic cyclo-addition to, and cleavage of unsaturated and aromatic bonds. As the only product of ozone conversion is oxygen, so one would expect that the ozonation process would be the environment friendly pathway of raw vegetable materials processing. The goal of this research was to study the kinetics of wood ozonation, to find out the relationship between the ozone demand (OD) value and the delignification degree of the substrate. Properties of cellulose extracted from wood treated with ozone were also in the sphere of our interest. Ozonation of aspen wood of various (8 -160%) moisture content (MC) was studied. The wood transformations as well as lignin conversions with ozonation of the wood were investigated by UV- and FT-IR spectroscopy. It was determined the acid insoluble lignin content of the samples treated with ozone. Holocellulose as well as cellulose were extracted from the wood samples by standard procedures. It was determined the average polymerization degree (PD) of cellulose based on viscosity measurements. Cellulose molecular mass distribution (MMD) curves were obtained with turbidimetric method. OD value corresponding to completion of the sample ozonation was found to increase with increasing MC. This result was explained by swelling of wood in the presence of water vapor. Moreover, ozone interaction with some products of aspen wood ozonation is responsible for OD increasing. As found, some of them are soluble in water presenting in the wood structure. IR and UV data indicate that lignin oxidative destruction occurs first of all. Carbohydrates disturbance is observed under ozonation, too. As for the chemical processes occur under the ozonation conditions, we suppose that apart from molecular ozone OH•- radicals formed owing to ozone reactions with water could be also the active species that oxidize lignin as well as carbohydrates of the wood. The delignification degree of wood depends on OD strongly. Aspen wood delignification is accompanied by increasing cellulose yield, and PD decreasing from PD = 700 (initial sample) to PD = 220. This PD value corresponds to the sample of 93% delignification degree. The MMD data indicates that cellulose obtained in this case is characterized by the uniform MMD. The content of cellulose in the samples treated with ozone is about 75-78 %. It was shown that direct ozonation of deciduous wood is attractive for producing fiber material of high cellulose content.

129 A STUDY ON THE EFFECT OF EXTRACTS ISOLATED FROM ONOPORDUM TAURICUM WILLD. SPECIES ON REPLICATION OF RAT HEPATOCYTES

R. Mammadov Pamukkale University, Turkey [email protected]

Medicinal plants are considered as healthy sources for the life. Therapeutical properties of medical plants are also known in the cure and their advantages are 100% as natural. Nowadays people are focused on thousand of unhealthy products, the level of sensibility infront of diseases is very high and that's why the use of medicinal plants can represent the best solution. There are many plants used for medicinal purposes. Onopordum tauricum Willd. is an important species used for medicinal purposes. Onopordum tauricum Willd. (Taurian Thistle or Bull Cottonthistle) is a species of thistle. It is native to Eurasia and is known in the western United States as anintroduced species. Etheric oils are available of in these types as active substance. Onopordum acantium includes seed oil in view of its fatty acid compositions. Seed oil of Onopordum acantium also contains 2.14% of steroric acid ,4.46% of palmitic acid and 71.77 % of linoleic acid. Furthermore ,myristic, palmitolinoleic,cicosanoic and cicosenoic acid are found in trace amounts. In the experiments carried out on rats, the upper right part of the abdomen was cut with 3 millimetres incision and %50 percent of the liver were dissected then these operation were classified into three groups. One of these groups was control group (n=5), second group (n=5) and third group(n=5). After the dissection of the hepatic tissue, the abdomens of the rats were implanted to perpetuate their lives. The extractions obtained from the extractions of Crataegus pseudoheterophylla Pojark(hawthorn) (to second groups of rats in %0.5 and to third groups of rats in % 1.0 concentration) were added into the water of rats to enable them drink it orally. The liver enzymes of ALT, AST, GGT, which were regularly taken from cardiac area during six weeks, and UREA rate, whose variation in blood could be observed in the kidney functions, were altogether taken into consideration. The extract of 1.0% concentration was determined to be more effective on hepatocyte replication.

ESSENTIAL OILS OF NEPETA AMOENA STAPF FROM AZERBAIJAN

Z. Mammadova, R. Mammadov Pamukkale University, Turkey [email protected]

Nepeta is a one of the largest genera of the Lamiaceae family, considering the number of species. Some species within the genus have medicinal importance and their extracts have been used for medicinal purposes. Nepeta species are widely used in folk medicine because of their effects such as antispasmodic, expectorant, diuretic, antiseptic, antitussive, antiasthmatic and febrifuge activities. Nepeta is a genus of perennial or annual herbs and distributed in Asia, Europe and North Africa. Nepeta cataria (Catnip) is the most important species of Nepeta. It has used as a tea in Europe before real tea was imported from the orient. The flowering tops of plant have also been used as a sedative drug. The genus Nepeta are compose of about 250 species, of which, 26 are found in Azerbaijan. In this study, aerial parts of N. amoena Stapf was subjected to hydrodistillation and the chemical composition of the isolated essential oil was analyzed by GC/MS method for first time. These types of rate etheric oil 0.2%, retention index (RI) of the etheric oil was determined as the 1543. The major constituents of the sesquiterpene-rich oil of N. amoena Stapf were spathulenol (24.44%), beta caryophyllene (13.07%), caryophyllene oxide (10.53%), β- caryophyllne (11.27%), alpha cadinol (7.71%). The oil contains: monoterpene hydrocarbons, oxygen-containing monoterpenes, sesquiterpene hydrocarbons and oxygen-containing sesquiterpenes. These components of N. amoena Stapf species reveal that the structure of etheric

130 oils has a rich-forming. This rich structure are gained the therapeutic property to the genus Nepeta L., such as the type of N.amoena Stapf.

VOLATILE BIOLOGICALLY ACTIVE SUBSTANCES AND ANTIMICROBIC ACTIVITY OF FOREST PHYTOCENOSIS

N.V. Marina, G.N. Novoselova, V.A. Kryuchkov Ural state forestry engineering university, Ekaterinburg, Russia [email protected]

The unique property of plants is their ability to emit huge amounts of volatile substances in to environment and just this ability is responsible for these plantations antimicrobic role. Nowadays there are no data describing quantitative and qualitative composition of volatile substances that are produced by plants in natural conditions. Partly it is explained by the fact that plants volatile substances are multicomponent mixtures with the moderate concentration of different nature compounds and lack of simple and reliable methods of their analysis in the field conditions. We succeded of their analysis revealing 42 individual compounds in the composition of volatile substances including coumarines, terpenes, aldehydes, alkaloids, menthol, prussic acid, thymol, amines. Preliminary classification of plants according to groups of released compounds has been worked out, peculiarities of their production and antimicrobic activity has been studied. It was revealed that almost all plants posses antimicrobic activity but to a different extent. Antimicrobic activity of coniferous is kept up at a high degree during the entire season, for deciduous it is closely connected with the stage of growth and for the whole vegetative period it can vary from bactericidic action to stimulating one or indifferent. Volatile substances of wood plants, as a rule possess not only bactericidic, bacteriostatic action but they increase sensitivity of pyogenic microorganisms as well, and that is especially valuable they increase the sensitivity of gram-negative polyresistance cultures for antibiotics. Studies of air environment in multiherbaceous, sedge-moss (sphagnum), berry pine stands, sedge- moss spruce stands, sedge birch stands showed that the forest phytocenosis in the Middle Urals produce sufficiently large amount of volatile substances. The basic components in air environment of coniferous stands are monoterpenic hydrocarbons, in birch stands – coumarines, amines, formaldehyde and benzaldehyde. Antimicrobic activity of pine and birch stands has a complicated character of rhytmicity. Synchronism of splashes and failures of standing timber antimicrobic activity caused be amount of released antimicrobic substances attracts special attention. Thus, forests, parks and biological systems that are forming around cities serve as their natural health-improvement protection. However, they become insufficiently effective without knowledge of their biosynthesis ability and producing biologically active substances into air as well as their antimicrobic activity when these is no purposeful regulation of living systems.

PRELIMINARY EVALUATION OF GLYCEROL PRETREATMENT OF SUGARCANE BAGASSE FOR ENZYMATIC HYDROLYSIS OF CELLULOSE

C. Martin1, J. Puls2, B. Saake3, A. Schreiber3 1 - Department of Chemistry and Chemical Engineering, University of Matanzas, Cuba; vTI-Institute for Wood Technology and Wood Biology, Hamburg, Germany 2 - vTI-Institute for Wood Technology and Wood Biology, Hamburg, Germany 3 - Hamburg University, Wood Science Centre, Chemical Wood Technology, Germany [email protected]

Novel utilisations are required to manage with the overgrowth of glycerol production as consequence of the expansion of the biodiesel industry. A potential use of glycerol is as a pulping agent for component separation in lignocellulosic biorefineries. The drawback of the energy- intensive recovery of glycerol from liquors can be solved by transferring it, together with lignin,

131 into crosslinked epoxy resins. In the current work, the glycerol pretreatment of sugarcane bagasse is evaluated. Sugarcane bagasse was cooked with aqueous glycerol (40, 60 and 80% (w/w)) either in presence of sodium hydroxide or sulphuric acid, or without any chemicals. The pretreatment was performed at 190oC, 10% biomass load and for one to four hours. All the pretreatments resulted in cellulose-enriched fibres as a result of the solubilisation of lignin and xylan. In the pretreatments with NaOH addition and without any chemicals added, cellulose recovery was close to 100% after 1 h independently of glycerol concentration, and decreased slightly with pretreatment time, while in the pretreatments with H2SO4 addition it decreased from 83.6% at 1 h to 36.8% at 4 h. Xylan solubilisation was almost complete in the experiments in presence of H2SO4 independently of glycerol concentration and reaction time, whereas in the other experiments it was lower and decreased with the increase of glycerol content in the pulping liquor and with the length of the pretreatment. Lignin solubilisation increased proportionally to glycerol concentration. Lignin content in the fibres rose with the extension of reaction time for pretreatments with H2SO4 addition and without chemicals, but remained nearly constant for the alkaline pretreatment. For all the experimental conditions, glycerol pretreatment resulted in enhanced enzymatic hydrolysis of cellulose. The highest overall enzymatic convertibilities of cellulose, based on the raw material, were achieved in the pretreatment without chemicals (84.7-94.0%). Overall convertibility decreased sharply with time for the acidic pretreatment, and increased slightly for the other ones. The enzymatic hydrolysis of the xylan remaining in the fibres was maximal (67.8%) for the NaOH- assisted pretreatment, and in general it increased with glycerol concentration and decreased with time.

QUALITY CRITERIA FOR LIPPIA ALBA AND LIPPIA ORIGANOIDES ESSENTIAL OILS

J.R. Martinez, A.J. Agudelo, E.E. Stashenko Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

There is growing interest on the Lippia alba and Lippia origanoides (Verbenaceae family) essential oils, due to their potential applications in the food and cosmetics industries. We studied oils of the most common Colombian chemotypes of these species, the carvone-rich L. alba oil and the carvacrol-rich L. origanoides oil. The marketing of these essential oils requires the establishment of value ranges for the physicochemical parameters used in their data sheets. These two species were cultivated at various altitudes (600 – 1600 m) in experimental plots (2000 m2) with different fertilization, plant density (20000, 30000 plants/ha) and harvest frequencies (3, 4, 5 months). The essential oils obtained by steam distillation from the resulting vegetal material showed large differences in their composition, determined by gas chromatographic analysis (Agilent Technologies 6890 GC with FID and 6890 GC with MSD 5973, DB-5MS column). We followed ISO standards to measure 8 physicochemical characterization parameters (acid value, AV; ester value, EV; flash point, FLP; optical rotation, OR; refractive index, RI; moisture, H; density, D; and freezing point, FP). The following intervals correspond to 95% of the population of essential oils examined, which were obtained under diverse agricultural and post-harvest conditions which caused changes in their composition. For L. alba oil: Carvone (30.2- 32.3%), AV (0.254-1.79 mg KOH/g), EV (118.1-228.1 mg KOH/g), FLP (56.3 - 65.8 °C), OR (18.67 - 179.1°), RI (1.485- 1.491), H (0.18- 0.41%), D (0.892 - 0.910 kg/m3) and FP (-2.5 - -0.5°C). For L. origanoides oil: Carvacrol (44.8-52.0%), AV (5.41 - 9.82 mg KOH/g), EV (7.81 - 14.0 mg KOH/g), FLP (51.2 - 58.7°C), OR (53.56 - 88.94°), RI (1.502 - 1.509), H (0.96 1.2%), D (0.921 - 0.932 kg/m3) and FP (- 1.4 - -0.8°C).

132 PREDICTION OF THE RELATIVE AMOUNTS OF MAIN ESSENTIAL OIL CONSTITUENTS FROM PHYSICOCHEMICAL PROPERTIES: APPLICATION TO LIPPIA ALBA AND LIPPIA ORIGANOIDES ESSENTIAL OILS

J.R. Martinez, A.J. Agudelo, E.E. Stashenko Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Composition is the main determinant of essential oil properties and commercial value. However, small producers cannot afford the infrastructure or the cost of the chromatographic analysis (GC- FID, GC-MS). Also, certain field experiments require a prompt approximate knowledge of essential oil composition to establish extraction conditions. On the other hand, the determination of a number of physicochemical properties does not require expensive instrumentation or infrastructure. We followed ISO standards to measure density, flash point, freezing point, moisture, refractive index, optical rotation, and ester and acid values, on essential oils obtained from Lippia alba and Lippia origanoides (Verbenaceae family) cultivated under diverse agricultural conditions. Gas chromatographic analysis of these oils showed that carvone (30 – 45%) and limonene (15 – 35%) were the main L. alba oil components, while carvacrol (45 – 50%) was the main L. origanoides oil component. The main component relative amounts so determined were compared with the values predicted by several mathematical models constructed with several of the measured physicochemical properties. Ordinary least squares (OLS), partial least squares and principal component regression were used to construct several models which employed different sets of physicochemical properties as independent variables. The mean square error of prediction showed that OLS models which employed only 4 physicochemical parameters (density, refractive index, ester and acid values) showed the best performance. The predicted main constituent relative amounts differed between 2 and 6 units from the measured values (relative amounts of 30 – 60%).

LIGNIN QUANTITATIVE DETERMINATION AS WELL AS LIGNIN-DEGRADING PRODUCTS AT CULTIVATION OF LIGNIN-DECOMPOSED MICROORGANISMS

E.A. Martinson, S.G. Litvinets, A.A. Zlobin, E.V. Starkova Vyatka State University, Kirov, Russia [email protected]

Currently it is important to develop biotechnology methods of plant biomass recycling involving destruction of plant cell wall cellolignin complex by fungal and bacterial enzymes. From mold plant raw material (sprucewood), forest soil and from hydrolyzed lignin refuses, the pure cultures of cellulose-decomposed and lignin-decomposed bacteria and fungi have been separated. Separations have been conducted on Czapek’s medium; silicagel plates of Getchinson’s medium with cellulose plates; synthetic nutrient medium containing furulic acid (800 mg/l); synthetic nutrient medium containing hydrolyzed lignin. Pure cultures have been separated by standard methods of cultivation and an “exhaustive” one to produce single colonies. The separated micromycetes have been assessed on ability to utilize hydrolyzed lignin and to accumulate protein during growth on complex media that contain rye straw, saw dust (spruce), hydrolyzed lignin and mineral traces (NH4N03 – 0.3; КH2Р04 – 0.1; К2НР04 – 0.1; MgSO4·7H2O – 0.05;

NaCl – 0.05; FeSO4 – traces). 9 bacterial cultures have been separated capable to use ferulic acid as single carbon and energy sources. According to morphological, cultural physical and biochemical features and accoding to Bergi determinant, one culture among separated microorganisms belongs to Azomonas genus, the other two belong to Pseudomonas genus. Generic and specific assignment of the other cultures is currently determined. The separated bacterial cultures have shown capability to partially destruct lignin-containing compounds.

133 19 types of fungi have been separated in pure culture, generic assignment has been determined among 13 types (Geotrichum, Fialophora, Trichoderma, Bisporomyces, Acremonium, Botrytis, Cladophialophora and Fusarium). The dynamics of lignin content inside the nutrient media containing rye straw, saw dust (spruce) and hydrolyzed lignin has been determined as well as raw protein accumulation during surface cultivation for 7 separated strains-micromecetes. It was determined that some separated micromecetes cultures are capable to growth onto lignin-containing raw material. Lignin maximum consumption occurs after 3 days of cultivation (loss from 4.7 to 25.2 % from initial lignin content in medium). Delay in lignin consumption occurs in 10-20 days of cultivation (loss from 7.3 до 31.1% from initial lignin content in medium) by micromecetes cultures. Thus, we can make a conclusion that separated micromecetes cultures are rather active as regards enzymes participating in lignin oxidative destruction. Content of raw protein in surface micromecetes cultures is determined by Kjeldahl method. One of the most active protein produces are fungi of Cladophiolophora, Fusarium and Trichoderma genera. Cultures belonging to the genera can be used for lignin-containing wastes processing including feedstuff manufacture. The more preferable medium is the one containing not only lignin but pulverized straw as well. The medium containing pulverized saw dust is less preferable except for one culture Cladophiolophora sp.

DEVELOPMENT OF TECHNOLOGY AND STANDARDIZATION METHODS OF FOLIA BETULA PENDULA DRY EXTRACT

T.M. Medvedeva St. Petersburg State Chemical Pharmaceutical Academy, St. Petersburg, Russia [email protected]

Betula pendula is known as a rich source of such biologically active substances (BAS) as flavonoids, polyphenols, triterpene glycosides and minerals. Gemmae, juvenile leaves, sap and cortex are widely used in medicine. Folia Betula pendula are of interest as ready available and renewable medical plant resources. Acute respiratory infections take the first place in human morbidity patterns. But lots of synthetic drugs that are used in this case have different side effects and only eliminate the symptoms. Phytopreparations render combined and mild effects. That is why administration of phytopreparations can be safer and more reasonable. Folia Betula pendula contain a number of biologically active supplements that are responsible for anti-inflammatory, antipyretic, detoxification and anaesthetic effects of the extracts. These effects are necessary while treating the cold-related diseases. But nowadays Betula pendula extract is included into a formulation of only one biologically active supplement. Thereby it is of immediate interest to develop a new technology of folia Betula pendula dry extract and to work out a formulation of аnti-cold remedy that will possess anti-inflammatory and antipyretic effects. During the selection of the extraction conditions following factors have been studied: fineness degree, raw material:extragent ratio, duration of extraction, extragent origin. The extraction was carried out by the methods of maceration with agitation and by the method of percolation. The extraction recovery was evaluated by the content of flavonoids and tanning substances. For this sort of medicinal plant raw material the method of maceration was more effective than the method of percolation. So it was used in further experiments. It was established that when the extraction is conducted on raw material with grinding size of 1- 3mm the optimal yield of BAS is provided and the technological characteristics make it possible to agitate the mass effectively in contrast to the particles with grinding size of 3-5mm. At the same time this material does not bridge the pores of the filtering material. We have studied the dependence of the BAS-yield from raw material:extragent ratio. The ratios explored are as follows: 1:5, 1:10, 1:15, 1:20, 1:25, 1:30 and 1:35. It was discovered that the

134 optimum mash ratio was 1:20 w/v. With increase of the ratio from 1:20 to 1:35 the completeness of the extraction remains unchanged with the concentration of BAS going down because of dilution. In the following series of experiments the extraction with the ethanol-water solutions with different polarity was studied. It was shown that ethanol 50% demonstrates the best extraction capacity against flavonoids and tanning substances. The yield of flavonoids was about 53% and that of tannins was about 55%. The extraction capacity substantially increased during the process of extraction with heating up to 70оС. The yield of flavonoids rose to about 63% and that of tannins was about 92%. It has also been established that the time of the extraction should be at list 45 minutes but not more than one hour. From this liquid extract the dry extract was obtained. The extract is brown powder with characteristic odor. The following characteristics of folia Betula pendula dry extract are recommended: flavonoids – not less than 7,0%; tanning substances – not less than 13,0%; coumarins - not less than 4,0%; humidity content – not more than 5%; heavy metals - not more than 0,01%.

HIGH YIELDS OF LEVOGLUCOSAN FROM THE CATALYTIC PYROLYSIS OF BEECH WOOD WITH ZEOLITES USING PY-GC/MS

D. Meier1, A. Azeez2, J. Odermatt3 1 - vTI, Institute of Wood Technology and Wood Biology, Hamburg, Germany 2 - University of Ado-Ekiti, Department of Chemistry, Ado Ekiti, Nigeria 3 - University of Hamburg, Wood Chemistry Technology, Hamburg, Germany [email protected]

Different unmodified zeolite catalysts have been adopted for the conversion of beech wood (Fagus sylvatica L.) to study their effects on the emerging volatile products using analytical pyrolysis connected to a GC/FID/MS system. Two H-ZMS-5 type catalysts (MIF structure) with SiO2/Al2O3 ratios of 28 and 80, one FCC catalyst (MIF), and two mordenite structured (MOR) zeolites (MSM- 15) were used. A thoroughly mixed sample of the lignocellulosic sample with varying amounts of catalyst were pyrolysed at a fixed temperature of 500°C. From the chromatograms it was obvious, that the amounts of levoglucosan obtained were of the order 5-9 and 3-5 times higher in samples mixed with 10-40 wt.% MSM-15 and H-ZMS, respectively. The FCC catalyst induced the least effect based on levoglucosan yield. Substantial reduction in the production of hydroxyl propan-2- one and propanal and few among reverse aldolisation fragmentation products of holocellulose, indicated that the acidic catalysts greatly induced random cleavage of the glucosidic bond by substituting free hydroxyl group in the cellulose. Volatiles‘ composition appears to be highly selective depending on the method of sample preparation (mixing), the number of the active sites in the catalyst, and its crystal structure. All catalyst revealed no significant effect on the amount of most lignin derived volatile products.

135 CONVERSION OF FERN (PTERIS VITTATA L.) BIOMASS FROM A PHYTOREMEDIATION TRIAL IN SUB- AND SUPERCRITICAL WATER CONDITIONS

M. Mench1, M. Carrier2, A. Loppinet-Serani2, F. Marias3, C. Absalon4, C. Aymonier2 1 - Ecology of Communities University of Bordeaux, Talence, France 2 - University of Bordeaux, Pessac Cedex, France 3 - ENSGTI, Pau Cedex, France 4 - University of Bordeaux, Talence Cedex, France [email protected]

Unlike organic compounds, trace elements in contaminated soils cannot be degraded. To reduce pollutant linkages evidenced by risk assessment, the clean-up of many contaminated sites requires to remove trace elements in excess from the soil. Phytoextraction refers to the uptake and translocation of soil contaminants by plant roots into generally the aboveground plant parts, or less frequently any harvestable plant parts such as tubers and big root systems, to remove contaminants from soil and promote long term soil cleaning. Chinese brake fern (Pteris vittata L.), an arsenic (As) hyperaccumulator is an option to phytoextract As in contaminated soils. Post-harvest disposal of such trace element-contaminated plant biomass is a key-point to gain financial returns from phytoextraction and to support public, policy maker and stakeholder acceptance. Several disposal methods of post-harvest contaminated crop, e.g. composting, compaction, incineration, ashing, pyrolysis, direct disposal, and liquid extraction, have been described. Other innovative processes using sub and supercritical water treatments propose the complete oxidation of biomass or its conversion into valorizable products via gasification or liquefaction mechanisms. Supercritical fluids exhibit interesting physical and chemical properties. Their intermediate properties between gases and liquids make them an optimum media for solute transport. These properties can vary continuously from gas-like to liquid-like behaviour. Few works have investigated metal behaviour in biomass converted by sub- and supercritical conditions. This work aimed at converting in sub- and supercritical conditions frond biomasses of P. vittata from a phytoextraction trial carried out in large lysimeters, with special emphasis on As behaviour. Attention was additionally paid to an adsorption method for recovering As from the aqueous phase. Uncontaminated and As-contaminated fronds of Pteris vittata L., an As-hyperaccumulator fern used to phytoextract As from contaminated soils and water, were converted by sub-critical water (300°C, 25 Pa) and supercritical water (400°C, 25Pa) treatments. Frond biomass was reduced between 70 and 77%. Compared to sub-critical conditions, supercritical conditions decreased C and inorganic contents in both the solid and liquid phases for uncontaminated and contaminated fronds and promoted CH4 formation. Higher As, Fe and Zn contents in contaminated fronds promoted decreasing C contents and the formations of cyclopentenones and benzenediols in the liquid phase. Al, Fe, P, Zn and Ca mainly remained in the solid phase whereas As and S were transferred to the liquid phase for both phytomasses. As the temperature increased from 300°C to 400°C, the concentrations of cyclopentenones and phenols in the liquid phase rose while those of guaiacols and other compounds decreased for both phytomasses. Arsenic in the liquid phase was removed by sorption on hydrous iron oxide.

Acknowledgement This work was supported by the Aquitaine Region Council, Bordeaux, France. We thank Prof. J.-C. Bollinger, Univ. of Limoges, France for precious advice concerning amorphous iron hydroxide synthesis and D. Denux, L. Etienne, Dr H. Etcheber, Dr O. Atteia, and Dr. P. Rosa for their cooperation in this research.

136 ARABINOGALACTAN FROM A LARCHES SIBERIAN - THE PERSPECTIVE CARRYING AGENT FOR MEDICINAL SUBSTANCES

E.S. Meteleva1, A.V. Dushkin1, T.G. Tolstikova2, M.P. Dolgikh2, M.V. Khvostov2 1 - Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Science, Novosibirsk, Russia 2 - Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Science, Novosibirsk, Russia [email protected]

In a cycle of the investigations presented in the report, the mechanochemical synthesis and properties of adducts of some poorly soluble medicinal agents (MA) of anticoagulation, cardio protective, analgesic and anti-inflammatory action and natural polysaccharide - arabinogalactan from a larches Siberian and Gmelin. The opportunity of increase of solubility in water of investigated MA up to ~102 times due to formation of intermolecular complexes between molecules MA and macromolecules of polysaccharide is shown. Table 1. Change of solubility of medicinal substances in water due to complexation with arabinigalactan Structure of solid composition, Increase in solubility of medicinal substance weight ratio from the complexes Indometacin : arabinogalactane(1:10) In 9 times

Diazepam : arabinogalactane(1:10) In 3 times Clozapine : arabinogalactane (1:10) In 21 times Medazepam : arabinogalactane(1:10) In 47 times It is shown, that at dissolution of the received mixtures in water the substantial growth of solubility medicinal substance testifying to formation of intermolecular complexes medicinal substance - "carrier" is observed. Arabinogalactan in all cases are the most effective complexation agents and allow to achieve the greatest solubility of investigated MA. In both cases the molecules of MA are included in autoassociates of arabinogalactan macromolecules. Mechanochemical synthesis of compositions considerably (up to ~20 times) increases stability of intermolecular complexes, possibly, due to their formation in the waterless solid environment or during nonequilibrium dissolution processes of solid compositions. In toxic-pharmacological tests of synthesized compositions of polysaccharide and medicinal substances executed in Novosibirsk Institute of Organic Chemistry, the opportunity of decrease (up to 20 times) a mean therapeutic doze is shown at preservation of base pharmacological activity, as far as decreasing undesirable toxic effects.

ROTOR PULSE EXTRACTOR FOR EXTRACTION OF ARABINOGALACTAN FROM LARCH WOOD

N.P. Midukov, A.O. Nikiforov, V.S. Kurov Saint Petersburg state technological University of Plant Polymers, Department of Processes and Devices of Chemical Technology, St. Petersburg, Russia [email protected]

Arabinogalactan is applied in medical, cosmetic, food industries due to its immune-modeling, gastro-protective, antimicrobic and prebiotic to properties. Water extraction process of arabinogalactan from larch wood is widely studied by various researches, however the majority of them made extrogation in bulky, metal-consuming equipment

137 of periodic or semicontinuous action - in devices with a mixer, in autoclaves and in diffusion apparatus with extraction agent fed continuously. Carrying out the extraction process for water- soluble substances in mechanical oscillation field allows decreasing of extraction time by 1-2 exponents in comparison to the known methods and reaching almost full extraction of agents. From experimental researches it is known that extraction proceeds more effectively in a backlash between a rotor and stator. For this purpose a special device and plant for carrying out the extraction process have been developed (patents for useful model №70154 of the Russian Federation and for invention №2410148 Russian Federations). Despite a rather wide application of rotor pulse type devices for performance of extraction, the process mechanism is understudied. When extraction process for target component isn't complicated by chemical reaction at phase boundary, its velocity will be defined basically by the target component diffusion rate, and the process itself will consist of the following stages: 1- extraction agent intake to the surface of particle; 2 - diffusions of extraction agent inside the particle to the target component; 3 - extracted component dissolution; 4 bleed of the substance the particle surface; 5 – into the diffusions extraction agent allow kernel. A model of rotor-pulse extractor with a mixed structure of flows for water extraction of Arabinogalactan from larch wood is proposed.

STUDY OF MONOSACCHARIDE COMPOSITION OF POLYSACCHARIDES EXTRACTED FROM GRAIN SEEDS

E.A. Mikhailova, A.A. Shubakov Institute of Physiology, Komi Science Centre, the Urals Branch of the Russian Academy of Seiences, 167982, Syktyvkar, Russia [email protected]

Polysaccharides represent the group of carbohydrate-containing biopolimers of plant cell walls and play an important biological role, carrying out structural functions and the functions of ionic and water exchange. Polysaccharides have wide application in medicine, perfumery, and food- processing industry. It is difficult to investigate the constitution of polysaccharides and, in particular, of pectins because their macromolecules consist of different blocks and have an irregular character, without the repeating units. The purpose of our research was to develop a method of polysaccharide extraction from grain seeds and determine their monosaccharide composition. In order to extract polysaccharides from seeds of wheat Triticum aestivum L. and rye Secale cereale L. we carried out successive extractions of the plant materials under various conditions. As a result, we obtained five fractions, in which we determined the quality composition of neutral monosaccharides with the help of paper chromatography. With the purpose of quantification of monosaccharides, the polysaccharide fractions obtained were hydrolyzed with 2M triftuoroacetic acid, neutral monosaccharides obtained were quantitated by gas-liquid chromatography as the corresponding alditol acetates. The quantitative composition of monosaccharides was determined with the GLC. Analysis of sugar compositions of polysaccharides in seeds of wheat and rye shows that glucose (55,1-83,9%) prevails in three polysaccharide fractions of wheat, and mannose (64,9%) prevails in one. In the seeds of rye, glucose (85,5 and 23,7%) dominates in two polysaccharide fractions, xylose (32,5-42,3%) and arabinose (26,6-35,9%) prevail in two fractions, and the basic three monosaccharides - xylose (29,6%), glucose (25,9%) and arabinose (19,3%) prevail in one of the five fractions. That means that sugar composition of polysaccharide fractions of seeds of wheat and rye differs considerably in each of them. This can apparently demonstrate to complex and various compositions of wheat and rye seed polysaccharides. Aknowledgments: This work was supported by the grant No. 03-04-48136 of the Russian Foundation for Basic Research.

138 PREPARATION AND PROPERTIES OF TECHNICAL PULP FROM WASTE SUGAR CANE – BAGASSE

A.R. Minakova Urals state forest engineering university, Ekaterinburg, Russia [email protected]

In a rapidly growing demand for pulp and paper industry development prospects of this industry due primarily expandable resource base. This problem can be solved by using large-tonnage of agricultural waste, such as sugar cane – bagasse, which currently can not find a qualified application. Sugar cane is one of the major crops in Latin America. Waste from the processing of sugar cane are desugared feed pulp – bagasse (bagasse) and is 40%. Traditional methods of obtaining fibrous materials (sulfite, sulfate) for these regions are acceptable enough on economic and environmental reasons. The purpose of this study is to investigate the possibility of obtaining cellulosic materials from bagasse oxidation – organosolvent method, whose application is useful when processing of crop residues. To optimize the factors of the oxidation – organosolvent delignification studied by morphological and anatomical structure of the investigated materials, determined by its chemical composition. During the microscopic examination revealed that bagasse consists mainly of parenchyma cells, bast fibers libriformnogo nature and vessels. The chemical composition of bagasse: pulp (for Kyushneru) – 20,0 %, lignin (GOST 11960) – 22,7 % water-soluble substances – 15,2 %; substances extractable in organic solvents – 3,2 %; minerals – 0,3%; polysaccharides (easilyhydrolyzable – 37,2 % and difficulthydrolyzable – 15,2 %). To remove lignin and reducing the consumption of major reactants delignifitsiruyuschih bagasse previously subjected to alkali treatment, at which there is swelling and loosening of cell walls and intercellular substance. The result of this treatment is to reduce the mass fraction of lignin up to 15,7 %, water – soluble substances to 5,7 %, rising to 48,3 % of cellulose content. Thus treated bagasse delignifitsiruyut oxidation – organosolvent method way under the following conditions: the amount of peracetic acid – 0,4 g/g, cooking time - 90 minutes, the temperature - 90 0C. For technical cellulose identified strength and physical and chemical characteristics. Analysis of the results showed that the technical cellulose from bagasse, resulting oxidation- organosolvent method has satisfactory mechanical properties: breaking length – 7100 m; falling through and tear resistance – 150 kPa, 431 mN, respectively. It should be noted that the technical cellulose from bagasse has higher sorption and absorbent properties (adsorption capacity – 70,9 mg /g, sorption capacity – 60,7 %, swelling in a solution of NaOH – 710 %; capillary absorbency – 20 mm; absorption in unilateral wetting – 110 g/m2). Thus, the above-defined indicators of cellulosic material from the bagasse, allows us to consider it as a promising raw material for writing and printing paper, as well as in thethe manufacture of sanitary products.

REVISITED HYDRAZINE APPLICATION FOR A CELLULOSE BLEACHING

O.V. Mukuseva, G.A. Pazuhina Forest engineering academy of a name of Kirov St. Petersburg [email protected]

High regenerative ability of a hydrazine, ability to enter chemical reactions with carbonyl groups of carbohydrates and to prevent their destruction in the alkaline medium at the expense of “peeling” reaction explains the choice of the given reagent as decolouring and lignin disposing reagent at cellulose bleaching. In the course of research it is established that the hydrazine most effectively can be applied at a stage of delignification of not bleached sulphatic coniferous and deciduous cellulose. Thus the hydrazine can be used under two schemes. The first – two phasic processing

139 under the scheme a hydrazine – oxidizing alkalization. In this case the hydrazine is used as a reagent preparing a lignin to dissolution in the conditions of oxidizing alkali extraction and strengthening efficiency of this process. The second – hydrazine application in the alkaline environment that allows to accelerate and deepen the delignification cellulose process.

OLIGOMERISATION OF TERTIARY AMINE LACTATES

S.A. Mulyashov1, S.G. Beksaev1, F.S. Sirovski2, I.V. Ilushka1 1 - Krasnodar Branch of The Federal State Enterprise Bio Plant Protection Agents, Krasnodar, Russia 2 - D. Mendeleyev University of Chemical Technology of Russia, Moscow, Russia [email protected]

The sharp increase in oil prices in the middle of the last decade triggered the interest in renewable feedstocks for the manufacture of organic synthesis products. Mono- and dicarboxylic acids obtained by microbial fermentation could serve as a possible feedstock Currently the microbial steps of lactic acid synthesis together with subsequent its chemical transformation into lactates, acrylates, lactides and propylene glycol are the most developed ones. It means that lactic acid: the feedstock for new chemical products could be obtained from a renewable source, such as starch, treacle, molasses, etc. The removal of L-lactic acid from the culture fluid and its subsequent purification presents an important task. Three known methods exist: transfer into calcium lactate, esterification by C1-C5 alcohols and as tertiary amine salt. The last method is the most advantageous as there are no solid wastes as in case of calcium and no evaporation of large volumes of water and product distillation is required as in case of esters. Tertiary amines could be recovered and recycled back to the front end. The next step after the isolation of lactic acid is its oligomerisation. Tat step is present in all processes leading to lactates, acrylates and lactides. Lactates of tertiary amines are able to undergo polycondensation affording the oligomer and free amine. It makes possible to use these lactates directly in the synthesis, avoiding the isolation of the free acid. In this work we studied oligomerisation of trialkylammonium lactates at temperatures between 80 – 240 °C under vacuum. Trialkylammonium lactates were obtained by adding tertiary amines into the culture fluid with subsequent ligroin extraction. We obtained partition coefficients for a number of amines in water-ligroin system. The oligomerisation was monitored by HPLC with UV-detector and GC-MS. We identified several oligomers with n=1-4 and quantified them. It was shown that during polycondensation water and tertiary amine are separated. The same reaction with trioctyl ammonium lactates is inhibited by the presence of eliminated tertiary amine in the reaction mixture. The process mass balance and optimal performance parameters for the synthesis of oligomer with molecular mass 1,500-2,000 DA were determined on the existing pilot plant.

THE SYNTHESIS OF CORROSION INHIBITORS FOR OIL RIG EQUIPMENT FROM TALL OIL AND OTHER RENEWABLE FEEDSTOCK

The first ‘green’, i.e. low toxic corrosion inhibitors for the use on off-shore platforms appeared about 20 years ago. Water with these inhibitors could be dumped directly into the sea. Currently the inhibitors of this type are widely used on-shore as well. ‘Green chemistry’ is a favourite of the governments and blue chip chemical companies. US EPA defines the green chemistry as chemicals and technologies developed for the abatement or prevention of harm to humans or the environment. The mainstream in green chemistry research is directed at the increase in water, material and energy

140 efficiency, recycling, use of renewable feedstock, development of inherently safe processes and safe reagents. We have synthesised low toxic corrosion inhibitors for oil treatment equipment using tall oil from different sources, lactic acid and piperazine. These inhibitors were field tested at Western Siberia oil rigs. The process includes reaction of tall oil with hydroxyethyl piperazine obtained by ethylene glycol condensation with piperazine. The obtained amides react with lactic acid, methyl lactate or methoxymethyl lactate. All the above-mentioned product excluding lactic acid could be obtained in a single plant. Lactic acid is obtained by microbial synthesis from a renewable feedstock: starch, molasses, sugar, etc. At the development stages different tall oils with acid number 190, 130 and 95 were used. The best results in both lab and field tests were reached using tall oil with the highest level of acid resins. The choice of corrosion inhibitors for a particular oilfield depends on its preferred type: oil-soluble, water-soluble or water-dispersible. The selection of the reagent type is determined by the structure of gas-liquid stream in the protected equipment. In Western Siberia pipelines water cut ranges from 10 to 90%. That means that protecting effect is mostly determined by the inhibitor HLB rather than its adhesion to metal or film-forming properties. Optimisation of HLB is attained by changing reactants ratio in amidoamine synthesis employing additional ethoxylation and propoxylation steps. We studied the products of ethoxylation of tall oil acids and piperazine amides as water-soluble and water-dispersible corrosion inhibitors. Polyamides of ethylene and propylene oxide block copolymers were also researched. . The lab and field tests showed the feasibility of manufacturing amidoamine corrosion inhibitors with properties tailored in terms of both the protection effect and the partition coefficient in water- oil system.

THE TECHNOLOGY OF MAKING CARBOXYMETHYL CELLULOSE (CMC) BY METHOD MONOAPPARATUS

M.M. Murodov Tashkent Chemical Technology Institute [email protected]

Now days in every structure of our industry the process of localization is gone successfully. According to that objective many current technologies are going to be reconstructed. As we know the enterprise “Karbonam” which is situated in Namangan city make cellulose’s ether carboxymethyl cellulose (CMC). That technology is very long and it depresses the income. Because of these reasons the enterprise needs to be reconstructed. Result of research which took a long time, we fabricated the mono apparatus method of making CMC. According to that the main technical processes (mercerization, alkalization) are gone in mono apparatus. It effects on CMC’s features (deliquescence – 98, 9%, main amount of matter - 67%, degree of polymerization – 1300…) and decreases price of product. First cellulose is put in mono apparatus (5) and is get mercerization by alkali fusion (1). Get alkalization by sodium acetate, and cooked (6), dry (8), crushed by mill (9) prepared for ready product (10).

141

The advantages of the mono apparatus method is that we can change the processes work by contract, influence of parameters, modification of various inhibitors, connection of various factors. It lets us make CMC which has high molecular weight. It makes use CMC preparation for different spheres for instance oil and gas fields. Because destructive factors in drilling decreases CMC’s degree of polymerization. The making modification of inhibitors makes produce CMC which is stable to thermal destruction. Using lignin as a inhibitor lets us use local semi-products. Lignin make received radicals join to it and slows down the process of destruction. Because the composition of lignin includes phenol, benzene, hydroxyl groups, carboxyl groups. Lignin surrounds the molecules of CMC and decreases the contact between air oxygen and CMC. The mono apparatus method is universal method. We can use various plants’ cellulose, requirement of textile plants as a semi-product. By changing the contract we can make various types of CMC.

TECHNOLOGY OF MAKING CELLULOSE AND ITS ETHERS BY USING RAW MATERIALS

M.M. Murodov, G.R. Rakhmonberdiyev, M.Q. Urozov, P.J. Tojiev Tashkent chemical technology institute [email protected]

Cellulose is the most popular polymer in the nature. It composes most part of cells’ plants. 40–60% of trees and plants is made up of cellulose. Cotton, jute and hemps are celluloses. In industry cellulose is produced by various types of trees and is called wood cellulose. 96% of linter is cellulose. To produce cellulose by linter, 1.5% solution of NaOH should be boiled under pressure 0.3-1 M Pa for 3-6 hours. Received cellulose is made white by hypochlorite or hydrogen peroxide solutions. The degree of whiteness of cellulose which is made by this reaction is 98-99%. The degree of whiteness of high quality cellulose and chemical recycle cellulose’s should not be less than 94%. Cellulose’s physics, chemistry, mechanic and other features are depended on cellulose’s degree of polymerization, the reciprocal arrangement of macromolecules, the site of the elementary units depend on the their location to each other and they are part of macromolecule’s structure. The quantity of cellulose which is produced in industry and is used in sundry fields is higher than quantity of the whole synthetic polymers which are produced and used.

142 Cellulose’s hydroxyl groups react with all chemistry reactions. There are a lot of annual and perennial plants which include cellulose in our country. They are: wheat’s adobe, topinambour’s Culm, sunflower’s Culm, secondary commodities (radix, calm…) of perennial plants (poplar, osier…). They are used as basal semi products. The production and use of cellulose and its ethers have been searched for many years. The principle – technological chart below shows the production of cellulose and inherently its carboxymethyl-cellulose from plants which contain cellulose. CM cellulose is used in sundry purposes. The technology of making CM cellulose: first semi product (1) passes through crusher (2) and is sent to boiling cauldron (4). Boiling is carried out in required concentration of alkali (3). Centrifuge (5) washes received cellulose and it is sent to mono apparatus (8). Lignin (7) is the sediment of the washing and is used as an inhibitor. Production process of CM cellulose is sent to mono apparatus and received CM cellulose is prepared (11), desiccated (12), and sent to mill (13) to grange(15) for ready products. Innovation of this technology is that, it is possible to make cellulose which has sundry qualities by using sundry semi products via changing parameters, bills of chemical reagents. In addition, it is possible to make sundry sort of CM cellulose from cellulose and it satisfies the need for cellulose’s products and cellulose’s ether and ester in our country.

DETERMINING THE OPTIMAL SAMPLE VOLUME OF MSW TO RELIABLY DETERMINE THE MORPHOLOGICAL STRUCTURE

A.V. Musatov1, D.S. Yakshilov2, O.V. Ischenko2, A.A. Ageeva2, E.V. Karelina2, V.N. Mochna2, A.V. Garabadjiu2, G.V. Kozlov2 1 - Branch of the Federal State Unitary Enterprise, St. Petersburg 2 - Saint-Petersburg state institute of technology (technical university), St-Petersburg [email protected]

In the course of the pilot plant MPDW was marked by the fact that the use of methods for determining the morphological composition of MSW by the traditional method does not give reliable results. The reason for this is that the composition of solid waste has changed dramatically. We decided to determine the minimum sample size needed for reliable analysis in the present circumstances. The table shows the composition of solid waste at various sample mass.

Denomination Sample mass, kg of the fraction 10- 20- 47- 190- 247- 280- 410- 490- 820- 2000- 11 25 55 225 260 320 420 610 850 2100 Paper and cardboard 15,9 15,9 17,05 22,2 18,73 17,48 19,87 17,6 18,48 21,1 Food wastes 29,5 29,4 25,85 21,83 19,43 21,75 23,9 21,55 12,9 9,3 Wood 4,55 4,6 3,84,2 6,1 4,42 2,23 4,25 2,29 3,15

143 Textile 6,65 6,7 6,56,43 5 5,92 5,4 2,8 4,7 3,1 Leather and rubber 2,15 2,2 2,21,2 1,17 1,27 0,77 0,95 1,6 0,72 Plastics 13,7 13,7 18,713,23 9,43 11,93 11,53 9 13,75 11,3 Bone 0,9 0,4 1,30,3 0,33 0,1 - 0,1 0,38 0,1 Ferrous metal 3,95 3,9 0,8 2,03 1,8 1,87 2,4 2,1 2,11 1,5 Non-ferrous 00 metal 0,26 0,7 0,63 1,1 0,67 0,4 0,29 0,22 Glass 11,5 11,5 14,7512,73 12,27 11,62 9,6 13,05 13,75 9,1 Stones 1,85 1,8 1,282,93 2,25 1,9 1,8 1,3 2,19 1,2 Other material + Siftings 9,35 9,9 7,5112,22 22,86 20,64 21,83 26,9 27,56 39,21 The total 100 100 100 100 100 100 100 100 100 100

The greatest composition of solid waste from residential buildings meet the range of samples from 10 to 50 kg. Evaluation was performed by comparing the composition with the composition of solid waste from residential homes. For waste going to landfills and solid waste processing plants is optimal sample of 800 kg (6 cubic meters of container). Assessment is based on the output of compost.

DETAILED STUDY OF THE MORPHOLOGICAL COMPOSITION OF MSW ST. PETERSBURG

The table shows the data of morphological studies ststava MSW received at the Pilot Plant MPDW. Sample volume 850 kg (container 6 m3).

Size fraction, mm № Denomination of the fraction Total ≥200 200-80 <80 Board 2,30 - - 2,30 1 Paper Paper, newspapers, magazines 3,50 0,30 1,80 5,60 Laminated packaging 6,40 1,20 - 7,60 2 Food wastes 1,00 4,60 7,10 12,70 Polymeric materials 0,06 0,60 2,30 2,96 Polyethylene 4,90 1,30 0,14 6,34 3 Plastics Polyethylene terephthalate 3,80 0,20 - 4,00 High Density Polyethylene 0,40 - - 0,40 Ferrous Large 1,20 - - 1,20 4 metal Banks - 0,82 - 0,82 Technical аuminum 0,15 - 0,40 0,15 Non-ferrous 5 Food aluminum 0,10 - - 0,10 metal Aluminum cans 0,10 - - 0,10 6 Glass 8,40 1,30 - 10,10 7 Wood 2,90 0,38 - 3,28 8 Leather and rubber 0,70 - - 0,70 9 Textile 3,00 - - 3,00 144 10 Stones, concrete, brick 2,90 0,48 - 3,38 11 Bone 0,60 0,17 - 0,77 12 Hygienic diaper 2,85 - - 2,85 Metal - - 0,44 0,44 Organic wastes - - 18,76 18,76 13 Siftings Sand, glass 12,10 12,10 Plastics 0,35 0,35 Total 45,26 11,35 43,39 100,00

COMPARISON OF SOME TECHNOLOGIES OF EXTRACTION OF TERPENOIDS FROM THE PLANT MATERIALS

A.N. Narchuganov, A.A. Efremov Siberian Federal University, Krasnoyarsk, Russia [email protected]

Conifers growing in Siberia contain a large number of biologically active compounds. Among these compounds there are volatile substances belonging to the class of terpenoids. It is proved that terpenoids possess some important properties, such as anticancer and antimicrobial activity and anti inflammatory effect. Due to thermal instability of terpenoids and inherent tendency to chemical transformations, process of isolation these compounds from plant materials is a very difficult task. Steam distillation process is usually used to extraction of terpenoids. In steam distillation method plant material is located on a grid over the boiling water. Process of steam distillation is follows the Dalton's law and Raoult's law, and temperature of distillation of all volatile compounds is about 100oC. Other method, which can be used for isolation of terpenoids is long time extraction at room temperature with using a non-polar solvent as an extractant. This method is characterized by more soft conditions, and accompanied by a smaller number of chemical transformations, but it is more laborious and require special processing of extract for deleting fat and wax. The aim of this study was to compare chemical composition of essential oils (mixture of terpenoids), produced by steam distillation and extraction by non-polar solvent. For definition of components of essential oils was used gas chromatography-mass spectrometry method. GC-MS analytical system includes gas chromatograph Agilent 7890A (with low-polar column HP-5ms) and Agilent 5975 C mass-spectrometer as detector. Identification of components was based on calculation of identification points: retention index and relative intensity of peaks in mass-specters of individual compounds. Received data was compared with library data, for reliable identification at least 5 identification points should lie within the maximum permitted tolerances. In the steam distillation product were identified 40 components. In essential oil, received by extraction, were identified 46 components. Results of analysis (differences in composition of these products) shown in the table 1. Table 1. Differences in composition of essential oils, which were produced by different methods. Component Retention The presence of a component in the product obtained by Index method Steam distillation Extraction by non-polar solvent α-terpineol 1191 + - β-longhipinen 1401 - + cariophyllene oxide 1591 - + iso-elemenol 1615 - + amorphen-7-ol 1636 - + himacalol 1652 - + valerenol 1732 - +

145 Results of analysis show, that the essential oil produced by extraction method contains more low- volatile components (sesqui- and diterpens). It may be due to the thermal destruction (or other chemical changes) of this components in steam distillation. At the other side, product of extraction contains no α-terpineol. This component is an artifact, i.e. substance which is not contained in the initial plant material and was obtained in chemical reactions. Probably, α-terpineol is the product of isomerisation reaction, which was catalyzed by acids present in plant material. Comparison of two methods of isolation of terpenoids from plant material show that steam distillation (widely used in industry) is accompanied by some chemical reactions. Long time extraction at room temperature with using a non-polar solvent as an extractant is more precision process and oils, which produced by this method, more exactly reflect properties of initial plant material.

SYNTHESIS OF LIGNIN MODEL COMPOUNDS, CONTAINING BETA-O-4 ETHER LINKAGE

A.V. Nemceva, A.K. Platonov, D.S. Ryabukhin, A.V. Vasilyev, M.Ya. Zarubin Saint-Petersburg State Forest Technical Academy, Saint-Petersburg, Russia [email protected]

Lignin model compounds are widely used for study of various reactions of lignin, their mechanisms, and for investigation of lignin structure. We have synthesized the series of lignin model compounds (3,4,8,9). These models contain –O–4 ether bond, which is the most representative linkage between phenylpropane units in lignin. Several types of such model compounds, containing phenolic (3,4) or nonphenolic (8,9) units and -(or -) hydroxy- (4,8,9) or -keto-groups (3,8), have been prepared. The compounds (3,4,8,9) have been characterized by 1H, 13C NMR data, and structure of the compound (3) was confirmed by X-ray method. OH H3CO H3CO Br OCH 3 4 4 H3C O H3C O 1. O O NaBH4/ Br /CHCl H3C H3C 2 3 K2CO3/KJ/(CH3)2CO  O EtOH/CHCl3  OH  2. KOH/EtOH 

OCH3 OCH3 OAc OAc OCH OCH 1 2 3 3 OH 3 OH 4 OH H CO Br 3 OCH3 H3C O O O Br2/CHCl3 K CO /KJ/(CH ) CO CH O/K CO /EtOH 2 3 3 2 O 2 2 3

OCH3 OCH3 OCH3 OCH3 56 OCH3 OCH3 7

H3CO H3CO 4 4  O NaBH4/  O H C EtOH/CHCl3 H C 2  O 2  OH HO  HO 

OCH3 OCH3 OCH3 89OCH3 146

X-ray structure of the compound (3).

THE STUDY OF BIOLOGICALLY ACTIVE COMPOUNDS ISOLATION FROM RAW PLANT MATERIALS USING SUPERCRITICAL СО2 EXTRACTION

D. Nicolaeva1, V. Caragia1, M. Podogova1, V. Simac2, M. Deleanu3, C. Stavarache3, Ju. Golovco4 1 - Scientific&Practical Institute of Horticulture, Viticulture and Food Technology, Laboratory of Food Technology, Chisinau, Moldova 2 - Institute of Food Bioresurses, Bucharest, Romania 3 - Institute of Food Research, Bucharest, Romania 4 - "SVD-GROUP"SRL, Chisinau, Moldova [email protected]

The supercritical (SC) carbon dioxide (CO2) extraction of bioactive compounds from vegetal material assures a high ecological level of the process because the use of pure and inoffensive carbon dioxide as a solvent and excludes the possibility of environment and final product pollution. The SC-CO2technology permits to obtain highly concentrated biologically active extracts with preservation of their natural ratio or individual fractions, even target biologically active components for the pharmaceutical, cosmetic or food industry. In collaboration with pharmacologists we anticipated the possibility of isolation by SC-CO2 technique and comparative analysis of quality characteristics of extracts from small samples of endemic plants. The study included also pharmacokinetics and bioequivalence of individual natural biologically active compounds or extracts and their suitability for food and pharmaceutical products making. In the present communication we like to report the results of wheat germs grown in Republic of Moldova and Romania and Milk thistle (Silybum mariuanum L.) seeds extractions which were done on a laboratory pilot installation for SC-CO2 extraction equipped with a 1000 cm3 extraction vessel, two connected in series separators of 600 cm3 each, a supply line, a tank for co-solvent and a plunger pump which permits the use of pure or mixed fluids within 4±10% of co-solvent and a computer setup software of the process. The extraction of mentioned raw materials was carried out during 1h at 37-42ºC and a pressure of 35-40 MPa, with extract separation in the first separator at 45ºC and 14-17 MPa and at 35ºC and 6,5-7,0 MPa in second using 35 kg of extracting agent per 0.5 kg of the raw material. The continent of fat oil in according with SC-CO2 extraction was 8- 9 % for wheat germs and (26-28) % for S.mariuanum. The chemical compositions of both species of oil were analyzed by gas-chromatography coupled with mass-spectrometry (GC-MS) and high resolution liquid chromatography (HPLC), also their physical, chemical and quality parameters were measured. In correspondence with GC data (see table 1) both species have a high content of unsaturated fatty acids (including polyunsaturated) – 81,67% for wheat germs and 82,15%for S. mariuanum, respectively.

147 Table 1 Omega Omega 6 3 C16: C18:3 C20: C20: C22: C22: Acids C14:0 C16:0 1 C18:0 C18:1 C18:2 alfa 0 1 1 0 C24:0 M/mas 242.4 270.4 268.4 298.4 296.4 294.48 292.4 326.5 324.5 346.5 348.5 376.5 Wheat Germs 0,10 16,89 0,18 0,73 15,05 57,21 7,60 0,08 1,33 0.30 0.09 0,08 Milk Thistle 0,09 7,61 0,07 4,31 31,94 48,88 0,19 2,63 0,99 0,08 2,30 0,74 The content of vitamin E (α-, γ-,δ-tocoferol, mg/100 g of extract) depends of the used regime of extraction and has quite large limits (see table 2). Table 2 α-tocoferol γ–tocoferol Σtocoferols Wheat germs 123,6 67,55 191,15 Milk thistle 23,45 5,60 29,05

Acknowledgements : This work was supported by the project № 24/RoA.

Bibliography: 1. Reverchon,E., Marrone,C. Modeling and simulation of the supercritical CO2 extraction of vegetable oils. J.Supercrit.Fluid, 2001,19,р.161-175. 2. Lang,Q.; Wai,C.M. Supercritical fluid extraction in herbal and natural product studies-a practical review.Talanta, 2001, 53, р.771-782.

FULL PROCESSING OF LARCH WOOD

E.E. Nifantiev Moscow State Pedagogica University [email protected]

INHIBITION OF LIPASES - A PERSPECTIVE WAY TO IMPROVE THE QUALITY OF RAPESEED OIL

A.I. Nikitsenko, V.S. Boltovskii, V.N. Leontiev Belarusian State Technological University, Minsk, Republic of Belarus [email protected]

In recent years, much attention is paid to food: their quality, useful properties, biological activity. Vegetable oils are no exception. Production of vegetable oil has an important place in the fat and oil branch of food industry. Vegetable oils and products based on them are valuable food components. The most important role of these products is determined by their energy value (in fats, it is more than two times higher than that of carbohydrates and proteins and is 37,700 kJ / kg). The feature of global agriculture in recent years is the intensive cultivation increase of oilseeds that is the main raw material for the production of vegetable oils and a valuable source of feed protein. One type of such oilseeds is rape. Physiological value of the crop, and thus the products derived from it is determined by the content of essential substances for the body: fat-soluble vitamins A, D, E and K, essential fatty acids, which are not synthesized in the human body. 148 Climatic conditions of the Republic of Belarus are favorable for growing rapeseeds. Therefore, from 1995 to 2007, cultivated area under rapeseed has increased from 47.7 to 218 thousand hectares, and the gross harvest of the crop rose to 600 thousand tons. Accordingly, it is obvious that this direction is urgent and perspective not only for the Republic of Belarus but for middle zone of Russia as well. The purpose of the research - to examine the fatty acid composition and resistance for oxidation of different breeds of spring rapeseeds, cultivated in the climatic conditions of the Republic of Belarus, to identify the most suitable for processing. It was established during the analysis by gas liquid chromatography method that the content of unsaturated fatty acids in spring rapeseeds of some breeds, with 40–46% oil content, was 82,9-91,3%, while the amount of oleic acid constituted 57–63%, that brings the oil from the rapeseeds closer in composition to olive oil. However, since vegetable oils are a complex system, the main component of which are triglycerides of fatty acids with different chain length and number of double bonds, under the influence of environmental factors, they are easily subject to changes, including in most cases the hydrolysis splitting, catalyzed by enzymes and accompanied by the release of fatty acids and their oxidation, that always means the decrease of nutritional value. One of the significant factors affecting the resistance for oxidation and, thus, the quality of rapeseed oil, especially crude one, is the action of lipolytic enzymes that fall into the oil from the seeds in the process of removing it. Lipase (triacylglycerol acyl hydrolase, steapsin, tributiraza, triglyceride lipase EC 3.1.1.3) – an enzyme that catalyzes the hydrolytic cleavage of triacylglycerols to glycerol and fatty acids, increased content of which leads to deterioration of the final product quality – the increase of the oil acid value. The analysis showed that the activity of lipase isolated from the press cake of spring rapeseeds, which was obtained by direct cold pressing, varies for different breeds within 11-18 mkmol / h · mg protein. Therefore, to preserve the biological value of rapeseed oil obtained by direct cold pressing, the stage of lipase inhibition, in the absence of thermal processing of oil, should be provided.

NEW FUNCTIONAL PRODUCTS BASED ON LIGNOCELLULOSE SORBENTS FROM PLANT MATERIALS

A.A. Nikolaichuk, M.T. Kartel, N.Y. Borovitsky Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine [email protected]

The development of human civilization is impossible without a rational interaction with nature.

Despite the fact that since the "Chernobyl disaster" past 25 years, the problem of removal of radionuclides from the human bodies remains true today and will always have over the years, especially in connection with the recent events at Japanese nuclear power plant "Fukushima-1". So now a necessity arises to create new dietary supplements, functional foods, and combined materials with sorption, decorporative, radioprotective, and antioxidant properties. In the current situation, the leading role in protecting the population from chronic “environmental poisoning” belongs to efferent medicine, primarily-sorption therapy and prophylaxis. Recently vegetable enterosorbents are preferred because they, in contrast to synthetic ones, are substances biologically compatible with body and "soft" (according to the effect on the mucous membrane). To solve the problem, the tasks have been fulfilled as follows: - the structural characteristics (pore volume, specific surface area, pore distribution by size) lignocelluloses materials have been deferent; - the combined physical and chemical (electron microscopy, IR, NMR and mass spectrometry) studies have been carried out on the content of the compositionally heterogeneous lignin-cellulose 149 conglomerates and the nanostructured molecular organization of lignin and its biocomplexes with cellulose has been determined; - the technology of preparation of "Sorbents lignocelluloses" (Code U 15.8-03291669-008:2008) of plant material for use in the food industry as a dietary supplement and functional food products Сelisorb (Code U 15.8-03291669 -014:2010); - the experimental batch of products has been obtained; - the combined physical and chemical studies have been carried out on the composition and properties of new sorbents, a dependence has been shown of sorption properties (removal of heavy metal (Cu, Pb, Sr, Ni, Cd, Cs) ions and organic dyes (substances - markers): Methylene Blue, Methyl Violet, and Congo Red from model solutions under static and dynamic conditions) of composite lignocelluloses conglomerates on their structure; - the organoleptic and physical-chemical parameters have been studied that enable an implementation of the materials obtained into to medicine and food industry as (entero)sorbents, antioxidants, and bioactive admixtures to solve many environmental and health problems; - the clinical studies have been carried on the assessment of decorporative and therapeutic efficacy concerning 137Cs for children aged 7-17 years - permanent residents of territories contaminated with radionuclides. Approaches to processing plant material were based on the "green chemistry" principles, that exclude the use of toxic reagents and can minimize the ecological press on the environment. When developed, the technology for modification of biomass has been shown to enable producing sorbents with high ion exchange capacity and selectivity to heavy metal ions, dyes, and radionuclides. The results of applied research serve as the scientific basis for environmentally sound and practically useful lignocellulose sorbents that will enable their practical use in solving some problems of chemical engineering, ecology, and medicine.

OPTICALLY ACTIVE DITHIOPHOSPHATES ON THE BASIS OF BYCYCLIC MONOTERPENOLS

I.S. Nizamov, L.A. Almetkina, Ye.M. Martianov, G.T. Gabdullina, R.A. Cherkasov Kazan (Volga region) Federal University, Kazan [email protected]

The importance of chiral terpens and their derivatives as well as phosphorylated esters is related to their potential metabolic regulation activity. We have involved in chiral bycyclic monoterpenols such as (1R)-endo-(+)-fenchyl alcohol, (1S)-endo-(-)-borneol and (1R,2S,3S,5R)-(+)-isopinocampheol into the interactions with tetraphosphorus decasulfide. On this basis, novel optically active O,O-diterpenyl dithiophosphoric acids were obtained. These acids were transformed into the corresponding ammonium salts.

S O 8 + P4S10 4 P -2 H2S O SH OH S OH OPO 8 + P4S10 4 HS -2 H2S

Silyl and plumbyl derivatives of O,O-diterpenyl dithiophosphoric acids were prepared on the basis of the reactions of ammonium salts of corresponding acids with monochloro- and dichlorosilanes, monochloro- and dichloroplumbanes.

150 _ + S S NH4 OPO R ECl 2 2 O R O 2 S S P P S S-E-S - 2 NH Cl S 4 O R O

E = Si, Pb

Novel S-organyl O,O-diterpenyl dithiophosphates were obtained by the reactions of ammonium O,O-diterpenyl dithiophosphates with epichlorohydrin, methyl chloroacetate and benzoyl chloride. R O S Cl R O S P + + S NH P S R O 4 O -NH4Cl R O O

R =

The derivatives of chiral dithiophosphoric acids prepared possess antimicrobial activity.

SILYL AND PLUMBYL DITHIOPHOSPHONATES ON THE BASIS OF TERPENS

I.S. Nizamov1, G.T. Gabdullina2, L.A. Almetkina2, Ye.M. Martianov2 1 - Kazan (Volga region) Federal University, Kazan; A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan 2 - Kazan (Volga region) Federal University, Kazan [email protected]

The interest in dithiophosphonic acids and their silyl and plumbyl derivatives is due to their potential biological activity. We deemed it to be necessary to prepare novel dithiophosphonic acids containing asymmetric centers in organic substituents. For this purpose, we have synthesized dithiophosphonic acids by the reactions of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with chiral monoterpenols. We have used chiral terpenols such as (1S)-endo-(-)-borneol, (1R)-endo- (+)-fenchyl alcohol, (1R,2S,3S,5R)-(+)-isopinocampheol and (1R)-(-)-nopol. Optically active O- terpenyl aryldithiophosphonic acids were obtained when these chiral terpenols were involved in reactions with 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides. These thioacids were transformed into the corresponding ammonium salts.

151 S S O P OH P OH O SH SH

OH OH

S S HO P P OH S S OH OH

S S OH P OH P OH O SH O SH S

P OH R3ECl O S - NH4Cl

OH S

E = Si, Pb P OH O SER 3

New silyl and plumbyl derivatives of aryldithiophosphonic acids were prepared on the basis of the reactions of ammonium salts of corresponding acids with triorganylchlorosilanes and chloroplumbanes. The silyl and plumbyl derivatives of aryldithiophosphonic acids with chiral possess appreciable antimicrobial activity.

THIOPHOSPHORYLATED DERIVATIVES OF NATURAL DIOLS AND TRIOLS

I.S. Nizamov, Ye.M. Martianov, L.A. Al’metkina, G.T. Gabdullina, D.S. Terenzhev, R.A. Cherkasov Kazan (Volga region) Federal University, Kazan [email protected]

Thiophosphorylated derivatives of natural diols and triols are necessary to develop convenient methods of preparing new products with biological activity. We have tried to develop convenient methods of synthesis of organothiophosphorus derivatives of some chiral natural diols and triols such as pinanediols, dimethyl L-tartrate, and glycerol, as well as vitamins such as pyridoxine hydrochloride and tocopherol. 2,4-Diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides have brought about to react with trans-3,4-pinanediol or dimethyl L-tartrate with the formation of arylbisdithiophosphonic acids. The similar tristhiophosphorylated derivative was prepared in the case of glycerol. Arylbisdithiophosphonic acids obtained were transformed into the corresponding diammonium salts. The diammonium salts of bisaryldithiophosphonic acids seem to be efficient intermediates for synthesizing their organoelement derivatives by the substitution reactions with appropriate organoelement halides. New silyl and plumbyl derivatives of arylbisdithiophosphonic acids were prepared on the basis of the reactions of diammonium salts of corresponding acids with triorganylchlorosilane, chloroplumbane, diphenyl dichlorosilane and diphenyl dichloroplumbane. We have developed facile method for the thiophosphorylation of vitamins containing a few hydroxyl groups. We have found that pyridoxine hydrochloride reacts with 2,4-diaryl 1,3,2,4-

152 dithiadiphosphetane-2,4-disulfides in benzene at 80оС for 2 h to give the corresponding tristhiophosphorylated derivatives.

S OH S P-Ar SH S O SH HO Ar-P S OH S Ar-P P-Ar + O S O P-Ar S N. HCl N. SH HCl Ar = HO

Vitamin B6 was also involved in the reaction with 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides in transformed form. Thus, we have used acetone protection of two hydroxyl groups of pyridoxine. The dithiophosphonic acid as internal salt was formed with the participation of only single hydroxyl group. S OH O S Ar-P S _ P-Ar S O S O Ar-P HO O HCl HO S O OH O - 2 H O N. 2 N HCl + N Ar = HO H

Thiophorylated derivates of natural diols and triols showed appreciable antimicrobial activity.

BIOENERGETICAL COMPLEX «BIOCHECK»

K.V. Novikov, V.A. Kozlov, D.A. Ionova, D.A. Sosnov Chuvash state teachers training university after named I.Y. Yakovlev, Cheboksary, Russia [email protected]

The birds’ dung treats to the second class of toxicity of industrial wastes and it’s a dangerous waste of poultry-factories. In ground waters at places of storage of the birds dung the maintenance (ml/l) of nitrate nitrogen exceeds its maintenance in drainage waters from cattle farm fields by 2 times, ammoniac nitrogen – by 8 times, phosphorus – by 11 times, potassium – by 10 times. As a result we have the wasting of the rivers, landlocked ponds and lakes by nitrogen and phosphorus that causes their rough eutrophication. The problem of safe recycling of the birds dung is actual nowadays and it isn't solved yet. The traditional ways of recycling of the birds dung are ecologically unsafe and economically insolvent. We’ve designed the technology of two-line biological recycling of the birds’ dung [1]. The entity of the offered invention is in the creation of special complex (special name: Bioenergetical complex «BioCHECK» (Figure 1)). It realizes pioneer technology of deep year-round biological recycling of sewage, silt and other wastes. The technology is self-sufficient and the necessary power and thermal energy is provided by biogas methane which is got as a result of interaction between water vegetation of Eichhornia crassipes Martius and sewage or industrial wastes. The main technical result of the invention – synergetic effect of all-the-year-round deep biological processing of the waste with the simultaneous electricity and thermal energy production which is enough not only for an independent work of the complex, but to sale the energy to external customers.

153

Figure 1

The bioenergetical complex is characterized by the presence of interconnected gas turbine/gas cylinder piston power plant and covered system of raw material gasification (SRMG). SRMG contains the module of purification facilities (MPF) for hydrobotanical recycling of wastes, the module of gas production (MGP). Also there is the control module (CM).

REFERENCES

[1] V.A. Kozlov, R.A. Zurnadjyan, D.A. Ionova, K.V. Novikov, Yu. D. Karpenko, V.A. Elenkin, V.A. Gartfelder, O.G. Dmitrieva. Bioenergetical complex (BIOCHECK) for wastes’ processing. Patent onto a beneficial model. MPK: В 09 В 3/00, С 02 F 3/00 Е 04 Н 5/00. Priority 154 number №2010101403 from 18. 01. 2010. The decision about an issue of patent onto the beneficial exemplar №2010101403/22(001933) from 26. 03. 2010.

THE INFLUENCE OF DIFFERENT GROWTH REGULATOR CONCENTRATIONS ON IN VITRO CALLUS FORMATION IN CONIFERS

E.N. Novikova, N.N. Sheveleva Mari state technical university, Yoshkar-Ola, Russia [email protected]

Depletion of forest genetic diversity and lack of sufficient planting material because of the difficulty of vegetative propagation of valuable forest genotypes leads to deterioration in the quality of forest plantations. Application of the methods of culture of isolated organs and tissues in vitro holds promise for the accelerated production of high-quality planting material for establishment of plantations for various purposes. Conifers are one of the most complicated objects for in vitro cultivation. This is connected with their slow growing, difficult rooting and content of secondary compounds (phenols, terpens, etc.), which are activated in isolated tissues. The process of propagation depends on cultures` ability for plant regeneration directly from the explant or via a callus phase. [1] The aim of this study is to research growth regulators influence on callus formation in Picea abies and Pinus sylvestris culture. Apical meristems of 1-year plus tree shoots were taken as explants for introduction in vitro culture. They were washed in tap water with addition of several drops of «Tween 20», and then disinfected by immersion in 70 % ethanol for 30 s and in 50 % sodium hypochlorite for 15 min, rinsed three times with sterile distilled water.

154 The basal medium used for induction of callus from Picea abies apical meristems consisted TE medium containing 0,01 mg/l α-napthaleneacetic acid (NAA) and various concentrations of benzyladenine (0-5 mg/l) (BA), 30 g/l sucrose, 6 g/l agar. Explants were grown at 21-22 ° C with 16-h photoperiod and 1800 Lx light intensity. After 2 months of cultivation the maximum callus induction frequency (57, 1 %) was obtained on TE medium supplemented with 0,01 mg/l and 0,5 mg/l BA. The apical meristems of Pinus sylvestris were cultivated on MS medium including different combinations of auxins with their total concentration 2 mg/l. After 1 month of cultivation callus formation was observed on medium 1 with 1 mg/l 2,4-dichlorophenoxyacetic acid (2,4-D) + 1 mg/l NAA (13,3 %,), medium 2 with 1 mg/l 2,4-D + 1 mg/l IBA (7,5 % %,) and on medium 3 with 2 mg/l NAA (5,0 %). These experiments allow to choose convenient concentrations of plant growth regulators for callus induction, and also to determine the direction of further research. Vegetative propagation of superior coniferous forest trees has the potential to deliver a stable supply of superior seedlings for forest plantations. [2]

References 1. Mariev A. N. Priority directions of forest biotechnology: from research to practice / A. N. Mariev / The sixth Moscow international congress Biotechnology: State of the art and prospects of development: Book of abstracts, part 2. - Moscow, 2011. 2. Klimaszewska, K.·Initiation of somatic embryos and regeneration of plants from primordial shoots of 10-year-old somatic white spruce and expression profiles of 11 genes followed during the tissue culture process / K.·Klimaszewska, C. Overton, D. Stewart,·R. G. Rutledge / Planta, Springer, 2008.

RESEARCH OF SUBSTANCES EXTRACTION KINETICS FROM AN OAK CHIPS

I.V. Novikova1, T.S. Kornienko2, A.V. Korostelev1, S.V. Vostrikov1 1 - VSTA, Technology of Industrial Fermentations and Wine Making, Voronezh, Russia 2 - VSTA, Analytical and physical chemistry, Voronezh, Russia [email protected]

Extending use of wood extracts by working out of compoundings of strong alcoholic drinks demands improvement of technology of their manufacture, definition of optimum duration of process and extraction degree components from the wood, causing organoleptic properties of a ready drinks. The research problem included studying extraction kinetics of target components at a filtration an aqueous-alcoholic solution through the oak chips layer and an establishment of functional communication of concentration of an extract with duration of process. At contact of firm porous particles to a liquid in the beginning there is its penetration into a free part porous spaces under the influence of the capillary forces, accompanied by transition of taken substances in solution. For finding-out of laws of process at an impregnation stage experiments on the installation including a glass column in internal diameter of 55 mm with a shirt for temperature stabilizing, pressure head capacity, the thermometer are made. The column worked in a semi-continuous mode: through a motionless layer in height of 65 mm thermally processed oak chips passed water solution (50% vol.) of ethyl spirit arriving in the bottom part of the device. For uniform distribution of a liquid on column section wood the chips placed between two layers of inert spherical bodies in height on 40 mm. It is established that the optical density of extract and its concentration are connected by linear dependence. Last circumstance has allowed to find substances concentration in tests in a constancy assumption in time of a parity of components, and also their concentration in exhausted cheaps, using the equation of material balance. The experimental material is correlated by simple dependence Е=0,021 θ / (1+0,065 θ), where Е =1 – С1/С0 – extraction degree; С0 = 0,122 seasoned 3 wood, g/sm - concentration substances in raw materials; C1-corresponding concentration in

155 exhausted cheaps, g/sm3; θ = τ / τ ' – frequency rate of contact cheaps with a liquid; τ – duration of process, s; τ ' = L/U – the liquid pass time through a layer, s; L – layer height, m; U = Vzh/S • ε – 3 average speed of a current in layer channels, km/s; Vzh – liquid giving, m /s; S – the area of section of a column, m2; ε – porous spaces in the layer. The problem of the second series of experiences included studying of diffusive characteristics of wood. It is visible that after 96 hours the extraction process was sharply slowed down, the components concentration in exhausted cheaps came nearer to constant value. The part of substances, concentrated in remote areas, it is expedient to exclude a part from kinetic calculations because presence of such zones doesn't allow to reach full extraction or causes considerable lengthening of process in time. The substances represent group of the connections differing with diffusive characteristics. In such objects consider set of all taken substances as uniform «a target product». Permeability of covers of vegetative cages is provided with that their structural basis is made by cellulose – polymer with the linear macromolecules connected in fibrills, with diameters 1 - 10 nanometers.The particle of wood cheaps can be considered as an unlimited plate as its width b and length l which essentially exceed a thickness δ (l / δ = 22; b / δ = 16). In an unlimited plate the one-dimensional diffusive stream in a direction of the minimum size is established. The received extracts can be applied as bases to preparation of strong alcoholic drinks with using of oak wood. The maintenance flavour - and aroma- components taken by spirit from wood, renders a great influence on organoleptic indicators of products. In this connection the received dependence allows to define the maintenance of the substances taken from wood in extracts for control of technological process at preparation of components of alcoholic beverage products with use of wood raw materials.

BIOCHEMICAL AND TECHNOLOGICAL ASPECTS OF BAS OF FUCOIDS OF THE BARENTS SEA

E.D. Obluchinskaya Murmansk Marine Biological Institute, Laboratoty of algology, Murmansk, Russia [email protected]

Fucoids as well as other brown seaweed is natural sources of important polysaccharides - alginate, fucoidans, laminarans. Polysaccharides of brown seaweed are used in medical and the food- processing industry, in agriculture and in chemical branch. Seaweed as raw materials of a natural origin, differ variability of a chemical compound. It is known, that synthesis of polysaccharides each kind of species is defined by conditions of growth or cultivation seaweed, i.e. light exposure, intensity of movement of water, degree of random sea, salinity, temperature, substratum type, and also ontogenetic factors. Biochemical specials of fucoid seaweed of the sea Barents sea are studied insufficiently. For the decision of technological questions at processing of treatment of raw materials standardization of its chemical compound - the important problem. Earlier by us it has been shown (Obluchinskaya, 2008), that the Fucus vesiculosus from the coast of the Barents sea contains the high concentration of fucoidan within all year, and the greatest quantity alginic acid during the summer-autumn period and is the most perspective resource for extraction of polysaccharides among fucoids of the Barents sea. Also it has been established, that the quantity of polysaccarides at a F. vesiculosus is changeable at harvesting in different places of growth. On the basis of the long-term researches in Murmansk Marine Biological Institute on studying of biology, physiology and biochemistry of brown seaweed, and also investigation of conditions of their growth, we make attempt to estimate of effect of salinity and intensity of movement of water on concentration of polysaccarides of F. vesiculosus from the Barents sea. By us it is established, that the quantity of alginic acid is subject to the bigest changes under the influence of environment factors in comparison with the quantity of fucoidan. Thus variations of salinity of 12-25 ‰ and intensity of movement of water 0,012 - 0,007 mg*g/h are optimum for 156 accumulation of alginic acid and fucoidan. The concentration laminaran increase by external conditions with very high values intensity of movement of water or low salinity. The harvesting seaweed F. vesiculosus for extract of polysaccharides and for cultivation it is more preferable to choose habitats of the protected coast with running streams. And we also develop and patent the optimised technologies of complex treatment of fucoids of the Barents sea with production of several biologically active substances (BAS) (the Patent of the Russian Federation № 2337571). The general scheme of complex treatment of fucoids is a basis of technology of seaweed of the Barents sea with production in a uniform work cycle individual substances and complex preparations. The method suggests to use as raw materials for production of BAS nonconventional species of resource - fucoids of the Barents sea (Fucus vesiculosus, Fucus serratus, Fucus distichus and Ascophyllum nodosum). As end-products receive: a lipidno-pigmentary complex in the form of a dense extract, mannitol, complex of polysaccharides in the form of a dry extract and sodium alginate. As a result of long-term researches methods of complex treatment of four species of fucoids of the Barents sea with production BAS with standard characteristics for application in medicine, a himiko-pharmaceutical industry and in the food-processing industry are developed and patented. By optimisation of technologies of treatment of fucoids it was possible to increase an yield of target products by 5-17 % depending on a species of seaweed at simultaneous increase in degree of their cleanliness, including from a F. vesiculosus on 7-17 %, namely: LPC - on 15-17 %, mannitol - on 7 %, fucoidan - on 10-17 %, sodium alginate - on 8-16 %; from a F. distichus: LPC - on 5 %, mannitol- on 4-7 %, fucoidan - on 14-17 %, sodium alginate - on 6-15 %; from a F. serratus LPC - on 9 %, mannitol - on 6-8 %, fucoidan - on 9-14 %, sodium alginate - on 6-15 %; and Ascophyllum nodosum: LPC on 15-24 % at the concentration of a chlorophyll not less than 8 %, mannitol 11-13 %, complex of polysaccharides of 18-24 % and sodium alginate on 12-15 % (Plot. 1). The literature list. Obluchinskaya E.D. Comparative research of brown seaweed OF the Barents sea // Appl. Biochemical and microbiology. 2008. Т. 44. № 3. P. 377-342. Obluchinskaya E.D. Method of complex treatment of fucoids (variants). The patent of the Russian Federation № 2337571//B.I. № 5, 2008.

100 90 80 70 60 50 40 30 20 Yield of fucoidan,% 10 0 method 1 method 2 method 1 method 2 method 1 method 2 F.distichus F. serratus A. nodosum

10% ethanol 20% ethanol 30% ethanol

Plot. 1. Effect of extraction method from yield of polysaccharide complex - fucoidan Method 1 – general scheme; Method 2 – optimum mode for each species of seaweed

157 PHYSICAL - CHEMICAL PROPERTIES OF MODIFIED СELLULOSE ETHERS - THICKENERS WATER – DISPERSION SYSTEMS

I.I. Osovskaya1, A.L. Kovjgina2, J.A. Kukharenko1, A.V. Milutina1 1 - Saint-Petersburg state technological university of plant polymers 2 - Saint-Petersburg state technological institute [email protected]

Thickeners based on cellulose ethers are the most common rheological additives for water- dispersion paints, whose primary functions are: thickening effect, rheology control, stabilization, and water retention. When considering the whole sequence of "life colors", ranging from its production onwards - storage, application and drying, revealed that all of the following aspects way or another depend on the choice of cellulose ether: - crushing or dispersing pigment and filler; - the existence of foam formed in the grinding process; - the viscosity of the aqueous phase and the finished paint; - stabilization, providing good stability during storage of paint and lack of effect of syneresis; - resistance to microbial degradation; - preventing flocculation or coagulation of pigment particles. In connection with the purpose of this study was to investigate the physicochemical properties of modified cellulose ethers are used as thickeners composite water- dispersion paints. The objects were chosen both traditional) and associative thickeners based on cellulose ethers. In viscosimetric method the relative and the viscosity of the samples. When measuring the viscosity to suppress the polyelectrolyte effect of the solvent used 2% aqueous solution of sodium chloride. The paper shows the effect of viscosity of cellulose by a number of properties of water-dispersion paints. In particular, the thickening efficiency decreases when changing the type of cellulose ether with high viscosity on the type of medium viscosity. On the instrument Du-Nui were obtained isotherms of surface tension (σ). Construction of a semi- logarithmic coordinates σ from lgC to determine the critical micelle concentration. Based on the colloid-chemical studies of various cellulose ethers as thickeners aqueous dispersion of hydrophobic material selected is a modified hydroxyethylcellulose, which combines the unique properties of the regular product hydroxyethylcellulose with rheological properties typical for synthetic associative thickeners. Content in the molecule hydroxyethylcellulose hydrophobic groups makes it possible adsorption on the surface of film-forming, forming in the aqueous micellar phase, associative complexes. The influence of the nature of thickeners on the formation of coatings and water-resistance of formed films were studied. The optimal thickeners are Natrosol 250 HHBR, Natrosol Plus 330, PA Mecellose FMS 8821.

THE RATING OF EXTRACTIVE SUBSTANCES CONTENT IN LARCH KNOTS AND ROOTS

L.A. Ostroukhova, N.A. Onuchina, V.A. Babkin A.E. Favorsky Institute of Chemistry Russian Academy of Sciences Siberian Branch, Irkutsk, Russia [email protected]

It is not desirable to use wood knots due to shorter fibres and large amount of extractive substances in cellulose and paper production. Both shorter fibres and extractive substances absorb the chemical reagents used in cellulose production to the greater degree. In addition, high energy consumption in chopping of knots is needed so as the last are much harder than the common wood. There are the methods of knot wood chopping and separation from the base fraction for cellulose production in order to use it as stuff for biologically active substances production [1].

158 With the purpose of obtaining of the new effective phytopreparations from the inexpensive renewable raw material, the complex wasteless processing technology of the biomasses of Siberian larch and Gmelin’s larch has been developed [2]. High antioxidant properties of knot wood hydrophilic extracts of some commercially important tree species, including two larch species (L. lariciana и L. sibirica), have been shown with the help of the lipid peroxidation inhibition and peroxil radicals catch possibility tests [3]. According to our data, the main phenol compounds of the knots of Siberian Larch and Gmelin’s Larch, growing in the Eastern Siberia, are flavonoid dihydroquercetin and lignans with the predominant content of secoisolariciresinol. Considerable content of polysaccharide arabinogalactan has been also discovered. Taking into consideration the high biological activity of these natural compounds, the investigation of chemical composition and processing of larch knots and branches of the Siberian species is urgent. The root system of larch in usual conditions is vigorous, ramified and without pronounced taproot. For the purpose of practical use of presently nonutilizable larch roots, the root extractive substances content dynamics analysis has been conducted on an example of one tree (sampled from one tree of L. sibirica Ledeb. of the age of 120 years at the suburbs of Irkutsk, Eastern Siberia, Russia). It has been established that the minimal content of the extractive substances in roots is observed in January and February, increases by July and tops in August. The extractive substances content in root is greater than the one in trunk over a year. Flavonoid accumulation dynamics is analogous to extractive substances content dynamics in the investigated members of a tree. The content of the main flavonoid of larch wood dihydroquercetin in roots exceeds the one in trunk 2-6 times over a year. These values for roots and trunk are approximate only in May and June. Over a period of observation the content of resins in roots has been a few less than the one in trunk. Quantity of water soluble substances (polysaccharide arabinogalactan) reaches the maximum by October – January and begins to decrease in February, and faster in roots than in trunk. It reaches the minimum by March – June. Thereby, both the roots and the knots may serve as an additional rich source of the main valuable products of larch biomass: dihydroquercetin, lignans and arabinogalactan. References 1. Eckerman, C, Holmbom, B. Method for recovery of knotwood material from over-size chips // Finn. Patent N 112041. - 2003. 2. V.A. Babkin, L.A. Ostroukhova, S.Z. Ivanova, at all. The Products of Penetrating Chemical Processing of Larch Biomass. Obtaining Technology and the Application Perspectives., Mendeleev commun, 2004, v XLVIII, 3, p. 62 – 69. 3. Pietarinen S.P., Willfor S.M., Ahotupa M.J. et al. Knotwood and bark extracts: strong antioxidants from waste materials // Journal of wood science. - 2006. - V. 52. - N 5. - Р. 39-51.

CATALYTIC PRODUCTIONS OF BIOLOGICALLY ACTIVE COMPOUNDS

Z.P. Pai, V.N. Parmon Boreskov Institute of Catalysis SB RAS [email protected]

Integrated processing of natural renewable raw materials, including wood using industry waste, makes it possible to produce industrially claimed materials, such as epoxides, mono and dicarboxylic acids. These materials have found a wide application in different fields. The carboxylic acids, involving along with carboxylic groups some other functional groups, can be used as matrixes and building blocks for synthesis of medical preparationts or their precursors. The method of phase-transfer catalysis with bifunctional homogeneous catalysts based on the peroxopolyoxotungstates is a very promising way to perform oxidation transformations of natural raw materials into novel biologically active materials. The peroxo compounds formed in systems H2O2 – H3PO4 – Na2WO4 and H3PW12O40 – H2O2 are sufficiently stable and anion 159 3- {PO4[WO(O2)2]4} exhibits high activity in the oxidation reactions [1]. A simultaneous application of phase-transfer catalysts as quaternary ammonium cations (Q+) and oxidation catalysts as peroxopolyoxotungstates permits one to perform oxidation processes during one technological step. In the present work we have screened different substrates such as cycloolefins, unsaturated fatty acids and their ethers, lupane-type triterpenoids and coumarins. The oxidation reaction was performed in a two-phase system in the presence of Q3{PO4[WO(O2)2]4}. Most of the resulting products – derivatives of betuline, peucedanine and unsaturated fatty acids – exhibit antiviral, antiinflammatory and anticancer action [2].

The work was supported by the Russian Foundation for Basic Research (Project 09-03-00395-а) and Branch of General and Technical Chemistry RAS (Project 5.7.3.).

References: 1. Z.P. Pai, D.I. Kochubey, P.V. Berdnikova, V.V. Kanazhevskiy, I.Yu. Prikhod’ko, Y.A. Chesalov, J. Mol. Catal. A: Chemical, 332, No 1-2 (2010) 122–127. 2. G.A. Tolstikov, O.B. Flekhter, L.A. Baltina, Chemistry for Sustainable Development, 13, No 6 (2005) 1-30.

OBTAINING OF SILICON AND SILICON DIOXIDE FROM VEGETABLE RAW MATERIAL

A.E. Panasenko, L.A. Zemnukhova, G.A. Fedorishcheva, N.V. Polyakova, E.A. Tsoy Institute of Chemistry FEB RAS [email protected]

Manufacture of elementary silicon plays an important role in modern chemical industry, metallurgy, and electronics. Among all the silicon compounds, silicon dioxide having a wide application takes the first place. In particular, it is used in production of glass, building materials, catalysts, sorbents as well as in light and chemical industry. In connection with growing volumes of consumption of silicon and its compounds, the problem of search of new sources of raw material which would be the cheapest and convenient in technological aspect, is actual. Vegetable raw material may be one of such sources. Thus, rice production waste making up about 100 million tons per year contains to 7% of silicon. At present it is utilized as a chemical raw material less than half. The quality of such a kind of renewable raw material consists in the fact that silicon dioxide is in the active (amorphous) form, suitable for processing and allowing to obtain high pure silica and silicon under easy technological conditions. The present work contains the results of investigation on obtaining of silica and elementary silicon from various kinds of vegetable raw material: rice (Oryza sativa) production waste — hull and straw, horsetail (Equisetum hyemale, Euisetum sylvaticum) and larch-tree (Larix dahurica) needles. For comparison we used reagent SiO2 (GOST 4214-78) and silicon dioxide obtained from a mineral raw material — diatomite (Ausralia). Silicon dioxide was obtained by acid hydrolysis of the initial raw material with following calcination of the solid residue at the temperature about 750°C [1]. Maximum purity of SiO2 samples obtained by this way achieved 99.999%. High specific surface (about 300 m2/g), sorption capacity relative to heavy metal ions, small size of the particles are its valuable properties. According to the electron microscopy data, silica particles keep the porous structure of the vegetable tissues. Elementary polycrystal silicon was obtained by reduction of SiO2 with metal magnesium and following washing with acids for purifying from by-reactions products. Silicon samples were identified by the X-ray diffraction and IR spectroscopy methods. Its yield achieved in our laboratory equaled 40 kg per ton of rice hull. Depending on the initial raw material, purity of the substance obtained differed in a great degree. Silicon prepared contains 99.2—99.8% of the main substance, i. e. corresponds to the technical silicon by its purity. Moreover, the technology of its obtaining is easier than the known carbothermal method that is important for organization of mass 160 production. The silicon samples prepared were investigated by the scanning electron microscopy method and their morphology was described.

1. Properties of amorphous silica produced from rice and oat processing waste Zemnukhova L. A., Egorov A. G., Fedorishcheva G. A., Sokol'nitskaya T. A., Barinov N. N., Botsul A. I. // Inorganic Materials. 2006. V. 42, No 1. P. 24-29.

INSTALLATION FOR RESEARCH OF CONDUCT OF THE MATERIAL IN THE CONDITIONS OF OVERALL COMPRESSION

E.I. Panov, I.I. Prilepina, V.P. Hanin Orenburg State University, Department «Machinery and equipment of chemical and food productions» [email protected]

During the materials processing of materials by pressure there are conditions in which structural changes of materials, their transition from one condition to another take place. For example, at the beginning of wood sawdust pressing we have a loose product, during pressing we receive an elastic- lamellar body, and as a result we receive a solid product. In a consequence with it, unequivocally it is impossible to define physicomechanical properties during the work. On the machinery and equipment of chemical and food productions department of the Orenburg state university the experimental installation for material studying in the conditions of overall compression was worked out. In working cavities of the installation there were conditions for materials reception in the conditions of plasticity, at the expense of material portion closure in the calibrated aperture and material compression to necessary pressing effort. Stress conditions of the fine-dispersed material in cylindrical die channels of pressing machinery are defined by type action of working bodies, power consumption of pressing processes, quality of received products. However straightforward experimental researches in working cavities of machinery are complicated because of the introduction in investigated system additional elements in the form of the measuring systems, are also influencing on the process. In this connection the design of the installation for research of wood sawdust tension into the die channel is offered. The installation consists of squeezer on which basic surface of the device with measuring tenzometric system is placed. The device supports the cylindrical basis in which on the measuring bush the compression chamber connected with forming die is located. Material squeezing is made by plunger which with a small backlash enters into the compression chamber. The backlash is chosen to exclude material reverse motion at its squeezing. Besides the measuring bush tensometric sensors also are located on the external surface of the forming die along its length. In the installation there is a possibility to choose various length and various diameter of the dies channels. The device works in the following way: at the beginning a portion of raw materials is given to the compression chamber, of a retrace of the press this portion of raw materials is given by plunger, piston reverse motion take plunger from the compression chamber, this process is repeated up to the full filling of the compression chamber, then is effort increase on the piston and pressing into the die channel begins, thus indications of tensometric measuring system are registered. A similar installation allows to create conditions identical to occurrence in single die of the forming press. Results of the measurement are qualitatively transferred on all die channels of the forming press. Identical conditions are considered at achievement of pressing effort on the plunger, being comparable with efforts to working bodies of investigated machinery.

161 THE STABILITY OF COMPOSITIONS OF POLYETHYLENE AND RENEWABLE NATURAL RAW MATERIAL TO THERMAL-OXIDATIVE DEGRADATION

P.V. Pantyukhov, T.V. Monakhova N.M. Emanuel Institute of Biochemical Physics, Laboratory of synthetic and natural polymeric composites, Moscow, Russia [email protected]

The trend of creating biodegradable polymer materials started to develop recently (from the end of 20th century). Every year the volume of output of such materials increases. At Firstly they were created for the medical application (bioresorbable threads, dowels, plates, prosthesis and so on). But now it is more essential to develop biodegradable materials for the packaging use. The life cycle of packaging materials is not longer than one year, but the utilization period of such materials made from synthetic polymers in the environment under the influence of sunlight, moisture, atmospheric oxygen, soil microorganisms lasts from decades to centuries. The problem solving is the creation of biodegradable polymers, which would have the same functionality as traditional polymers but when they are dumped they would quickly decompose into safety low-molecular matters. There are to ways of creating such materials, the first is the synthesis of new polymer materials with the biodegrade ability, the second is the modification of traditional polymers by various additives.

In this work was used low-density polyethylene (LDPE) as a polymer matrix and different fillers from renewable natural raw materials. Five lignocellulosic waste products appears as fillers for the polymer. We used textile manufacture waste (TMW), oil manufacture waste (OMW), papermaking waste (PMW), food industry waste (FIW) and dried grass (DG) in two-part compositions with LDPE. The compositions were made by mechanical mixing at a temperature 140-160oC followed by accompanied pressing films. The samples were exposed to different tests, in particular to oxidation. The laboratory method of oxidation models the real long-term process of oxidating in the environment. The samples are put into glass test-tubes with oxygen. Test-tubes with the samples inside are put into warmed-up thermostat at a temperature of 130 oC. Oxygen absorption strength is determined during the certain time intervals. The findings are in need of the mathematical treatment because the mass of the samples is a bit different. As a result, it is possible to appreciate the role of every filler in the process of oxidation. The oxidation of polymer materials is one of the processes in the environment which contribute to biodegradation of the samples. So, using the data for the oxidation it is possible to appreciate the biodegradability of the materials by implication. For the full investigation of biodegradability it is also necessary studying water absorption, ultraviolet irradiation and the influence of soil microorganisms.

Table 1. The oxidation of materials. Material Absorption period of 0,2 mol of the oxygen, min LDPE 330 LDPE + TMW 100 LDPE + OMW 130 LDPE + FIW 330 LDPE + DG 460 LDPE + PMW No oxidation effect

162 MODIFICATION OF PVA DISPERSION WITH EXTRACT OF TREE VERDURE

E.V. Petrenko1, V.N. Parshikova1, R.A. Stepen2 1 - Krasnoyarsky State Institute of Economics and Trade, Krasnoyarsk, Russia 2 - Siberian State Technological University, Krasnoyarsk, Russia [email protected]

It is well known that placing new furniture in houses and business premises is accompanied by offensive odors. These odors are typical for the furniture stores and shops. However, toxic effects of migrants that are not always tangible are even more dangerous. The reason for this is the excretion of formaldehyde and other harmful compounds by the adhesives used in the manufacture. To mitigate their action the compositions are enriched with acceptors of migrants and additives. In connection with the prospects of development of biochemical hydrolysis production in the Krasnoyarsk Territory it appears to be effective to use ethanol extracts of conifers as a modifier. In addition to reducing the toxicity of migrants in furniture it will contribute to recycling wood waste and creating new jobs in forest areas. The purpose of this study is to examine the possibility to use an alcohol extract of tree verdure of fir and spruce as a modifying additive to the polyvinyl acetate (PVA) dispersion, which is widely used to bond structural components made of wood. Ethanol extract was obtained by extracting chopped verdure of fir and spruce (1:1) in a Soxhlet apparatus on a boiling water bath for 3 hours with 60% ethyl alcohol (2:1 The bulk solvent re-used in the experiments was removed from the extracts using a distillation apparatus. The greatest part of the remaining water and ethanol was evaporated in the evaporating dishes on a steam bath, the other part with air conditioning at room temperature. The product obtained with a density of 1.32 g/cm3, corresponding to dry matter content of about 60%, was added in PVA dispersion in appropriate proportions (5, 10, 15 and 20%) with careful stirring. In this study it was used as a modifying agent in the composition to bond wood plates. The indicator characterizing the adhesive properties of the composition was chosen as a quality criterion for samples glued. To estimate the strength of adhesive joints of wood products samples were tested on cleavage of the glued layer along the wood grain (according to GOST 15613.1). Blanks for testing were 100 mm long, 50 mm and 20 mm thick plates of pine wood with moisture 8%. Their surfaces were treated with sandpaper and dusted. Then both bonding surfaces were applied with glue and placed under 12.8 kgf/cm2 press for 1 hour. Ready-glued blocks were kept for 3 days at room temperature (20 ± 2 0 C) and relative humidity of 65 ± 5%. Then each of them was cut to four 20 mm wide samples. The samples obtained were placed in a test fixture and loaded to failure. The cleavage was carried out on test machine UMM-20. The speed of movement of the loading head was 1 mm / min. To make a fair presentation of the bond strength of wooden sticks for PVA dispersions and adhesive compositions based on (5, 10, 15 and 20% extract) a series of 10 trials was conducted. Studies have shown that modifying PVA dispersion with the ethanol extract in the range of 5-15% has a minor impact on the strength of the glued parts. The observed differences in breaking load have the form of trends. The tensile strength of parts, decreases monotonically with increase of proportions, albeit very slightly. When it makes about 20%, its value, as well as the value of breaking load, decreases significantly (by 10% in comparison to the control sample), indicating a significant deterioration in the quality of the product.

REGULARITIES OF THE LOGGING RESIDUES FORMATION ON THE CUTTING AREAS

M.A. Piskunov Petrozavodsk State University, Department of technology and forest complex equipment, Petrozavodsk, Russia [email protected]

In logging process, the logging residues are formed in the large amounts (about 20% from harvested merchantable volume). The logging residues are potential resources for biofuel production.

163 For carry out the operations collecting, preparation to recycling, for fulfill technical and economical substantiations of the logging residues utilization as a biofuel, it is necessary to obtain information about the formation logging residues on the cutting areas. Various factors have effect on the formation process: forest taxation characteristics; type of logging and also important factors group, affecting on regularities of forest residues formation, is machine system and sequence order of primary technological operations (felling, delimbing, bucking, skidding) and also some technological and organizational solutions in the main logging process (harvesting of stem wood). The location logging residues on the cutting area are the main characteristics for the description of their formations after the harvesting of stem wood. There were determined the main technical characteristics: 1. place preferential accumulation of the logging residues (places on the cutting area, where the volume logging residues is at least 90% of the total amount); 2. the average density of the logging residues per unit area (cubic meter residues per one square meter area). Experimental investigations have been carried out. The aim was to determine the connection between the technical characteristics of the formation logging residues and machines systems, and also various sequence of primary technological operations were considered. The investigations were fulfilled in production conditions on the timber enterprises, which were not interested in harvesting logging residues, and how it had been forming the logging residues (comfortable or uncomfortable for the further utilization process) after the main loggings, there were not important for these enterprises. The following machines systems were examined: 1. felling with a chainsaw + delimbing with a chainsaw + choker skidding to the tree tops; 2. felling, delimbing with a chainsaw + collection limbs in the piles + choker skidding to the tree butts; 3. felling + clam-bunk skidding for the tree butts + delimbing, bucking with a chainsaw; 4. felling, delimbing, bucking with a chainsaw + round wood assortments skidding (forwarder skidding); 5. harvester + forwarder; 6. feller-buncher + skidder + field delimber. There were determined for the machines systems: place preferential accumulation and the average density. These characteristics depend on forest taxation parameters of the cutting area significantly. The average density was defined per conventional units (c.u.), to find out only the machines systems influence on the residues formation. As the one conventional unit (c.u.) was used the average density of the logging residues for unsystematic formation. The unsystematic formation is the logging residues formation, when the whole residues volume uniformly is distributed on the square of the cutting area with equal density. The investigations were fulfilled on the timber enterprises of the Russian North-West. There were obtained data: unsystematic formation – the average density – 1 c.u.; place accumulation (square of cutting area covered by the logging residues, %) – cutting strips (100%); scheme 1 – 2,2 c.u., cutting strips, skidroads (50%); scheme 2 – 71,4 c.u., cutting strips (2 - 5%); scheme 3 – 90,5 c.u., upper landing (1 - 2%); scheme 4 – 9,5 c.u., skidroads (20%); scheme 5 – 5 c.u., skidroads (20%); scheme 6 – 67 c.u., upper landing (1 - 2%). The difference of the average density is due to fact, that some schemes contain the piles of the logging residues and some schemes contain the logging residues scattered throughout the cutting area. The average density and place accumulation determine the technologies of the logging residues harvesting and also amount irrecoverable losses of secondary wood recourses. The average density less, the amount irrecoverable losses greater. The place accumulation influences on technical characteristics of the logging residues, so their formations on the skidding trails leads to mixing soil and residues, that consumer characteristics become worse and their harvesting becomes impractical. The average density defines productivity of forest machine for the harvesting logging residues, technical parameters equipment (output, engine power, boom).

164 SYNTHESIS OF FLUORINE-CONTAINING BETULIN ESTERS

Yu.A. Piven1, T.S. Khlebnicova1, V.A. Nikolaevich1, F.A. Lakhvich1, V.T. Nguyen2 1 - Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus 2 - Institute of Chemistry, Vietnam Academy of Science and Technology [email protected]

Betulin (1) is an abundant naturally occuring lupane type of triterpene and it is found predominantly in bushes and trees. The birch bark contains up to 30% of betulin. Betulin and its derivatives possess high biological activity (antiviral, antitumor, anti-inflammatory, etc). The selective introduction of fluorine atoms or fluoroalkyl groups into the structure to modify the bioactivity of organic molecules is an well-established practice.

OCORF

F 29 R COCl, Py, CHCl3 HO 30 20 19 21 2а-d 18 22 12 17 11 13 OH 25 26 9 14 28 F 1 16 1) R COOH, DCC, 2 10 8 15 5 27 DMAP F 3 6 7 OCOR HO 4 2) (RFCO) O, 23 24 2 1 DMAP, Py RFOCO 3а-c

F F F F 2a: R = C3F7; 2b: R = C7F15; 2c: R = 3F-C6H4; 2d: R = C6F5 3a: RF = CF ; 3b: RF = C F ; 3c: RF = 3F-C H 3 2 5 6 4

On the basis of betulin (1) we synthesized its fluorine-containing mono- (2) and di- (3) esters. Betulin (1) has in its structure a secondary hydroxyl group at position C-3 and primary hydroxyl group at position C-28 which can be a subject of acylation to give mono- or diacylated products depending on the reaction conditions. 28-O-acylbetulins (2a-d) were obtained by treating betulin (1) with perfluorocarboxylic acid chlorides in the presence of pyridine in chloroform. Synthesis of 3,28-O-diacylbetulins (3a,b) was performed via an acylation of betulin (1) with excess of perfluorocarboxylic acid anhydrides in the presence of N,N-dimethylaminopyridine in pyridine. An acylation of betulin (1) with 3-fluorobenzoic acid in the presence of N,N-dicyclohexylcarbodiimide and N-dimethylaminopyridine gave diester (3c).

ION-EXCHANGING PROPERTIES OF POROUS CARBON MATERIALS PREPARED FROM VEGETABLE RAW

E.L. Pliekhova, Yu.O. Lesishina, A.F. Dmitruk Donetsk national university of economics and trade named after M. Tugan-Baranovsky, Chemistry, Donetsk, Ukraine [email protected]

The results of ion-exchanging properties of porous carbon materials (PCM) prepared from vegetable raw are presented; the dependence of these properties upon the presence of mineral constituent in PCM material is also discussed.

165 Initial vegetable raw (fallen leaves) was treated by multiple pulse thermal shock at T = 600 ºC (PCM_0). Additional samples were prepared for comparison purposes, sample PCM_HCl was initially treated by hydrochloric acid and sample PCM_C was prepared from cellulose. Utilizing X-ray and IR technique data it was concluded that main mineral constituent in PCM_0 sample (ash content 12,5 %) is calcite (CaCO3), samples PCM_HCl and PCM_C (ash content 6,00 and 0,05 % respectively) have shown the lack of the latter. 2+ 3+ Adsorption of Cu and Fe ions by PCM samples from water salt solutions of CuCl2 and FeCl3 without correction of suspension pH was studied. Cation concentration was measured using atomic absorption analysis. Concerning high calcite concentration in PCM_0 sample, the concentration of Са2+ cations in solutions was also monitored. Surface adsorption of Cu2+ and Fe3+ ions by PCM_HCl and PCM_C samples does not occur, contrary sample PCM_0 has shown the decrease in concentration of Cu2+ and Fe3+ ions and increase of Са2+ concentration. It should be noted that appearance of Са2+ ions in suspension does not connected with ions washout from PCM_0 sample since concentration of Са2+ ions in suspension PCM_0 – distilled water was 0 and remained constant for twenty-four hours. 2+ 3+ Adsorption kinetics of Сu and Fe ions from water solutions of salts (CuCl2, FeCl3) along with desorption kinetics of Ca2+ ions follows first order kinetic equation: A = A0(1-exp(-k·t)) where А0 – limit value of adsorption (desorption); k – reaction rate constant; t – reaction time.. Kinetics curves of Сu2+ and Fe3+ ions adsorption and Ca2+ desorption for PCM_0 sample at T =293 K are shown in figure and their parameters in table: A , 0 k, min- A , mmole/g k, min-1 mmole 0 1 /g Сu2+ Ca2+ 0,735 0,012 0,935 0,015 Fe3+ Ca2+ 9,05 0,038 2,44 0,045

Adsorption of Сu2+, Fe3+ ions and desorption of Ca2+ are connected by reaction time and reaction rates are comparable for each pair of ions. However limit values of Fe3+ ions adsorption and Ca2+ ions desorption are not equivalent. This difference may be connected with the parallel reaction process caused by alkali medium of PCM_0 water suspension. It can be concluded that adsorption of Сu2+ and Fe3+ ions on the surface of the PCM_0 sample is governed by ion-exchanging mechanism.

EVALUATE THE RESPONSE OF THE TRANSESTERIFICATION OF TRIGLYCERIDE BY THIN LAYER CHROMATOGRAPHY

E.I. Pomeshalkin, G.V. Kozlov, A.V. Garabadjiu, V.A. Galynkin, A.V. Bilyk, A.V. Kryukova St-Petersburg state institute of technology (technical university) [email protected]

Using thin layer chromatography (TLC) allows quickly and cost effectively evaluate the process of transesterification. In order to maximize the separation of methyl esters of fatty acids and triglycerides were carried out selection of solvent systems, some of which are presented in the table. To detect the spots of triglycerides and methyl esters of fatty acids on the chromatographic plates, 166 analyzed a number of color reagents (iodine vapor, a 5% alcoholic solution of sulfuric acid, 20% aqueous solution of ammonium sulfate, rhodamine G).

Table – Solvent systems for separation of triglycerides and fatty acid methyl esters № Solvent systems Ratio 1 90:10:1 2 80:20:1 Petroleum ether - diethyl ether - acetic acid 3 70:30:1 4 82:12:1 5 90:10:1 6 Hexane - butyl acetate-acetic acid 90:7:1 7 90:5:1 8 90:10:1 Hexane - ethyl acetate - acetic acid 9 80:20:1 10 Chloroform - acetone 96:4 11 Petroleum ether - chloroform 15:85 12 Hexane - isopropyl ether - diethyl ether - acetone - acetic acid 85:12:1:4:1

The best separation, in our opinion, observed when using the system petroleum ether - diethyl ether - acetic acid in a ratio of 90:10:1, respectively, and hexane - butyl acetate - acetic acid in a ratio of 90:5:1, respectively. Best visualization on chromatographic plates was observed by staining of 20% aqueous solution of ammonium sulfate and dried at 160-180 °C for 20-30 minutes with further exposure the plate in a chamber saturated with iodine vapor.

ISOLATION OF URSANE AND LUPANE-TYPE TRITERPENOIDS, STUDY OF BIOACTIVITY OF COMPOSITIONS AND DERIVATIVES

S.A. Popov1, B.H. Um2, A.V. Shpatov1, E.A. Hohrina1 1 - Novosibirsk Institute of Organic Chemistry 2 - Natural Products Research Center, Korea Institute of Science and Technology (KIST) Gangneung Institute, Gangwon-do, Korea [email protected]

Ursane-, oleanane- and lupane-type triterpenoids are both promising as synthons for synthesis of new compounds and as components for cosmetics compositions and functional foods. In NIOCh SB RAS the versatile isolation and purification technologies of major plant metabolites - triterpenoids from various raw material have been created. Purified extracts of sea buckthorn, cranberry press-residues containing concentrates of ursolic, oleanolic and pomolic acids mixtures were investigated as prospective dietary supplements and ingredients for cosmetics. In vivo testing has been accomplished for these compositions. “Hypurhol” preparation possessing hypolipidemic, cholagogic, hepatoprotective activity, is produced basing on these results. The processing methods of berry juice waste-residues resulting in concentrates of triterpenoid acids’ production have been created. Using different kinds of raw material (cranberry, cranberry and chokeberry press-cakes) pure ursolic acid is produced in pilot-plant scale with purification technology depending on the type of raw material. Ursolic acid and synthetic compounds with ursane skeleton were tested for recombinant human aldose reductase (rhAR) inhibitory activity for development of diabetic complications. The greatest activity was revealed for aminoacids’ derivatives. Cost-effective and environmentally friendly technology of birch-bark’ betulin extraction and purification technology has been worked out and implemented in pilot-plant scale.

167 Betulin is available synthon for preparation of derivatives with new types of biological activity. Derivatives with lupane frame were obtained in preparative amounts and their bioactivity’ studies in vivo were performed. Basing on betulonic acid novel technology for betulonic acid’ alanine amide with hepatoprotective, antioxidant and antimetastatic activity was elaborated. Development of skin protection remedies is carried out using derivatives of lupane and ursane series .

GRANULOMETRIC COMPOSITION OF THERMAL MODIFICATION HYDROLYTIC LIGNIN PRODUCTS

O.V. Popova, M.Y. Serbinovsky, D.I. Chernobrovkina Taganrog Technological Institute of Southern Federal University, Taganrog, Russia [email protected]

In composite materials technology to study the possibility of direct application of hydrolyzed lignin (HL) or products of its thermal treatment is of interest. The essential question of a composite materials rational technology is a question about when and how to produce material grinding for obtaining desired granulometric composition. According to results of our experiments, the effective HL grinding duration in a ball mill of different factorys differ very slightly, about 1 h; the relative amount of HL in the drum should be 70-80% and the relative volume of milling bodys 10-13%. Grinded HL is a raw for its chemical and electrochemical modification, small-sized fractions are used as filler and ingredients for composites. However, as we have found, using lignin as a raw for thermolysis, no need to grind hydrolytic lignin. During thermolysis at 600°C grinding of large fractions causes, so granulometric composition m,90 % 1 2 of the carbonic material is rather little depends 75 on granulometric composition of original lignin. 60 Fig. 1 shows a comparative histogram of the granulometric composition of hydrolyzed lignin 45 corn stalk powder (HLCS) obtained after 2.5 30 hours milling, and carbonic material powder 11 2 22 from HLCS not exposed to a grinding. Slightly 15 1 more large fraction content in the carbonic 0 material is connect, probably, with the fact that >>100 100 75-100 75-100 45-75 <45 <45мкм some agglomerates remain mechanical related, 1234 however they are very fragile, as after a short Particle size, m grinding are completely disappear. In the study Fig. 1. Histogram of granulometric of granulometric composition of thermolysis composition HLCS after grinding for 2.5 h products of hydrolyzed lignin from a different (1) and carbonic material from HLCS wood raw similar results were obtained. without grinding (2) Granulometric composition of the obtaining carbonic material allows to use it without additional grinding technology of different materials and in artificial graphite obtaining. After carbonic material graphitization granulometric composition of powder changes a little, although the number of small fraction particles is slightly increase (less than 45 m and 45 ... 75 m). Thus, the graphite powder from lignin can be attributed to the small-dispersed material.

168 INTERACTION OF IONIC LIQUIDS AND CELLULOSE – PROMISE OR HINDRANCE ?

A. Potthast, M. Schrems, P. Vejdovszky, F. Liebner, T. Rosenau University of Natural Resources and Life Sciences, Department Chemistry, Vienna, Austria [email protected]

In solutions of cellulose in ILs, both the ionic liquid and the cellulose are evidently not inert. Side reactions can be distinguished according to whether they involve the cation or the anion of the ionic liquid or just autodegradation products of the IL. Ionic liquids with 1-alkyl-3-methyl-imidazolium cations react at C-2 with cellulose at its reducing end (and, if present, other aldehyde functionalities along the chain), forming a carbon-carbon bond. There is a linear correlation between the carbonyl content of the cellulose and the amount of covalently bound IL. The side reaction is strongly catalyzed by bases, so that commonly present impurities in ILs, such as their thermal degradation products, promote this reaction. These thermal degradation products are mainly imidazole, N- alkylimidazole, N-methylimidazole and methylene-bridged dimers. Another strong interaction between cellulose and ILs is the degradation of the biopolymer depending on the conditions used. The present study provides insight into the dissolution behavior and degradation mechanisms. Beech and spruce wood and rye straw were dissolved in EmimOAc as the ionic liquid of choice which is currently one of the most frequently used cation-anion combinations among ionic liquids for biomaterial processing. The dissolution was followed by selective precipitation of cellulose, hemicelluloses and lignin. The obtained lignin was analyzed with Curie-point pyrolysis /- gas chromatography / mass spectrometry (Cu-Py-GC/MS), the separated cellulose/hemicellulose fractions with gel permeation chromatography (GPC). Time- dependence of the dissolution process was studied on rye straw, eucalyptus kraft pulp and beech sulfite pulp.

POLYSACCHARIDE-BASED SUPERABSORBENT HYDROGELS

A. Pourjavadi, R. Soleyman Sharif University of Technology, Department of Chemistry, Tehran, Iran [email protected]

Superabsorbent hydrogels are three-dimensional hydrophilic crosslinked networks, which are able to absorb and retain large amounts of water, saline or biological fluids, without dissolution. They are widely used in baby diapers and female hygiene absorbents, agriculture and horticulture, sealing composites, biosensors, artificial snow, drilling fluid additives, firefighting and food packaging. Their over-increasing applications could be correlated to the various medical fields such as wound dressings, drug delivery systems, dental applications, transdermal systems, injectable polymers, implants and ophthalmic applications. Superabsorbent hydrogels can be roughly divided into natural-based and full synthetic ones. Natural materials (such as polysaccharides) have been used as the main backbone of superabsorbents because of their exceptional properties, i.e., biocompatibility, biodegradability, renewability and nontoxicity. In our polymer research laboratory, many works have been reported on the synthesis and applications of superabsorbents based on polysaccharides. In this field, many bioresource plant materials such as starch, chitosan [1], carboxymethyl cellulose (CMC) [2], sodium alginate [3], carrageenan [4], pectin [5], agar [6] and salep [7, 8] have been used. Recently, based on salep and CMC, superabsorbents were synthesized which one gram of them has capability to absorb four liter of distilled water, surprisingly. Also, on the basis of the plant material, hydrogels were prepared as new scaffold for the preparation of nanoparticles, artistically.

References 1. G.R. Mahdavinia, A. Pourjavadi, M. J. Zohuriaan-Mehr, J Appl Polym Sci, 99 (2006) 1615- 1619.

169 2. A. Pourjavadi, F. Seidi, H. Salimi, R. Soleyman, J Appl Polym Sci, 108 (2008) 3281-3290. 3. A. Pourjavadi, H. Ghasemzadeh, R. Soleyman, J Appl Polym Sci, 105 (2007) 2631-2639. 4. G. R. Bardajee, A. Pourjavadi, R. Soleyman, Adv Polym Tech, 28 (2009) 131-140. 5. A. Pourjavadi, Sh. Barzegar, Starch/Stärke, 61 (2009) 161-172. 6. A. Pourjavadi, B. Farhadpour, F. Seidi, J Polym Res, 16 (2009) 655-665. 7. A Pourjavadi, R. Soleyman, G. R. Bardajee, Starch/Starke, 60 (2008) 468-475. 8. G.R. Bardajee, A. Pourjavadi, S. Ghavami, R. Soleyman, F. Jafarpour, J Photochem Photobiol B, 102 (2011) 232-240.

DEVELOPMENT OF THE OPTIMAL COMPOSITIONS OF BIOFUEL MIXTURES BY PHYSICO-CHEMICAL MODELING

I. Povar1, V. Cerempei2, T. Lupascu1, N. Timbaliuc1, B. Pintilie1, O. Spinu1, I. Molotcov2, D. Ruschih2, I. Chirau2, I. Habasescu2 1 - Institute of Chemistry of the Academy of Sciences of Moldova 2 - Institute of Agricultural Technique "Mecagro" [email protected]

The main goal of this work is the optimization of the energy indexes of the biofuel mixtures based on the physico-chemical models, taking into consideration the chemical composition of mixture components and their stability toward combustion as well the practical accomplishment of the research results. The base of our research is the creation of the physical-chemical models for biofuels that allows the omission of the large analytical studies during the development of new compositions. Practical use of these models offers the opportunity to design and manufacture the installation for preparation of optimized fuel mixtures that use the maximum energy potential extent of each component in the mixture. Checking the quality of biofuels is running according to the standard tests that depend on such fuel properties as the specific mass, vapor pressure and distillation curves. These properties are closely related to the composition of biofuels and their prediction is based on peculiarities of their components. The biofuel composition will be determined experimentally by the gas chromatography method as small series of pseudo- components. Taking into account the composition of biofuels, their volatile and weight specific properties will be determined using thermodynamic relations. By means of the developed model will be possible to predict the specific gravity, vapor pressure and the most part of the distillation curve. In this way, the physical-chemical model becomes an effective instrument for assessing fuel properties and will be used for the research of composition mixtures and as an alternative tool for the quality control. Moreover, physico-chemical modeling of biofuel properties will allow excluding subjectivity in the preparation of the fuel mixture compositions; will provide the opportunity to optimize their composition according to the energy indexes, while raising the maximum effectiveness of their use. The significance of this work, planned for Moldova and other states, consists in increasing the competitiveness of biofuels due to the optimization of their composition by the parameters of specific heat and combustion completeness as well as the process efficiency.

STRUCTURE-PRESERVED HOT-WATER EXTRACTION OF GALACTOGLUCOMANNAN FROM SPRUCE WOOD

A.V. Pranovich, T. Song, B.R. Holmbom, S.M. Willfor Abo Akademi University, Laboratory of Wood and Paper Chemistry, Turku/Abo, Finland [email protected]

Hemicelluloses constitute 25-30% of the wood in conifers. They have a large potential value as starting materials for production of various biofuels and sugar-based chemicals, and are also of

170 interest as natural polymers in applications as hydrogels and packaging films. Hemicelluloses also have various bioactive properties and might find use as food additives or even as pharmaceuticals. In order to preserve the polymeric structure and acetylation degree of extracted galactoglucomannan (GGM) and achieve a high extraction yield, ground spruce sapwood was subjected to a series of consecutive two-stage extractions with plain water at 170°C using an Accelerated Solvent Extraction apparatus. A healthy, mature Norway spruce tree was felled in South-West Finland. Sapwood was taken out and cut to chips by hand. The chips were air-dried overnight, ground and fractionated to obtain a fraction with a particle size of 0.25-1.0 mm. An Accelerated Solvent Extractor (ASE 200, Dionex, Sunnyvale) equipped with 33-ml stainless steel cells was used to perform a series of two-stage water extractions of the ground wood (ca 14 g o.d. wood). The extractions were done with plain water at 170°C with 1 h total extraction time. After extraction, the water extracts were cooled to room temperature and their end-pH measured. Total Dissolved Solids (TDS) in water extracts were weighed after freeze-drying of aliquots to constant weight. The amount of acetyl groups split off from wood during hot-water extraction was monitored by analysis of acetic acid in the extract solution by HPLC. Total carbohydrates in the water extracts, and in the isolated products, were analysed by GC after acid methanolysis and silylation. Molar-mass characteristics of dissolved carbohydrates in the water extracts and in the isolated products were determined by HPLC-SEC equipped with MALLS (miniDAWN, Wyatt Technology) and RI detectors. In order to characterize the carbohydrate-derived oligomers isolated from water extracts they were acetylated with a mixture of Ac2O and pyridine and then analysed by HPLC/SEC equipped with two DVB columns andan LT-ELSD detector and THF as eluent. About 4% of the wood material was dissolved already during the first minute of extraction. The total yield of dissolved material after a total extraction time of 1 h was almost the same, about 25% of wood, irrespectively of the time ratios between the 1st and 2nd extractions. The yield of hemicellulose polymers, consists of mainly GGM, with an average molar mass of 8-10 kDa during the 1st stage extraction followed a Gaussian-type curve with a maximum at 20 min extraction time. The maximum yield of hemicellulose polymers was about 7%, on dry wood basis, which comprises about half of the total dissolved solids extracted in 20 min. During the 1st extraction the released acetic acid increased steadily and the end-pH value decreased gradually, down to 3.4. Thus, along with the progress of extraction the molar mass of the hemicelluloses decreased and hemicellulose- derived oligomers became dominant. Accordingly, the average molar mass decreased with time from 35 kDa to 3.5 kDa. The hemicelluloses and some pectin comprised 83-90% of the precipitated polymeric material, and the content of GGM in the precipitates was about 80%.

DELIGNIFICATION LINEN FIBERS

A.N. Prusov, S.M. Prusova Establishment of the Russian Academy of Sciences Institute of Solution Chemistry [email protected]

In the process of obtaining cellulose from flax fibers are the most difficult task is to delignification. Flaxseed is rich in raw lignin (4 ... 8% and higher), compared with cotton, which contains only traces of this component. Lignin is associated with pectin substances and cellulose, which permeates and creates lignification. It can be separated from the pulp only by the action of strong reagents capable of altering its chemical form. The change in lignin content in flax fiber in the process of oxidative, hydrolytic and oxidative- hydrolytic degradation. From comparative analysis of the kinetic curves that most of the lignin is removed within 25-35 minutes, and as a result of oxidative degradation - mostly in the surface layer of cow tissue and epidermis. Hydrolytic degradation of polymer during processing of mineral acid is accompanied by additional intensive removal of lignin, concluded between the elementary fibrils. Removal of residual lignin by vnutrifibrillyarnoy diffusion is possible with increasing temperature, and by changing the composition of chemical solutions and the introduction of additional stages of 171 processing. So delignification during the oxidation-hydrolytic degradation of the fibers in an aqueous solution of sulfuric acid or acetic acid in the presence of hydrogen peroxide and a catalyst proceeds effectively. Lignin content by processing the fibers in the two-stage aqueous solution of sulfuric acid and potassium permanganate is 1.63%. With increasing treatment temperature up to 900C residual fiber lignin content - 0,88%. Is more effective peroksouksusnaya acid, using a residual lignin content in pulp - 0,68%, but the yield of cellulose product lowest. Intensity delegnifikatsii flax during hydrolytic degradation varies in the presence of additives alcohols. Lower content of lignin, cellulose is obtained by using aqueous solutions of nitric acid containing butanol. The depth of delignification of flax fiber depends on the processing time and increases with solution temperature up to 950S. In this case, removing most of the lignin takes place on the stage followed by alkaline cooking. Pre-machining of flax fiber to rotary pulse setting helps intensify the process of delignification and can significantly reduce the time of chemical treatments. The resulting pulp has a high degree of purification from the accompanying substances and has high reactivity. Made based on this prototype are characterized by a degree of substitution of nitrocellulose 13.3% N, samples of sodium carboxymethyl cellulose - a degree of polymerization of 1000 to 2500 and the degree of substitution equal to 0,8-1,2.

PREPARATION AND PROPERTIES OF CELLULOSE IN POWDER FORM

S.M. Prusova, A.N. Prusov Institute of chemistry of solutions of RAS [email protected]

From flax, wood, raw cotton by mechanical and mechanochemical on-velopments, including hydrolysis of solutions of nitric acid, obtained samples of the powder-hand pulp with varying degrees of polymerization (70-250). Conducted their analysis of variance and studied the physical and chemical properties: specific surface area, bulk density, sedimentation stability of aqueous dispersions, the structural characteristics - the degree of crystallinity, the transverse and longitudinal crystallite size, interplanar interatomic distances, unit cell parameters of cellulose. To determine granulomet-stoichiometric powder cellulose used laser microanalyzer size particles ditch "analysette 22. Equilibrium water content in the samples of powdered cellulose was determined using a moisture analyzer MX-50. The IR spectra of cellulose were obtained using a spectrophotometer with Fourier-transform (IR Prestige-21). Radiographic studies were performed using a DRON-3, using monochromatic CuKα radiation double filter Ross. Established that the basic physical and chemical characteristics of samples of cellulose powder, depending on the method of production and to a lesser extent on the nature of tsellyulozoso- containing raw materials - linen, cotton, wood. Cellulose, obtained under joint action of pressure and shear deformations, has the lowest degree of crystallinity, the STP. In this case the mechanical activation, which is implemented through the plastic-parameter deformation and the accumulation of energy in the crystallites in the form of defects or other change in the equations of rigid-chain polymers. Birth, migration and annihilation of defects is of core implementation mechanism of plastic deformation. Thanks to last for cellulose becomes more accessible to the action of reagents. This eliminates the morphological features of flax, cotton, wood raw material for obtaining microcrystalline cellulose, which has identical physical and chemical characteristics and high reactivity power. The interplanar distances and unit cell parameters of cellulose obtained by acid hydrolysis, depending on the nature of raw materials. Longitudinal and transverse dimensions of crystallites flax and wood pulp depend on how it is received. The largest transverse and longitudinal dimensions of crystallites has cotton microcrystalline cellulose. It is shown that the specific surface area of the powder timber and flax 2 times more than inpulp, obtained by the mechanochemical method in the case of the chemical. The bulk density of cotton, timber and flax cellulose, obtained by chemical means, respectively, equal to 0.32, 0.29, 0.47 g/cm3. As a result, the mechanical and chemical treatment, samples of powders of cotton, linen and wood pulp with a bulk density of 0.55, 172 0.59 and 0.57 g/cm3 respectively. Revealed that the two factors that affect the sedimentation of sustainable powdered cellulose - the bulk density and specific surface area, the last of them is decisive. Sedimentation stability of powder cellulose depends on the method and properties of a dispersive medium. Blending of ethanol and dimethyl sulfoxide in water promotes the growth of the number of particles with size less than 500 nm and specific surface area of cellulose an increase in  2 times.

THE GERMAN LIGNOCELLULOSE BIOREFINERY PROJECT

J. Puls1, B. Saake2, R. Lehnen1, A. Schreiber2 1 - vTI-Institute for Wood Technology and Wood Biology, Hamburg, Germany 2 - Hamburg University, Wood Science Centre, Chemical Wood Technology [email protected]

The "German Lignocellulose Biorefinery" project has been funded by the Federal Ministry of Food, Agriculture and Consumer Protection (BMELV). It was the aim of the 15 partners of this collaborative project to develop a component separation process based on hardwood for individual recovery of extractives, cellulose, hemicelluloses and lignin. Equal weight should be given for the use of all these components. The project partners came from industry, small and medium-sized enterprises, research institutions, and universities. The outcome of the project was the technical conception of a lignocellulose feedstock biorefinery pilot plant, which will now be realized in a 2nd stage project phase.

Figure 1: Process scheme for the production of wood sugars, lignin, and wood extractives from hardwood according to the organosolv principle

The decision to use only hardwood (beech, birch, poplar) was made due to the availability of this resource and to avoid a competitive situation with the pulp- and woodworking industry, which is mainly based on softwood. A main task of the project was the optimization of the pulping process. Different mix ratios of low boiling alcohols with water have been tested with regard to solvent:wood ratio, temperature, time, and catalyst (H2SO4) on a 1-kg-scale batch. The results of the optimization could be scaled successfully to a 10-kg batch process, and also be transformed to a continuous pulping process.

173

After ethanol:water treatment hemicelluloses and lignin were dissolved in the pulping liquor, whereas the almost delignified fibers were retained as insoluble fraction to be separated by filtration. The more critical step was the separation of hemicelluloses and lignin. Lignin precipitation was performed either by distillation or by addition of water. Within the hydrolysis step of the fibre fraction to monomeric sugars up to 85 % of the theoretical yield of the hydrolysis of cellulose to glucose was achieved. The xylan fraction could also been enzymatically hydrolyzed, if necessary. In case sulphuric acid was added in catalytic amounts during pulping most of xylan was already hydrolysed to monomers. The fermentation capabilities of the achieved sugars have been verified by ethanol fermentations, using C5- and C6-sugars utilizing yeasts. Inhibitory effects were not detected in this case, but testing the sugars in different fermentations indicated that the growth rates of some microbial strains were reduced or their lag-phases were extended. The lignin fraction was tested in duroplastic and thermoplastic applications. As a main result it was shown that phenol based resins with up to 30 % substitution of phenol by lignin can be used in wood construction board applications. The results of the economic calculation showed, that for the construction and operation of this lignocellulose biorefinery with a capacity of 400,000 tons dry wood/year expenditures of about 183 €/t will incur. Each ton dry beech wood will be converted to about 340 kg glucose, 240 kg xylose, and 160 kg sulphur free lignin. By applying the estimated production costs onto lignin, and based on the assumption that the produced sugars will be sold for 207 €/t (world market price, 2009) as credit for the lignin production, the lignin production costs can be calculated to about 395 €/t. For the profitability of the lignocellulose feedstock biorefinery it is necessary to sell the lignin at a high price. It was demonstrated in this project application that realizations of prices of more than 400 €/t exist. The application of sulphur free lignin as direct substituent for phenol (about 800 €/t) in resol resin production is one example. Other intended uses for sulphur free lignin as a renewable source for aromatic compounds are under investigation in ongoing and future research activities.

SCREENING OF YEASTS – LIPASE PRODUCERS

M.A. Pushkarev, O.G. Shpironok, T.B. Lisitskaya, A.V. Garabadjiu, V.A. Galynkin St-Petersburg state institute of technology (technical university) [email protected]

Among of all known enzymes, lipase increasingly attracted scientific attention. These hydrolases do not require a cofactor during catalysis. In addition to their natural function of the hydrolysis of carboxylic ester bonds, lipases catalyze the esterification reaction that leads to the synthesis of ester from fatty acids and alcohols in non-aqueous medium. Transesterification reaction is central reaction in the production of biodiesel, which can also be catalyzed by lipases. Biodiesel is currently produced from wastes and surpluses of vegetable oils using chemical process with an alkaline catalyst. Many disadvantages of chemical catalysis in biodiesel production can be eliminated through enzymatic processes. Traditional sources of biodiesel in laboratory and industry are such crops as canola, soybean and sunflower. Also used corn, olive, salicornia, oil cotton, borage, algae and other vegetable oils. We carried out screening for the presence of lipase activity among the 39 museum cultures of yeast. Screening was performed on agar medium containing 1% Tween-80. Twins are highly soluble in water, have a neutral reaction. The presence of lipolytic activity of strains was determined within 5 days of cultivation at 28 ° C by the formation of zones of calcium salts of fatty acids along the stroke grown yeast culture. On the third day of cultivation growth was observed in all investigated cultures of yeasts, and area of hydrolysis of Tween was observed in six cultures. On the fifth day of cultivation the area of calcium salts was observed in 11 out of 39 investigated cultures. These eleven yeast cultures were selected for the further research as potential producers of extracellular lipases. 174

Table 1 – Yeast cultures showed lypolytic activite on agar medium Presence of lypolitic activity Microorganisms 3 day 5 day Candida parapsilosis + + Candida pseudotropicalis strain № 9 (20-10) + + Candida tropicalis - + Candida tropicalis strain № 9 (20-10) + + Rhodotorula sp. - + Sporobolomyces salmonicolor - + Torula fomata + + Torula rubra strain 5 (649) - + Torulopsis anomala + + Trichosporon strain 26/4 + + Yeast isolated from soil - +

COMPONENT COMPOSITION OF ESSENTIAL OILS OF ARTEMISIA FRIGIDA AND ARTEMISIA GLAUCA, AND THEIR INDIVIDUAL FRACTIONS

E.S. Pushkareva, A.A. Efremov Siberian federal university, Krasnoyarsk, Russia [email protected]

Pharmacy practice requires constant increase in the variety and quantity of medicinal raw materials of vegetable origin. Expanding the range of medicinal plants is possible through the introduction of plants used in folk medicine to the medicine practice. Species of the genus Artemisia are valuable medicinal and essential oil plants and are widely used in medicine. Of special interest is the study of flora in Siberia due to the fact that this territory is one of the richest region by the diversity of Artemisia (76 species). In this work we investigated the component composition of essential oils of Artemisia frigida and Artemisia glauca, collected in the south of the Krasnoyarsk Territory. Essential oils in the samples was isolated by the method of exhaustive hydro-steam distillation. Fractions were collected at different times. Dynamics of the isolation of essential oils and their individual fractions was studied. During the first hour there was rapid release of fractions of essential oils, which is associated with the content of easily volatile components. As the essential oils were isolated, component composition varies and the latter fractions contain semi-volatile sesquiterpenes, which slows down the release of essential oils. Component composition of essential oils was investigated by method of Chromato-Mass- Spectrometry (CMS). 59 components were identified in the oil of Artemisia glauca, the percentage of which was more than 0,1% of whole oil. The main components of the obtained essential oil and of its individual fractions are shown in Table 1.

Table 1 – The main components of the essential oil from Artemisia glauca and of its individual fractions Component Component composition , % Fr. 1 Fr. 2 Fr. 3 Fr. 4 Fr. 5 Whole oil α-pinene 8,67 5,49 2,82 1,23 0,07 2,12 β-myrcene 11,25 6,03 2,95 1,44 0,38 1,83 benzyldiacetylene 17,01 20,20 16,12 10,80 6,03 7,12 methyl eugenol 6,93 9,11 10,13 10,43 9,41 10,01 ar-curcumene 7,71 13,16 19,12 19,30 15,91 9,35 175

By the СMS method we found that the essential oil of Artemisia frigida contents at least 76 components, among which 74 components were identified. The main components of the obtained oil are shown in Table 2.

Table 2 – The main components of the essential oil from Artemisia frigida and of its individual fractions Component Component composition , % Fr. 1 Fr. 2 Fr. 3 Fr. 4 Fr. 5 Whole oil 1,8-cineol 16,35 9,66 3,01 2,21 1,32 8,29 camphor 46,47 61,76 59,32 57,85 56,31 47,19 borneol 3,80 5,43 8,86 12,89 14,32 6,94 terpinen-4-ol 0,74 1,22 1,85 1,99 2,13 1,77 bornyl acetate 1,86 1,99 2,49 2,56 2,72 2,54

NANOFIBRILLATED CELLULOSE (NFC) FROM BIRCH PULPS

E. Quintana1, I. Filpponen2, O. Rojas3, M. Osterberg2, J. Laine2 1 - Textile and Paper Engineering Department. ETSEIAT. Universitat Politиcnica de Catalunya, Terrasa, Spain 2 - Aalto University, Department of Forest Products Technology, School of Science and Technology, Aalto University, Finland, Aalto 3 - Department of Forest Biomaterials, North Carolina State University, Raleigh [email protected]

Renewable and sustainable products based on nanofibrillated cellulose (NFC) may be alternatives to petroleum-derived materials. NFC is defined as cellulosic fibrils disintegrated from the plant cell walls, with diameters in the range of 5-100 nm. The production of nanofibrillated cellulose is based on the combination of mechanical and chemical treatments. The use of NFC as a source for new materials is expected to increase and to provide a range of possibilities to obtain superior end- product performance and properties. One potential application for NFC is in packaging because NFC exhibits competitive barrier and mechanical properties. Therefore, this work deals with the characterization of NFC films made from birch pulp containing different amounts of lignin (unbleached, oxygen bleached and fully bleached pulps). The results will be explained in light of the complex effects of lignin in the production and properties of NFC films.

THE BASIC CONDITIONS FOR OBTAINING OF BIOSTABLE PARTICLEBOARDS

A.A. Rabysh, A.A. Leonovich Saint Petersburg State Forest Technical Academy [email protected]

For long protection of particle boards must use of fixed wood preservative, one of which is the HM- 11 (chromium-copper type). Introduction of HM-11 into composition of board leads to the deterioration of acid-base conditions of gelatinization and wetting of urea-formaldehyde resin (UFR), which requires increase consumption of gelatinization agent (Fig. 1) and use for surface-active agent (SAA) (Fig. 2).

176

Thermomechanical analysis (Fig. 3) of UFR shows, that the combined gelatinization agent (CGA), consisting of NH4Cl и (NH4)2Cr2O7, promotes deeper gelatinization of urea-formaldehyde resin and leads to improved shear strength of adhesive joint (Fig. 4). Its application in addition to the surface active agent provides a biostable particle boards, which satisfy the requirements of GOST 10632–2007.

LIGNIN CHEMISTRY AND ITS EFFECTS ON LITTER DECOMPOSITION IN FOREST ECOSYSTEM

M.M. Rahman Graduate School of Agricultural Science, Ehime University, Matsuyama, Japan [email protected]

Litter is an important and particular component of forest ecosystems and is extremely important to forest health. Litter decomposition, a major determinant of ecosystem functioning, is strongly influenced by the litter quality of different species. The rate of litter decomposition is controlled by three main factors: climate, litter quality (chemical and physical) and the nature and abundance of the decomposer organisms. Lignin is a major component of plant litter. Lignin comprises a complex class of organic compounds whose concentration differs greatly both between and within plant species. Lignin plays a significant role in the carbon cycle, sequestering atmospheric carbon into the living tissues of woody perennial vegetation. Lignin is one of the most slowly decomposing components of dead vegetation, contributing a major fraction of the material that becomes humus as

177 it decomposes. Being a hard-to-decay component, lignin modification could also exert effects on litter decomposition and, consequently, affect the interactions with soil organisms and nutrient transformations. Lignin is highly correlated with decomposition of litter. Thus, there is evidence that the lignin concentration is a more influential factor than the other chemical concentrations, in determining the rate of leaf litter decomposition of different forest ecosystems. However, a great majority number of researches have addressed lignin’s role on litter decomposition, but still there are many aspects of lignin biogeochemistry that are not known. This lack of information hinders complete amalgam of lignin effects on litter decomposition processes and dynamics of nutrient cycling. This paper describes the lignin chemistry and its effects on litter decomposition in forest ecosystems.

RECONSTRUCT THE DEPARTMENT OF MAKING CARBOXYMETHYL-CELLULOSE (CMC) IN THE ENTERPRISE “KARBONAM”

G.R. Rakhmonberdiev, M.M. Murodov, M.Q. Urozov, P.J. Tojiev Tashkent chemical technology institute [email protected]

In the world CMC is produced by wood cellulose. Because a most part of macromolecule of wood pulp is a morph, its degree of crystallize is low therefore wood cellulose’s reactionary ability is higher than cotton cellulose’s. Wood cellulose is cheaper than cotton cellulose. There are several ways of making CMC which are investigated by researches about high fractional substitutionality, high degree of polymerization. The principle – technological chart below shows the production CMC which is used in the enterprise “Karbonam”.

1-rolgang; 2-conveyer-furnisher; 3-mercerizer; 4-filter; 5-capacitance for satisfying percentage of alkali; 6-mass pump; 7-meter pressure; 8-oppressive press; 9-mixer apparatus for alkali cellulose; 10-apparatus for cooling alkali cellulose; 11-collecter volume for alkali cellulose; 12-dosing unit; 13-collector volume for NaMXUK; 14-dosing unit for NaMXUK; 15-mixer apparatus for alkali cellulose with NaMXUK; 16-baking reactor for CMC; 17-sending reactor for CMC; 18-dessication apparatus; 19-ventilation; 20-cyclone; 21-mill; 22-prepackage aggregate. NaMXUK– sodium chloroacetic acid. Invented the new easier method of making CMC. According to the method eliminated unnecessary part of technology which used to be used. According to the new easier method cellulose is sent directly to the mono apparatus. Dose in need of alkali is added to cellulose. The processes – mercerization, cooling alkali cellulose, alkalization are gone there step by step. Appeared semi product will be kept working on and desiccated sent to mill to grange. The separated part of the

178 principle - technological chart is easier method of making CMC. Now a day to reconstruct the department of making CMC in the enterprise “Karbonam” is one of the most important objective in our country. Now days the updating process of technology in the enterprise is going to be finished. Soon the enterprise will start working with updated technology and it makes cheaper the product.

SYNERGY BETWEEN THE NEW FERULOYL ESTERASE FROM THERMOBACILLUS XYLANILYTICUS AND OTHER HEMICELLULASES FOR THE HYDROLYSIS OF LIGNOCELLULOSIC BIOMASS

H. Rakotoarivonina, B. Chabbert, C. Remond UMR614 Fractionnement des Agroressources et Environnement Joint Unit Universite de Reims Champagne-Ardenne - INRA, 2, Reims Cedex 2, France [email protected]

Arabinoxylans are the predominant form of hemicelluloses in graminaceous plant. These polymers consist of -1,4 linked chains in which xylose residues are periodically and mainly substituted by arabinose, glucuronic acid, feruloyl, coumaroyl or acetyl ester groups. Arabinoxylans hydrolysis requires several enzymes including xylanases and debranching enzymes such as -L- arabinofuranosidases and esterases. In the aim of developing a biorefining concept from lignocellulosic feedstocks, efficient biocatalysts are needed to improve enzymatic fractionation of polysaccharides in plant cell walls. Major fungal and bacterial enzymes are found to be optimally active at or near mesophilic temperatures. These enzymes are rarely efficient in industrial process applications (which need high temperatures allowing easy mixing, better substrate solubility as well as enzyme efficiency and thermostability). Recently a new thermostable feruyloyl-esterase (Tx-Est1) was isolated in the genome of the hemicellulolytic bacterium Thermobacillus xylanilyticus (1-2). This enzyme is active and stable at high temperature and presents activity against various methyl esters of hydrocinnamic acids and feruloylated arabino-xylotetraose, exhibiting high specificity and affinity for the latter. Tx-Est1 alone is able to release phenolic acids from lignocellulosic biomass such as wheat bran and wheat straw. In the aim to investigate the interest of Tx-Est1 for lignocellulosic biomass fractionation, synergism experiments were conducted with three thermostable hemicellulases from T. xylanilyticus (Tx-Xyn11 and Tx-Xyn10 xylanases and Tx-Abf51 arabinosidase) (3-4-5). Synergism was studied by measuring the release of phenolic acids as well as the hydrolysis of xylans from lignocelluloses.

1. Rakotoarivonina, H., et al., A thermostable feruloyl-esterase from the hemicellulolytic bacterium Thermobacillus xylanilyticus releases phenolic acids from non-pretreated plant cell walls. Applied Microbiology and Biotechnology, 2011. 90 : p541-552. 2. Touzel, J.P., et al., Thermobacillus xylanilyticus gen. nov., sp nov., a new aerobic thermophilic xylan-degrading bacterium isolated from farm soil. International Journal of Systematic and Evolutionary Microbiology, 2000. 50: p. 315-320. 3. Connerton, I., et al., A single domain thermophilic xylanase can bind insoluble xylan: evidence for surface aromatic clusters. Biochim Biophys Acta, 1999. 1433(1-2): p. 110-121. 4. Debeire-Gosselin, M., et al., Purification and properties of 22 kDa endoxylanase excreted by a new strain of thermophilic Bacillus, in Xylans and Xylanases, J. Visser, et al., Editors. 1992, Elsevier: Amsterdam. p. 463-466. 5. Debeche, T., et al., Genetic and biochemical characterization of a highly thermostable a-L- arabinofuranosidase from Thermobacillus xylanilyticus. Applied and Environmental Microbiology, 2000. 66(4): p. 1734-1736.

179 STUDY OF OPERATIONAL VARIABLES IN THYME (THYMUS VULGARIS) EXTRACTION WITH SUPERCRITICAL CO2

E.A. Ramirez, C.A. Ruiz, G.P. Arias, A.J. Arias, J.R. Martinez, E. Stashenko Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Supercritical fluid extracts of thyme are antioxidants, mainly due to their content of caffeic ursolic and rosmarinic acids. Thyme was cultivated in experimental plots in the field (2 ha). We used not only yield, but also antioxidant activity (ORAC) and total phenols content (Folin-Ciocalteau) as criteria for the selection of operational variables of thyme (ground leaves and stems, 0,2 – 0,5 mm, 7-2 dried at 50 °C) extraction with supercritical CO2 (Thar SFE-2000). A fractional factorial 2 experimental design was used to examine the effect of flow, static and dynamic extraction times, and extraction and separation temperatures and pressures on extract yield (weight, %), antioxidant activity, and total phenols content. Temperature, dynamic extraction time, extraction and separation pressures and static time had significant effect on the three observable parameters. The largest response consisted of a 1,8% yield, an antioxidant activity of 1,93±0.01 µmol Trolox®/mg extract and a total phenols content of 672±3 mg/L gallic acid equivalents. Liquid chromatographic analysis (Agilent Technologies LC 1200, DAD, Zorbax C-18 column) of the best extract did not detect the presence of any of 11 antioxidants (phenolic acids, phenolic diterpenes, flavonoids) studied, but gas chromatographic analysis showed the presence of thymol in large relative amounts.

COMBINED OPTIMIZATION OF ANTIOXIDANT ACTIVITY, PHENOL CONTENT AND YIELD OF SAGE (SALVIA OFFICINALIS) EXTRACTS OBTAINED BY SUPERCRITICAL CO2 EXTRACTION

E.A. Ramirez, C.A. Ruiz, G.P. Arias, A.J. Arias, J.R. Martinez, E.E. Stashenko Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Supercritical fluid sage extracts are strong antioxidants, mainly due to their content of carnosol and carnosic and rosmarinic acids. Sage was cultivated in experimental plots in the field. We used not only yield, but also antioxidant activity (ORAC) and total phenols content (Folin-Ciocalteau) as criteria for the simplex optimization of sage (ground leaves and stems, 0,2 – 0,5 mm, dried at 50 C) 7-2 extraction with supercritical CO2 (Thar SFE-2000). A fractional factorial 2 experimental design was used to examine the effect of flow, static and dynamic extraction times, and extraction and separation temperatures and pressures on extract yield (weight, %), antioxidant activity, and total phenols content. Dynamic extraction time, flow, extraction pressure and separation temperature had significant effect on the three observable parameters to be followed during the optimization. A simplex with 5 vertices was used in the optimization, which required the evaluation of 10 different combinations of values of the 4 factors to find an extract with 1,7% yield, an antioxidant activity of 2,8±0.1µmol Trolox®/ mg extract and a total phenols content of 730±11mg/L gallic acid equivalents. Chromatographic analysis (Agilent Technologies LC 1200, DAD, Zorbax C-18 column) of the final extract showed the presence of ursolic and carnosic acids among 11 other antioxidants (phenolic acids, phenolic diterpenes, flavonoids).

180 TOWARDS A BETTER UNDERSTANDING OF CELLULOSE SWELLING AND DISSOLUTION AT THE MOLECULAR LEVEL

T. Rosenau1, A. Potthast1, C. Jaeger2, K. Mereiter3, F. Nakatsubo4, A. French5 1 - BOKU University Vienna 2 - BAM Berlin 3 - Vienna University of Technology 4 - Kyoto University 5 - USDA New Orleans [email protected]

The exact structure of the hydrogen bond networks and the changes of these networks upon swelling and dissolution processes are current ‘hot topics’ in cellulose research. H-bonds are responsible for the allomorphism of cellulose, for the typical properties of cellulose, and for reactivity and chemical behavior. The use of isotopic labeling with modern solid-state NMR techniques in combination with X-ray crystal structure analysis is a powerful approach to obtain solid state and gel structural data of cellulose and cellulose model compounds, so that we now come close to an understanding of cellulose swelling and dissolution on a molecular level, and might even successfully address the old and unanswered question about the special nature of cellulose solvents. The studies showed that swelling is a reversible process of 3-4 stages, connected with cleavage of hydrogen bonds mainly to/from OH-6 and OH-2. Dissolution, by contrast, is irreversible and involves in addition H-bonds to/from OH-3. The solvents can be distinguished by (1) the order in which specific H-bonds are broken, (2) the number of distinguishable swelling stages, (3) the number of solvent molecules per anhydroglucose unit, and (4) the solvent distance to the different AGU carbons. In addition to common O-H hydrogen bonds, non-conventional C-H hydrogen bonds are present in solutions of cellulose, and thus formation of these bonds might be the distinguishing feature between highly swollen and dissolved cellulose and thus a prerequisite to cellulose dissolution. In solution (confirmed so far for the solvents DMAc, NMMO and BMIM-OAc) the cellulose molecules are surrounded by a layer of tighly bound solvent molecules which are not undergoing dynamic exchange, comparable to primary “solvent shells” known in inorganic chemistry. All these molecular level data are available for the first time and provide a consistent picture of the molecular mechanisms of swelling and dissolution of cellulose and cellulosic model compounds, which will be presented in this lecture.

POTENTIOMETRIC CHEMICAL SENSORS BASED ON LIGNIN-DERIVED POLYURETHANE NANOCOMPOSITES

A. Rudnitskaya1, D.V. Evtuguin2 1 - CESAM/Department of Chemistry, University of Aveiro, Aveiro, Portugal 2 - CICECO/Department of Chemistry, University of Aveiro, Aveiro, Portugal [email protected]

In the field of potentiometric sensors, conducting polymers are employed primarily as ion-to- electron transducers allowing fabrication of all-solid-state polymeric sensors [1,2]. The purpose of this study was synthesis of lignin-based elastomeric copolymers for the fabrication of all-solid-state potentiometric chemical sensors. A set of technical lignins (kraft lignin, lignosulfonates and organosolv lignin) doped with multi-walls carbon nanotubes (MWCNTs) were involved in step- growth polymerization with tolylene 2,4-diisocyanate terminated poly(propylene glycol) according to previously developed methodology [3] giving rise crosslinked elastomeric polyurethanes. Obtained polymers were characterized by Fourier Transform Infra-Red spectroscopy with Total Attenuated Reflectance (FTIR-ATR), thermal (thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)) and imaging (Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM)) analyses. Doping of lignin-based polyurethanes with CNTs allowed

181 radical enhancement of their electrical conductivity without significant deterioration of thermal and viscoelastic properties. The former polymer composites displayed low percolation threshold at CNT concentration of 0.18 % (w/w), which was explained by the oriented distribution of CNTs along lignin clusters. All lignin-based polyurethanes doped with CNT at concentrations above percolation threshold are suitable for sensorial applications. Lignin-based polyurethans doped with MWCNTs (0.72 % w/w) were employed for the sensors elaboration. Chemical sensors were prepared by drop casting of viscous pre-copolymer on the surface of carbon glass or platinum electrodes been finished at 60 ºC for 4h. Sensitivity of the sensors towards wide range of transition metals and pH were evaluated. Sensors did not display any response to Na, Ca(II), Zn (II), Cd(II), Hg(II), Cr(III), Fe (III) and very low response of about 12 mV/pM to Cu(II) and Pd(II) ions. pH sensitivity was rather low but linear practically in all studied range. Sensors’ response to Cr(VI) was not Nersntian and cationic, though chromate is an anion. Furthermore, redox response was studied in the solutions 3-/4- of two redox pairs Cr(III)/Cr(VI) and Fe(CN)6 . Low or no sensitivity was observed to all ions except Cr(VI) at pH 2, to which response of 39, 50 and 53mV/pX was displayed by the sensors based on kraft, organosolv and lignosulfonate lignins respectively. Redox sensitivity close to theoretical of 20 and 21 mV/pX for organosolv and lignosulfonate sensors respectively was 3-/4- observed in the Cr(III)/Cr(VI) solutions while very low response was observed in the Fe(CN)6 solutions. Therefore, it is plausible to suggest that response mechanism of the lignin sensors includes both specific interaction between chromate and lignin (ion exchange) as well as a redox process. Further experiments are necessary for elucidation of the mechanism of the response of the lignin based sensors towards Cr(VI).Conducting composite polymers based on lignin-based polyurethanes doped with carbon nanotubes were demonstrated to be the promising materials for Cr(VI)-sensitive potentiometric sensors.

Literature: 1. Bakker E, Buhlmann F, Pretsch E. Chem. Rev. 1997; 97: 3083-3132. 2. Bereczki R, Gyurcsanyi RE, Agaic B, Toth K. Analyst 2005; 130: 63–70. 3. Evtuguin DV, Andreolety JP, Gandini A. Eur Polym J. 1998; 34(8): 1163-1169.

RECEPTION OF THE TANNIC EXTRACT FROM THE PINE BARK

T.V. Ryazanova, Yu.A. Tyulkova, P. Michura, O.N. Eremenko Siberian state technological university, Krasnoyarsk, Russia [email protected]

In our country wood processing industry is developed, but up to date wood processing is not highly rational. Huge amount of bark is collected in the dumps of enterprises polluting the environment.However, studying the chemical composition of softwood bark, we can say that it is a valuable raw material for many useful products with high added value, used in leather industry and in medicine. In practice, not all waste bark comply with the requirements for raw materials for the tanning- extrakt production both in species composition, in particular the bark of pine, and for content of timber in the form of flakes, whose share exceeds the requirements by 15-25%. To test the possibility of using the bark of pine as a feedstock for the production of tanning extract a series of experiments was carried where the object of the study were debarking pine waste. Previous studies have shown that bark pulp waste (spruce, fir) can be transformed into the category of raw materials for the tanning-extrakt production, if the extraction of tannins is performed by dilute aqueous solution of sodium hydroxide with subsequent improvement of extracts by the combined method, including neutralization on ion-exchange resin KU-2 to pH of 5.8 - 6, following processing by 1-2% solution of sodium sulfite and improvement of ultrafiltration on hollow fibers FFU-15. In this case, the bark of pine trees was crushed on disintegrator and subjected to extraction 1,25- 2,0% NaOH for 10-60 minutes at the temperature of 90 oC. 182 Study results of the received extract is shown in Table 1.

Table 1 - Characteristics of the bark extract pine

Indicator Guantity Yield, % 39 The dry residue (DR) g / L 24,4 Soluble, % of DR 98,8 Tannins, % от DR 53,4 рН 10,6

From the results shown in Table 1, we can conclude that the use of the resulting extract is limited, because of low purity. The practice shows that the use of the extract with a similar purity is possible in a bouquet of not more than 25%. To improve the quality of the extract were carried out researches on the modification of the extract in two stages. In the first stage was made processing by sodium sulfite and neutralization on the cation exchange resin KU-2. Based on studies conducted in SibSTU earlier we found out that process of neutralization is preferably carried out before processing by sodium sulfite. Results of extracts study showed that the resulting modification of purity is increased to 67-68%. In this case, from one ton of waste it is possible to get 0.5 tons of liquid extract with 67-68% purity.

LEVOGLUCOSENONE: A VERSATILE CHIRAL TEMPLATE OF CARBOHYDRATE ORIGIN

A.V. Samet1, V.V. Semenov1, F.A. Valeev2, L.Kh. Faizullina2 1 - N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 2 - Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences, Ufa [email protected]

Levoglucosenone ((1S,5R)-6,8-dioxabicyclo[3.2.1]oct-2-en-4-one or 1,6-anhydro-β-D-glycero-hex- 3,4-dideoxy-3-enopyranos-2-ulose) is a product of pyrolysis of acid-impregnated cellulose and cellulose-containing waste materials, like paper, cardboard etc. The nature of this compound as unsaturated ketone defines the scope of its possible chemical transformations; fixed absolute configurations of the two bridgehead stereocenters bring about stereoselectivity of these reactions; and the presence of an acetal (anomeric) center adjacent to the carbonyl group allows for various deep transformations of the primary reaction products.

183 OH OH

H O H OO H H OH H O OH H O H H HOH HOH cellulose n

H+ 300-400oC

O (S) O (R)

O levoglucosenone R O O OH

R' pheromones - aroma compounds grandisol O (pheromone) + HO H2N H O OMe OH N O O NH2 OH H O N HO O H (CH ) CH H OH 2 13 3 HO HO tetrodotoxin OH O phytosphingosine hongconin (drug)

A unique combination of all these structural features makes levoglucosenone one of the most promising and versatile chiral synthons that have found wide application for the synthesis of optically active natural compounds and their analogues of acyclic, carbocyclic and heterocyclic structure, possessing practically valuable properties and demonstrating different kinds of biological activity (carbohydrate derivatives, pheromones, aroma compounds, alkaloids, prostanoides, pharmaceuticals).

MONITORING BY HS-SPME-GC-MS SANSEVIERIA GUINEENSIS FLOWER SCENT DURING DAY AND NIGHT

B.E. Sanabria, D.C. Duran, J.R. Martinez, E.E. Stashenko Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Tropical flowers have unique and surprising fragrances. Flower scent study is very interesting from several points of view: plant secondary metabolism, circadian cycles, volatile compound emission, plant-insect relationships, and as a source of sui generis compounds which may constitute the basis for new perfumes and fragrances. Sansevieria guineensis (Rusaceae family) is a tropical plant from Asia and Africa, used in Colombia for ornamental purposes and popularly known as “mother-in-law tongue”. The goal of this work was the in vivo and in vitro determination of the chemical composition of Sansevieria guineensis flower scent at different times of day and night. Sansevieria

184 guineensis flower volatiles were monitored in vivo and in vitro by means of HS-SPME (30 min fiber exposition) with a PDMS/Carbowax (65 µm)-coated fiber, followed by GC/FID/MSD analysis (Agilent GC 6890N/FID/MSD 5975, DB-5 and DB-Wax, 60 m columns). In vitro sampling was performed at 9 am, 12, 3, 6, and 9 pm. In vivo samples were collected at 4 and 9 pm. A total of 40 compounds were identified in Sansevieria guineensis flower scent and their relative amounts changed during the day. There is no single, dominant component of the scent. Aldehydes (hexanal, heptanal, heptenal, nonanal, octenal, nonadienal, decanal), alcohols, ketones (6-methyl-5- hepten-2-one, 3-octen-2-one), benzyl, hexyl, octyl, 2-ethyl-1-hexyl, decenyl, decyl, dodecenyl, dodecyl, and tetradecenyl acetates, methyl and benzyl benzoate, methyl salicilate, eugenol, and cis, trans-α-farnesene, were identified as the main scent constituents. Among the samples collected at different hours, that taken at 9 pm, showed the largest difference in number and amount of components isolated.

OBTAINING CARBON SORBENT AND CHEMICAL SUBSTANCES FROM SOLID COTTON WASTES

K.A. Sartova, J.A. Oskonbaeva Kyrghyz-Turkish Manas University [email protected]

Carbon Sorbents are ecological state in protecting of environment and crucial in improving the quality of food products and drugs. They are used in water wastes, industrial wastes, gas emissions ın order to clean sugar syrups, wine, vodka and other drinks. They are also used in protectıng from chemicals and toxic productions that can harm people. In more industrialized countries used ın daily life of people and very large amounts of activated carbons variety is produced. Family history of active carbon stocks from each individual per 400 kg / year is equivalent to. The mainly used production of carbon adsorbents are willow, linden, spruce and activated carbon. In countries with limited forest resources to obtain activated carbon they use local raw materials - tropical plants, vines, cotton, Lignin, coconut,walnuts and rice birch. The biomass of cotton carbonizate in many experimental data ways are unable to reach industrial activated carbon. To improve the properties of carbonizates the adsorbents are activated later to be investigated at 6000C-8000 0C biomass of cotton pyrolysis.

HIGH CETANE BIOFUEL PRODUCTION VIA HYDROCRACKING PLANT OILS

S.A. Selishcheva1, R.G. Kukushkin2, V.A. Yakovlev2 1 - Novosibirsk State University, Novosibirsk,Russia 2 - Boreskov Institute of Catalysis, Novosibirsk,Russia [email protected]

The production of motor fuels from renewable resources has become important due to the exhaustion of fossil resources. Two types of biofuels are most widely used at present: bioethanol and biodiesel produced from sugar and vegetable oils respectively. Besides the biodiesel it may be received another type of biofuel so-called green diesel, or “Supercetane”, by hydrocracking triglycerides of fatty acids (palm, soybean, jatropha, canola oils). Green diesel is a mixture of alkane’s isomers from C12 to C18 hydrocarbons. Because of high content of alkanes, green diesel has an excellent cetane number ranging from 55 to 90 [1] and is positioned as improved additive to the traditional diesel. Usually the production of green diesel takes place in two stages. On the first stage vegetable oils undergoes by hydroprocessing with n-alkanes formation. The second stage is n-alkanes isomerization for improvement of biofuel. Generally, sulfided Ni-Mo [2], Ni-Co, Ni-W supported on the Al2O3 are used as catalysts for the first stage. For the second stage bifunctional catalysts, including both the acidic function (zeolites: ZSM-5 [3], ZSM-22, BEA; SiO2-Al2O3 [4]; silica

185 aluminophosphates SAPO-11, SAPO-31 [5], SAPO-41) and the ability of hydrogenation- dehydrogenation (noble metals Pt or Pd), are employed. However, the sulfide catalysts can quickly deactivated because of the low content of sulfur in the feedstock. Therefore the development of non-sulfided catalysts, based on Pt, Pd, Ni, Co, is actual. In the present work for the implementation of the first stage (canola oil hydrocracking) were used the following catalytic systems: Ni-Cu/Al2O3, Ni-Cu/SiO2, Ni-Cu/Al2O3 promoted with phosphorus and Ni-Cu/CeO2-ZrO2. The experiments were carried out in a laboratory fixed-bed flow reactor 0 -1 3 3 under T=360 C, P=8, 0 MPa, LHSV= 3, 0 h , H2/oil = 1333 Nm /Nm . Ni-Cu/CeO2-ZrO2 catalyst was determined as the most active catalyst. The total yield of alkanes was about 60% in the presence of this catalyst. Canola oil conversion was non-complete at mild conditions (T= 300- 3800C, P= 1, 0 MPa, LHSV= 2, 7- 9, 9 h-1). Influence of products distribution was studied in dependence on reaction conditions in the presence of Ni-Cu/CeO2-ZrO2 catalyst. It was shown that the intermediate products of hydrocracking rapeseed oil were free fatty acids and their methyl esters, waxes, ketones, aldehydes, alcohols and alkanes. The scheme and process kinetic model describing the transformation triglycerides of fatty acids was proposed taking into account the formation of intermediate products. Ni-Cu/CeO2-ZrO2 catalyst was investigated by different physicochemical methods such as elemental analysis, TPR, TEMHR, XRD, TGA, BET. The TGA analysis showed that the extent of coking this catalyst after reactions was about 3, 3%. It was shown that the presence of Cu in the catalyst Ni-Cu/CeO2-ZrO2 allows the NiO to be reduced at lower temperatures. Acknowledgement This work was supported by Project №P1088 dated 24.08.2009 within the FTP 2009-2013.

[1] Stumborg M., Wong A., Hogan E. Hydroprocessed vegetable oils for diesel fuel improvement// Bioresource Technol. – 1996. – V. 56. – P. 8-13. [2] Simacek P., Kubicka D., Sebor G., Pospisil M. Hyproprocessed rapeseed oil as a source of hydrocarbon-based biodiesel// Fuel. – 2008. – V. 88. – P. 456-460. [3] Katikaneni S., Adjaye J., Idem R., Bakhshi N. Catalytic conversion of a biofuel to hydrocarbons: effect of mixtures of HZSM-5 and silica-alumina catalysts on product distribution// Ind. Eng. Chem. Res. – 1996. – V. 35. – P. 3332-3346. [4] Calemma V., Peratello S., Perego S. Hydroisomerization and hydrocracking of long-chain n- alkanes on Pt/amorphous SiO2-Al2O3 catalyst// Appl. Catal. A: Gen. – 2000. – V.190. – P. 207-218. [5] Kikhtyanin O., Rubanov A., Ayupov A., G. Echevsky. Hydroconversion of sunflower oil on Pd/SAPO-31 catalyst// Fuel. – 2010. – V. 89. – P. 3085-3092.

THE INFLUENCE OF PULP BEATING ON ELECTROKINETIC POTENTIAL

R.O. Shabiev, A.S. Smolin St Petersburg State Technological University of Plant Polymers, Russia [email protected]

The report cites the influence of beating of different chemical pulp grades and cotton linter on electrokinetic potential. In the production of paper, cellulosic fibers are exposed to beating. During this process they are shorting, fibrillating, swelling and hydrating, last, but not least it caused the great amount of fiber fines. Apart the fibrillation the cell wall the dissolution and release of some components of the cell wall S2 take place. Such changes lead to an overall increase in specific surface of fibers. Moreover, the specific surface of fiber fines is in 4-8 times higher than the surface area of normal fibers. Owing to the formation of a powerful hydrated layer on the fiber surface, fibrillation and possible oxidative degradation, electrokinetic potential is reducing due to the shift boundary sliding. It is generally accepted [1] that the dissociation of acidic groups (mainly COOH- groups) is the true origin of the surface potential of cellulosic fibers. Nevertheless, the content of COOH-groups in the chemical pulp used for paper production is rather small and ranges from 5 to 100 mmol/kg. The origin of these groups are related to hemicelluloses [3], it is also possible having 186 some oxidation during the process of cooking, bleaching and processing of the hydroxyl groups of cellulose itself. Despite such minor maintenance of the basic acidic groups, cellulosic fibers show relatively high values of the electrokinetic potential [4], its value only increases with the chemical homogeneity of the cellulosic fibers, for example, cotton linter traditionally has the greatest value. This phenomenon induced the authors of the report to investigate the electrokinetic potential, surface potential and the total acidic content (mainly COOH-groups) in cellulosic fibers as a function of beating time. The beating process was monitored by the change in the degree of beating, the morphological characteristics and by the measurement of water retention value of individual fractions. The content of COOH-groups was determined by several methods. Measurements of the electrokinetic potential were carried out by the streaming potential method by means of the Magendans type device. Surface conductivity was compensated by the high bulk conductivity. Surface charge was evaluated by adsorption of cationic polyelectrolytes of different molecular weight, the residual content of which was determined by colloidal titration with the ortotoluidene blue indicator. The following cellulosic fibers types were taken: cotton linter, sulphate bleached hardwood pulp and bleached softwood kraft pulp. These studies have shown that the electrokinetic potential [modulus] at first decreases and then increases slightly over the refining time, although the along determination of COOH-groups showed that their content in wood pulp fibers with the beating time is reduced, and in cotton fibers increases slightly. Simultaneously it has been observed an increase in surface charge upon adsorption of polyelectrolytes of low molecular weight. These data do not agree with the generally accepted theory of the origin and neutralization of the negatively charged surface of cellulosic fibers. Thus, the experimental results put doubt on the connection of acidic group dissociation of cellulose with the observed electrokinetic phenomena of their hydrosuspention. The authors believed that on the hydrophilic surface of cellulose fibers could be oriented the dipoles of water, and the charge transfer associated with the water molecules dissociation.

LITERATURE Cited

1. Papermaking science and technology, in 19th books, edited by H. Paulapuro and J. Gullichsen, , Helsinki, FAPET/TAPPI, 1998-2002 2. Jurjev W.I. On surface (thermodynamic) potential of cellulose fibers: interuniversity collection of scientific papers, 6, L.: 1980. – pp. 44-46 in Russian 3. E. Sjöström, The origin of charge on cellulosic fibers, Nordic Pulp and Paper Research Journal no 2/1989 - pp 90-93 4. Smolin A.S. and others, On the origin of cellulose electrokinetic potential, transactions of VNIIB, issue 65, 1973. – pp. 69-77

TRITERPENOID GLYCOSIDES, AMINO ACIDS AND MICROELEMENTS IN ANTHYLLIS VULNERARIA L. GROWING IN THE EUROPEAN NORTHEAST OF RUSSIA

D.M. Shadrin, Y.I. Pylina, S.O. Volodina, V.V. Volodin Institute of Biology, Komi Sci Centre, Ural Branch, Russian Academy of Science, Syktyvkar, Russia [email protected]

Anthyllis vulneraria L. is a valued fodder plant. This plant is used in traditional medicine at treatment of inflammations of wounds and as a component of teas at organism intoxication. It was established that ethanolic extract of A. vulneraria possesses inhibitory effects on the reproduction of human herpes virus 1 and poliovirus 2 in vitro. It is shown that A. vulneraria contains triterpenoid glycosides which are derivatives of oleanolic acid. Probably these compounds caused healing properties of A. vulneraria. However data on the quantitative content of triterpenoid glycosides in plants A. vulneraria growing in the European northeast of Russia are absent. There are not data about amino acids and microelements.

187 The content of sum of triterpenoid glycosides (derivatives oleanolic acid) in plants A. vulneraria are determined. It is established that the maximum quantity of triterpenoid glycosides is accumulated in leaves and seeds (respectively 2.6 % and 2.7 %). In leaves the greatest quantity of triterpenoid glycosides was observed in the budding phase. The qualitative analysis of protein of plants A. vulneraria has enabled to define the quantitative content of 16 proteinogenic amino acids. Nine amino acids are essential: threonine, valine, methionine, isoleucine, leucine, phenylalanine, histidine, lysine, argenin. A. vulneraria contains adequate consideration of proteinogenic amino acids in comparison with known fodder plants such as a clover, a lucerne and a rump. The content of alanine and lysine in A. vulneraria exceeds content of these compounds in fodder plants mentioned above. High quantity of macro- and microelements such as magnesium, iron and manganese was determined in plants A. vulneraria collected in natural populations. The content of aluminum and heavy metals does not exceed maximum allowable concentration in plant raw materials. According our study plant A. vulneraria could be a source of valuable biologically active substances and microelements. It could be also recommended for an introduction in Republic of Komi as a fodder and a medicinal plant.

This work is executed with financial support of the Program of the Division of Biological Sciences of the Russian Academy of Sciences (project № 09-T-4-1002).

Reference: 1. Andrusenko S.F., Hodko A.V. Study of a chemical compounds and the development of complex processing of unabi (Zizyphus jujuba) // Materials of communications of the All- Russia scientific and practical conference «Biotechnology of plant raw materials, quality and safety of foodstuff», devoted to the 80th anniversary of Inkutsk Russian State University. Irkutsk, 2010. P. 29-33. (Rus). 2. Dejan G., Gordana Z., Katarina S.,VlatkaV., Nebojsa M. Antioxidant activity of nine Fabaceae species growing in Serbia and Montenegro // Fitoterapia, 2008. Vol. 79, P. 185– 187. 3. Nartowska J, Wawer I, Strzelecka H Triterpenoid sapogenin from Anthyllis vulneraria L. Acta Pol. Pharm., 2001. Vol. 58, N 4. P. 289-91. 4. Postnickov B. A. The Maral root and the basis of its introduction in to culture. Novosibirsk, 1995. 276 p. (Rus).

ADDITION OF PERFLUOROCARBOXYLIC ACIDS TO MONOTERPENS AS WAY OF THE SYNTHESIS TERPENILPERFLUOROACYLATES

M.V. Shafeeva, Yu.G. Trishin, L.A. Tamm, M.A. Yazvenko, E.A. Artemenko, G.V. Votintseva St. - Petersburg State Technological University of Plant Polymers, Department of Organic Chemistry, Saint- Petersburg, Russia [email protected]

Addition of perfluorocarboxylic acids (PFCA) to the olefins is one of the important methods of esters RFC(O)OR synthesis. The properties such esters vastly differ from characteristic anfluorinated analogues. Such compounds containing as R residue of terpens are very interesting as perspective biologically active material. We investigated addition PFCA to monoterpens. It was found that selectivity this process is mainly defined the structure of monoterpens which as is well- known in reaction with electrofilic reagents undergo the different rearrangements. Perfluoroacylation of camphene (1) by carboxylic perfluoroaliphatic acids carring out at the soft conditions is chemo- and stereoselective and result in isobornylperfluoroacylates (2) (yield 85- 90%). In reaction of such acids with limonene (3) according to conditions participate only exocyclic or both bonds C=C. As a result are formed terpinylperfluoroacylates (4) or terpinylbisperfluoroacylates (5) (yield 70-85%).

188

F R COOH O F R O 1 2 F OC(O)R F F R COOH 2R COOH Kat. F F OC(O)R OC(O)R

4 3 5 However addition of perfluorobenzoic acid to camphene and limonene occurs only in the hard conditions (heating, catalyst - a sulfuric acid) and is accompanied by the partial isomerization of monoterpens. The interaction PFCA with α- and β-pinenes (6, 7), α- and γ-terpinenes (8, 9) is characterized variety of rearrengements of the intermediates. This processes do not allow to get terpenilperfluoroacylates with predominance one of the isomers.

6 7 8 9 RF COOH RF COOH RF COOH

complex mixture

SYNTHESIS AND EVALUATION IN VITRO OF ANTIINFLAMMATORY AND CYTOTOXICITY ACTIVITY OF NEW DERIVATIVES LUPANE TRITERPENOIDS WITH ALLYL SUBSTITUENTS IN THE A-RING

E.R. Shakurova1, A.Yu. Spivak1, D.A. Nedopekina1, A.N. Ivanova2, N.V. Belska2, Y.P. Belsky2 1 - Institute of Petrochemistry and Catalysis Russian Academy of Science, Ufa, Russian Federation 2 - Scientific – research institute of pharmacology of Tomsk scientific center of Siberian department of RAMS, Tomsk, Russian Federation [email protected]

Chemo-, regio- and enantioselective methods to synthesize C-2-monoallyl and C-2-diallyl substituted betulonic acid or 3-oxo-betulin were developed by the reaction of allyl halogenides with potassium enoxytriethylborates A or potassium enolates B generated in situ under the action of t KN(SiMe3)2, KH or Bu OK followed by the addition of Et3B. The use of KN(SiMe3)2-Et3B reagent in 1,2-dimethoxyethane (DME) provides the generation of enolate anions with the kinetic control, which led to 2-β-propenyl derivative betulonic acid with high enantiomeric purity. At t thermodynamic equilibrium enolization of terpenoid 1 under the action of Bu OK-Et3B in DME followed by ButOK addition led to the 2α-epimers 3. Products of α,α-bis-allylation of 3-keto-lupane were synthesized by using of 2.5 molar equivalents of base ButOK and allyl halogenides are of interest as building blocks for new functionally substituted derivatives lupane terpenoids.

189 20

19 21 12 E 22 13 18 1 H H 25 11 26 17 CO Me 3' 1' R a C D b 2 2 14 16 R 10 1 15 AB 2' 9 5 A 63% (for 2) 2 10 8 20% + - 4 6 AB 42% (for 5) 3 5 7 K Et3B O 4 O O O 6 1, 4 23 24 3 2, 5 23 24 A c 65%

2 3' 10 AB 2' CO H 5 1' 2 - 4 + 6 2'' R d K O 3'' 1'' 87% 23 24 O B O 8 6, 7 R= CO2Me (1-3, 6); CH2OTBS (4, 5, 7) t Reagents and conditions: а. KN(SiMe3)2, BEt3, then C3H5Br, DME, 4 h; b. Bu OK, Et3B, then t t C3H5Br, DME, 20˚С, 1 h then Bu OK, 12 h; c. Bu OK, then C3H5Br, DME, 20˚С, 2 h; d. LiBr, DMF, 150˚C.

Pharmacological studies were carried out in vitro for compound 8 versus betulinic acid. The cytotoxic effects of these compounds in the MTT test and antitumor activity in cell lines on Ehrlich carcinoma and mastocytoma P-815 has been studied. The influence of these compounds on the functional state of macrophages was estimated from the nitric oxide (NO) production stimulated by lipopolysaccharides (LPS) macrophages and from the activity of macrophagal arginase. The results of pharmacological studies in vitro suggest that compound 8 effectively suppressed the production of NO in LPS-activated macrophages, acting as an antiinflammatory agent and showed stronger cytotoxic activity, than betulinic acid on Ehrlich carcinoma and mastocytoma P-815 cells in 10-25 μg mL-1 concentration range. This work was financially supported by the Russian Foundation for Basic Research (Project No. 10- 03-00105) and the Division of Chemistry and President of Bashkortostan Republic of Russia (Grant No 28 (10.03.2011)).

LIQUEFACTION OF LIGNIN IN ALIPHATIC ALCOHOLS AS A SOLVENT UNDER SUB- AND SUPERCRITICAL CONDITIONS

V.I. Sharypov, L.I. Grishechko, N.G. Beregovtsova, S.V. Baryshnikov, B.N. Kuznetsov Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia [email protected]

Lignin is a large-tonnage waste, which formed during bioethanol and biobutanol production from biomass by hydrolysis process. Thermochemical conversion into high added-value products like hydrocarbon liquids can be one of the most promising ways of lignin utilization. A several two- stage technologies including a depolymerization of a lignin (1st stage) and deoxygenation of formed products (2nd stage) are discussed for this purpose. In this paper, the process of thermal liquefaction of lignin in ethanol and iso-propanol under sub – and supercritical conditions was investigated. Samples of lignin, isolated from aspen wood by different methods (Alkali, Klason, and Organosolv) were used as feedstock materials. Liquefaction process was carried out in autoclave at the temperature 400 0C and pressures 4-20 MPa. Structural features of different samples of lignin were established by FTIR investigation. The highest content of carboxyl groups (by 2, 5–5 times higher as compared to the other samples) was found in Organosolv lignin. Klason lignin was characterized by a high level of aromaticity. Method of lignin isolating significantly influenced on a relative content of guaiacyl and syringyl units, which were calculated from the FTIR spectra as the ratio of the intensities of absorption bands at 1270 и 1330 cm-1.

190 According to TG/DTG-MS data the process of lignin thermal decomposition can be divided into two stages. The first stage has a maximum rate of decomposition at 250 - 311°C; this is due to the cleavage of relatively thermal unstable oxygen containing bonds. The second stage with a maximum rate of decomposition at 364 - 407 °C corresponds to the destruction of the basic structure of lignin with the ruture both of oxygen containing bonds and C–C bonds. Among the studied samples, the first stage has the dominant influence (weight loss 16 wt. %) in the decomposition of Organosolv lignin. In the process of thermal liquefaction of lignin in aliphatic alcohols, the type of the samples significantly influenced on the conversion degree and yield of liquid products. The maximum degree of conversion was observed for the Organosolv lignin (57.6 wt%), and the maximum yield of liquid products with b.p > 100°C (up 20.6 wt% ) was obtained with Alkali lignin. The composition and content of individual substances in the light liquid products of liquefaction of the different lignin samples were studied by GS-MS. It was found that they are mainly (more than 60 wt%) composed of phenol and its derivatives. In a condition of the process thermal liquefaction the liquid products from lignin react with aliphatic alcohols with the formation of alkyl substituted phenols. Liquid products from lignin obtained in a medium of isopropyl alcohol contain by 3 - 5 times more propyl phenols in comparison with products obtained in ethyl alcohol. The higher (by 2- 3 times) amount of ethyl phenol was detected in products of lignin thermal liquefaction in ethanol. Among the studied lignin samples, the Klason lignin gave the most alkylated liquid products.

SYNTHESIS AND REACTIONS OF METHYL 6-AMINO-3-AROYL-5-CYANO-4-ARYL-4H- PYRAN-2-CARBOXYLATES OBTAINED FROM DERIVATIVES OF OXALIC AND MALONIC ACIDS

V.P. Sheverdov1, O.E. Nasakin1, A.Yu. Andreev1, V.L. Gein2 1 - I.N. Ulianov Chuvash State University, Cheboksary, Russia 2 - Perm State Pharmacy Academy, Perm, Russia [email protected]

Oxalic acid contains in sorrel. One way to obtain it is the oxidation of carbohydrates. Malonic acid contains in beet roots. The use of oxalic acid leads to the obtaining of methyl 2,4-butanoates 1 and the use of malonic acid to of arylidenmalononitriles 2. O O 1 R C CH3 R1 Ar COOH COOCH3 O O 1 R CN COOH COOCH3 O 1 O O O NH COOH COOC H CN 2 2 5 ArCHO CN O 3 CN COOH CN Ar COOC2H5 2 We found that as a result of the interaction of methyl 2,4-dioxobutanoates 1 with arylidenemalononitriles 2 in propan-2-ol in the presence of catalytical amounts of morpholine methyl 6-amino-3-aroyl-5-cyano-4-aryl-4H-pyran-2-carboxylate 3 were formed. We discovered that cyclopentenones 4 had been formed when pyranes 3 had been heated in a mixture of sulphuric acid and water during 4-6h. The new ways of the synthesis of cyclopentenones have great importance because a cyclopentenone fragment is a part of numerous natural products and product-like compounds. 5-Oxopentanoic acids 7 are formed from pyranes 3 when heated in hydrochloric asid. They are used in the synthesis derivatives of pyrane-2-ones, 1,4-dihydropyridin- 2-ones, dihydrofuran-2(3H)-ones. The reaction of pyranes 3 with acetic anhydride in the presence of sulphuric acid reveals their high reactionary ability. By heating a mixture of pyranes 3, acetic anhydride and sulphuric acid up to 80- 90°C for 1 min the formation of pyran[2,3-d]pyrimidines 5 take place.

191 Another way to use pyranes 3 in the form of perspective synthons is realization and investigation of their reactions under base influence.We found that short heating of pyranes 3 for 1 min in alcohol (methanol, ethanol or ethylene glycol) in the presence of potassium hydroxide leads to pyridinecarbonitriles 6. Nicotinic acid nitriles 6 were synthesized for 1 min in our laboratory. 1 R1 Ar R Ar Ar

CN R2OH CN H2O O H SO HO KOH 2 4 CN O O Ar N OR2 O NH2 3 6 H2O 4 OH O HCl R1 Ar O (CH3CO)2O H2SO4 O Ar O O NH

O R1 OH O N 5 7 According data of the NCI (National Cancer Institute, USA) compounds 3-7 on some tests have shown antitumor activity.

THE COMPOSITION OF ESSENTIAL OILS FROM WASTE OF CEDAR PINES CONES

V.G. Shiretorova Baikal Institute of Nature Management SB RAS [email protected]

The decision of problems of complex processing of a vegetative biomass in valuable products of food and technical purpose is especially actual for Siberian region having of 19 % of world reserves of wood. Food and a herb of Siberia the pine Siberian (a cedar Siberian) is widely widespread. From ancient times its seeds - pine nuts were used in food, from a kernel received the cedar oil rich with polynonsaturated fat acids and vitamins, from a shell prepared for curative tinctures and broths. Annually in Siberia prepare more than 1 million tons of pine nuts, in places of which industrial processing a plenty of waste in the form of a peel cedar cones (shonor) which makes more than 50 % from weight whole cone will collect. In this connection for development of rational ways of their processing studying composition and properties of shonor and nuts shell is necessary. With the purpose of research of composition of essential oils from a waste of cones of Siberian (Pinus Sibirica du Tour) and Korean (Pinus Koraensis) cedar pines by the method of hydrodistillation were received essential oils and by the method of chromato-mass-spectrometry was determined their composition. The essential oils received from cones waste - a light yellow liquid with less pungent smell, an output of 0,9-1,5 %. The maintenance of essential oils was higher (almost twice) in samples of shonor pines Korean. Dominating components of essential oils from shonor of pines Siberian, % - α-pinen (2,02), α-campholenale (3,78), trance-pinokarveol (8,66), borneol (3,31), verbenon (8,09), bornilacetate (10,04); pines Korean - α-pinen (8,45), β-pinen (4,52), limonen (4,74), α-campholenal (7,34), trance-pinokarveol (12,59), verbenon (8,71).

CORROSION INHIBITORS BASED ON AQUEOUS SALINE EXTRACTS OF BARK

E.V. Shkolnikov Department of Inorganic and Analytical Chemistry, St. Petersburg State Forest-technical Academy named after S.M. Kirov [email protected]

On the pulp and paper industry (PPI) waste bark mostly are burned to generate heat energy or disposed in dumps. Combustion of wet bark and export it to the dumps economically

192 disadvantageous. A minor part of the bark is used for fertilizer production.Therefore the problem of ecologically safe and paying utilization of the bark is very urgent. Systematic studies in the Forest-technical Academy at the Department of Inorganic and Analytical Chemistry shown the promise of complex chemical processing of the bark to obtain effective corrosion inhibitors of metals and steels, as well as tanning agents, surface active substances and fertilizers (compost). The technological regimes of corrosion inhibitors production and draft technical specifications are devised for corrosion inhibitors based on aqueous and saline extracts of air-dried bark of asp(ECO), spruce(ECE), pine(ECS) and mixed breeds. Isothermal extraction of ground bark (l = 3−5mm) and evaporation of the extract can carry out in a steel autoclave or unit batch using heat exchangers, tanks for spent bark and evaporated extract, circulating pumps. The output of water-soluble extractive substances is 20−25wt.% of dry bark at the temperature 100 0C. At higher temperatures the water extraction process is accelerated , as well as the processes of oxidation and decomposition of extractives and the hydrolysis of polysaccharides. Evaporated to 40 10 wt.% brown extracts with a density of 1.15−1.3 g/cm3 and hydrogen index 3.4−5.9 are a mixture of water-soluble substances of the bark (tannins, glycosides, pectin, free di - and monosaccharides, catechol, saponin, ash components, etc.) with the inhibitory effect of γ = 2.5−5 (degree of protection Z = 60−80%) for acid corrosion of carbon and stainless steels. If necessary, the efficiency of wood chemical inhibitor increased (γ = 5−35, Z = 80−97%) by means of small addition (0.1 − 1 g /dm3) a specially selected mineral or organic synergist. Based on electrochemical studies using the potentiostat P5848 found that extracts from the bark of asp (ECO) and spruce ( ECE) inhibit the cathodic and particularly anodic process in acidic corrosion of steel 3 and X18H10T, and pine bark extract (ECS) slows mainly the cathodic process of hydrogen depolarization. Inhibitory effect is manifested in a positive shift of steady corrosion potential and in reducing the current density. Inhibitory effect is enhanced (synergism) when using a mixture of predominantly anodic inhibitor ECE (ECO) with cathodic inhibitor ECS. Corrosion inhibitors based on extracts of bark quite effective, are soluble in water and aqueous media, form a foam, non-toxic, fire and explosion safety and have a renewable source of raw materials (waste wood bark). Wood chemical inhibitors production is relatively simple and does not require complex technological equipment. According to the results of tests devised inhibitors can be used in acid pickling of carbon steels, for an acid washing and cleaning the steel digesters PPI, hydrolysis apparatus and heat exchangers.

L-LYSIN-A-OXIDASE BIOSYNTHESIS BY SOIL SAPROPHYTE TRICHODERMA HARZIANUM RIFAI

Yu.A. Shneyder1, I.P. Smirnova1, E.V. Karimova2 1 - Department of Biochemistry, Peoples Friendship University of Russia, Moscow, Russia 2 - Department of Genetic, plant cultivation and plant protection, Peoples Friendship University of Russia, Moscow, Russia [email protected]

Prevalence of Trichoderma in soil microflora indicates a certain role of this culture in ecology, and the practical importance of L-lysin-α-oxidase as the Trichoderma metabolite doesn’t arouse any doubts with regard to the possibility its use by creation of medical drugs. Cultivation conditions and formation of Trichoderma harzianum Rifai metabolite - L- lysine-α- oxidase were studied in submersed and surface cultivation. This study deals with the correlation of Trichoderma harzianum Rifai spore formation and L-lysin- α-oxidase enzyme biosynthesis in the epigenetics of the culture during submerged cultivation in the media with differing concentrations of (NH4)2SO4. The enzyme biosynthesis correlated with the number of the emerged spores. The amount of the used source of nitrogen in the form of (NH4)2SO4 influenced the process of Trichoderma spore formation and enzyme biosynthesis. Under the conditions of submerged cultivation and with the fungus spores used as the innoculum, the culture growth and biosynthesis of L-lysin-α-oxidase were slight. The extreme difficulty in

193 developing the technique for growing the fungi of the Trichoderma genus in order to obtain the enzyme under the conditions of submerged cultivation is explained by the fact that the species of this genus are able to form chlamydospore under the conditions of submerged cultivation and the subsequent reduction of the number of spores takes place. The fungus mycelium with the medium was used as innoculum in order to study the conditions under which maximum L-lysin-α-oxidase formation in merged cultivation occurs. The use of filamentous form of the innoculum led to the increase in the enzyme activity and it was used for fermentation of maximum L-lysin-α-oxidase formation. The study of the effect, that the degree of aeration has on the L-lysin-α-oxidase formation in merged cultivation of the fungus showed, that the aeration growth facilitates the rise in the enzyme activity, and the possibility for the secondary use of the initial substance [wheat bran] reduces the fungus cultivation period. According to literaturary sources [1,2], the optimum medium pH for the mycelial fungus cultivation is within the range of 5-6. We have studied the effect of initial pH on the fungus growth and the enzyme formation. The maximum enzyme formation has been observed on the first day of the fungus growth at pH 5,6. Under these conditions the culture growth was the best and increase of the protein amount. In the acidic medium at pH 4.5 the fungus forms biomass in the form of individual large granular colonies, however, the enzyme activity under these conditions is low. In a medium having initial pH 7,0, the enzyme activity was also quite low. When the medium is autoclaved for one hour at 1 atmosphere, the growth of fungus and enzyme activity was higher than during thirty-minute autoclaving. In addition, the growth of fungus was more active on the second day and the fungus forms more protein than by autoclaving the medium for 30 minutes. Apparently, complex sugars, polysaccharides and other components contained in wheat bran, are partially hydrolyzed and become more accessible to the culture growth and enzyme biosynthesis. The studies of various ways of cultivation and enzyme biosynthesis allowed accumulating the maximum amount of L-lysin-α-oxidase for its subsequent studies.

References 1. Alimova F.K. Industrial application of fungi of the genus Trichoderma. - Kazan, KSU, 2006 2. Kusakabe C.,Kodama K.,Kununaka A.,Yoshino H.,Soda K.- Extracellular producion of L- lysine-α-oxidase in wheat bran culture of a strain of Trichoderma viride-Agric.Biol.Chem. 1979

POTENTIAL OF VEGETABLE OILS HYDROGENATION FOR PRODUCTION OF DIESEL RANGE HYDROCARBONS

N.V. Shtertser, T.P. Minyukova, A.A. Khassin Boreskov Institute of Catalysis, Novosibirsk, Russia [email protected]

Vegetable oils are a source of renewable raw materials and are widely used by several companies for fuel and valuable chemicals production. Hydrogenation of vegetable oils consisting of fatty acids triglycerides, leads to the formation of linear hydrocarbons with a straight chain of carbon atoms, the length of which depends on the choice of initial oil (С8-С20). Hydrocarbons formed during hydrogenation of oils can be attributed to kerosene or diesel fractions. Since paraffinic hydrocarbons are characterized by most high cetane number, there is an advantage to process vegetable oils by hydrogenation in order to produce saturated hydrocarbons and then use them as a diesel fuels. Within the bounds of this work, studies were carried out using a model starting material – tristearin (triglyceride of stearic acid), which has a carbon chain length of C18 and contains no double bonds. The process of tristearin hydrogenation was performed using permeable catalytic monoliths (PCM) comprising copper containing oxide catalysts of different compositions. PCM was fixed in a specially designed reactor (Fig. 1) so as to ensure hydrogen supply to its centre, then hydrogen 194 passed through the pores structure of PCM to the reactor volume. Under the reaction conditions PCM imbibes liquid tristearin. Gas (H2) flow permeates through the partially wetted pore structure of the immersed PCM-monolith. So the PCM represents a three-phase system of gas flow, liquid and solid catalyst. Fig. 1. PCM and a specially designed reactor for its testing. After cooling, the hydrocarbon mixture in the reactor is enriched in high-boiling products. Volatile products of hydrogenation evaporate and condense downstream

The yield of 40% of saturated hydrocarbons (octadecane) is observed over CuCr oxide catalyst. The remaining components of the final reaction mixture are oxygenated and unsaturated hydrocarbons. Using CuZn oxide catalyst leads to the formation of about 20% saturated hydrocarbons. However, this catalyst has the highest activity in the reaction of ester group bounds hydrogenolysis of tristearin comparing to the all studied catalysts, and allows the achievement of almost 100% conversion of tristearin at 340oC. It should be noted that the final reaction mixture may contain fatty acids, whose presence in the fuel is extremely undesirable. However, the acid can be eliminated by carrying out more prolonged hydrogenation. The main product formed in the course of the hydrogenation of tristearin over all studied copper-containing catalysts was stearyl stearate, in which the yield could achieve 30 ÷ 60% at 340oC and 20 atm. Under reaction conditions stearyl stearat is in equilibrium with oktadecanol and stearic acid, from which it is formed. Consequently, it can be converted to saturated hydrocarbons with more prolonged hydrogenation reaction, i.e. with higher contact time. One of the ways of realization of prolonged hydrogenation consists in the using of a reaction scheme with two reactors connected in series, so that the products of hydrogenation, produced in the first reactor, come to the second reactor and again subjected to hydrogenation. That gives an increase in the yield of saturated hydrocarbons. In present work the tree-phase reactor containing porous copper as a catalyst for first stage and tubular reactor filled with copper containing catalyst for second stage were used. With this process organization the yield of octadecane can reach 50% over CuCr oxide catalyst, CuZn oxide catalyst allows to obtain about 90% of octadecane. Thus selectivity to saturated hydrocarbons depends on the composition of copper containing catalyst used in the reaction. Varying catalyst composition and reaction conditions of triglycerides hydrogenation allows obtaining saturated hydrocarbons of diesel fraction purposefully.

KRAFT LIGNIN/CHITOSAN POLYELECTROLYTE COMPLEX: INTERFACIAL PROPERTIES AND POTENCIAL APPLICATION IN POLYMER COMPOSITES

G. Shulga1, V. Shakels1, S. Skudra1, V. Shapovalov2, A. Valenkov2 1 - Latvian State Institute of Wood Chemistry, Lignin Chemistry Department, Riga, Latvia 2 - Institute of Mechanics of Metal-Polymer Systems, NAS of Belarus, Gomel, Belarus [email protected]

Soluble lignins, interacting with opposite-charged synthetic polyelectrolytes in aqueous solutions, form interpolyelectrolyte complexes (LPCs), which possess unique physical and chemical properties. Owing to them, LPCs have wide ranges of potencial applications, particularly, as macrosurfactants and stabilizers of suspensions and emulsions. It is known that the soluble lignins are active, but chitosan is inactive at the air-water interface. In the present work, the behaviour of LPC consisting of kraft lignin and chitosan (Ch) at different interfaces, depending on its composition and the environment, was studied. The softwood kraft 3 5 lignin (KL)( Mw = 4.1·10 by SEC) and chitosan (Ch)(DD = 78 %, Mw = 4·10 ) were used. For the preparation of aqueous solutions, Ch was dissolved in HCl. LPC was obtained by mixing the aqueous solutions of both polyelectrolytes within the wide range of pH, the composition (Z = Ch/L), the concentrations at 293±1K. The surface tension (σ) at the air-water and the heptane-water

195 interface was measured by the Wilhelmy and Du Nouy methods. The potentiometry, conductometry, spectroscopy and viscometry data show that the interaction between KL and Ch has a complicated mechanism with a prevalence of the electrostastic one. A possibility to form both non-stoichiometric (soluble) and stoichiometric (insoluble) products depends on Z of LPC and the environment. All the mixtures are characterized by remarkably lower values of σ at the air-water interface in comparison with the KL and Ch solutions. The greatest decrease in σ occurs in the mixtures with Z = 0.1-0.2, in which particles of the soluble LPC are characterized by the optimum ratio of the hydrophobic structural fragments, formed as a result of the interaction between the opposite-charged groups of KL and Ch, to their hydrophilic ones. With decreasing pH, increasing the concentration and the ionic strength, the adsorption ability of the soluble LPC particles at the air-water interfaces grows linearly. At the same time, σ at the heptane-water interface changes non- linearly with decreasing pH and increasing the LPC concentration in the water phase. It achieves the minimum values at the charge ratio (n+/n-) of 0.75 and has its maximum decrease at the transition from alkaline to weak acidic media, at which the degree of conversion in LPC remarkably increases. The optimal mutual screening of the charged groups in LPC reveals itself in the strengthening of association between the LPC particles, the formation of more dense and viscous interfacial layers and the decrease of the surface tension. The stabilizing effect of LPC was studies in the heptane-in-water emulsion. It known that KL is a weaker emulsion stabilizer than Ch. At the same time, the soluble LPC particles have a more pronounced stabilizing action on the heptane-in- water emulsions than Ch. The peculiarities of the LPC structure favours its good compatibility with both polypropylene matrix and wood fillers, including sawdust, wood flour and hydrolysis lignin. The good ingredients compatibility promotes decreasing the phase-to-phase tension and increasing the structuring processes at the filler-polymer interface that ensures the homogeneity of the composite material structure and results in its improved physicomechanical properties.

BIOMASS REMOVAL FROM THE MODEL WASTEWATER BY POLYETHYLENEIMINE AND ALUMINIUM SALTS

G. Shulga, S. Skudra, J. Brovkina Latvian State Institute of Wood Chemistry, Lignin Chemistry Department, Riga, Latvia [email protected]

The hydrothermal treatment of wood in a special basin is the first stage before its mechanical processing for production of veneer. During this treatment, autohydrolysis of wood takes place, involving the cleavage of hydrolysable bonds in lignin and polysaccharides. As a result, the wastewater of the basin of the wood hydrothermal treatment is dramatically polluted with soluble waste wood biomass, including low molecular lignin, hemiceluloses fragments, wood extractives. Keeping in mind the zero waste policy for rational use of bioresource and the possible usage of waste wood biomass (BM) in national economy, it is very important to quantitatively extract it from the basin’s wastewater. The aim of the study was to compare the effectiveness of the biomass extraction from the model wastewater of the wood hydrothermal treatment, using separately polymer cation and inorganic salts as coagulants. The hydrothermal hydrolysis of birch wood sawdust was performed in a weak alkaline medium at the modulus 1/50, 90°C and for 4 h. Polyethyleneimine (PEI) and aluminium salts: AlCl3, Al2(SO4)3 and polyaluminium chloride (PAC) (POLYPACS-30) were used for the biomass removal. The effectiveness of the biomass removal was determined after 2 h of the hydrolyzate treatment with the coagulants. The residual concentrations of BM in the filtrate were calculated from the concentration correlation curves obtained at 490 nm and 280 nm. COD and the colour of the filtrate were determined by ISO 6060:1989 and ISO 7887:1994, respectively. It is known that polyethyleneimine and aluminium salts represent coagulants, which are often used in water purification. The conducted study shows that the optimum рН values of the biomass precipitation for the applied coagulants vary in the range 5-6, in which the main part of lignin’s 196 phenolic hydroxyl groups is protonated, but a dissociation degree of carboxyl groups of low molecular lignin and hemicelluloses fragments less than 1. However, the effect of the рН values and coagulant dosages on the removal of the biomass, lignin, СОD and colour testifies the difference in the interaction mechanism of the BM components with PEI and aluminium salts. It was found that the extraction of BM with the low-molecular salts of Al is 81-83%, and that of lignin 55%, while these values for PAC are somewhat lower, namely, 80% and 53%, respectively. The most considerable differences among the Al coagulants are observed in the colour removal. PEI are characterized by the highest indices of the removal of both BM (93%) and lignin (64%), as well as wastewater colour, at the application dose 2-4 times lower than that for all the Al salts. The higher efficiency of the PEI as a coagulant may be governed by realization of the hybrid mechanism of the biomass precipitation, which includes its coagulation following the pattern of charge neutralization, and its flocculation following the pattern of bridge formation, in contrast to the Al salts, which precipitate BM mainly according to the heterocoagulation mechanism. This is favored by the high density of the charge of PEI macromolecules, its branching, and the high molecular mass. At the same time, the moderate COD removal index (40%) may indicate the presence of water soluble polyelectrolyte complexes in the hydrolyzate treated with PEI, as a result of its electrostatic interaction with the soluble fragments of low molecular lignin and hemicelluloses.

THE CHARACTERISTICS OF PEAT IN ALTAI MOUNTAINS AND PERSPECTIVE WAYS OF ITS USE

M.V. Shurova, G.V. Larina, A.Y. Sanayeva Gorno-Altaisk State University [email protected]

The republic of Altai is rich in various biological resources, healing mineral springs, organic mineral deposits, and peat. Tomsk scientific research institute of balneology and physiotherapy gave the characteristics of a resort potential to Altai Mountain [1]. According to the basic indicators the region of Altai Mountains is estimated as a special congenial region on the area of the Western Siberia with a high health resort and recreational potential. The development of a health resort and recreational region in Altai Mountains makes the development and involvement of recreational resources for practical use significant for the economy of Altai Republic. A perspective direction is working out and production of regional preventive, health-improving, and medical production. In Northeast Altai (Tourochaksky and Choisky districts) there are industrial stores of mountain peat. The specified peat is fen peat and is presented by sedge, wood-sedge and grass-bog peat kinds. Its degree of decomposing makes up 25-65 %. The considerable content of humic acids (HA) in the peat up to 58-60 % is quite typical, table 1. The HA are characterized by ash content up to 25-30 % the essence of which is comprised by Fe, Si, Ca, Mg, Al. In the paper a microelement composition of native HA, the structure of HA, chemical and biological properties are investigated. The sources of aromatic structural units of HA are the aromatic substances produced by the microorganisms of a peat layer and aromatic substances contained in the plants which form peat – lignine, anthocyans, flavonoids, chlorophyll, etc. Table 1. Physical and technical characteristics and the composition of organic matter of peat of Tourochaksky deposit, site 1 (Altai Republic) Depth, Peat kind R, % A, % B EHS HA FA HHS NHR cm % of organic matter 50-75 Sedge Fen 30 42,4 1,05 26,10 44,0 15,00 4,00 7,36 125-175 Sedge Fen 35 41,6 1,18 20,26 4,60 18,00 4,00 8,60 225-275 Sedge Fen 40 26,1 1,50 24,00 50,00 15,00 2,00 7,61 325-375 Sedge Fen 55 31,6 1,85 26,15 50,00 15,00 1,00 5,31 400-425 Sedge Fen 65 30,2 2,23 30,40 58,00 10,00 1,00 4,32

197 Notes: B - bitumens, EHS – easily hydrolysable substances, HA - humic acids, FA - fulvic acids, HHS (C) - hardly hydrolysable substances (cellulose), NHR (L) - not hydrolyzed remnant (lignine), R - a peat degree of decomposition, A - ash content of peat

The research of scientists shows that HA possess biostimulating, antiviral, and antineoplastic properties. They are non-toxic and do not possess cancerogenic, cumulative and mutagen properties. At the present time we work out some medications on the basis of a humic complex extracted from peat, and also on the basis of biologically active vegetative and mineral components. Compositions of phytomineral baths on the humic basis, the structure of gel solutions for application pelotherapy, the structure of contact medicinal mediums on the basis of a humic and mineral complex for the combined electrophoresis and vacuum electrophoresis are being developed. The potential consumers of the regional production are the following: sanatoria and preventative clinics, boarding houses, rest houses, the centers of regenerative treatment, rehabilitation centers, camp sites, and institutions for mud cures. The research is supported by the State contract № 02.740.11.0325. Literature: 1. Resort and Recreational Potential of Western Siberia. Under the editorship of E.F. Levitsky, V.B. Adilova. Tomsk, 2002. – 216 pp.

ISOMERIZATION OF ALPHA-PINENE OVER NATURAL CATALYSTS WITH DIFFERENT ACID PROPERTIES

А.Yu. Sidorenko1, G.M. Senkov1, V.Е. Agabekov1, N.D. Tuyen2 1 - Institute of chemistry of new materials NAS of Belarus, Minsk 2 - Institute of chemistry of the Vietnamese Academy of Sciences and Technology, Hanoi, Vietnam [email protected]

Catalytic isomerization of α-pinene underlies synthesis of camphene and dipentene – valuable terpene hydrocarbons, finding wide application in the chemical, perfumery and medical industry [1]. Studying of natural materials, which can be used as catalysts of this reaction is actual. Catalysts of α-pinene isomerization operate is specific. One of them leading of reaction mainly towards formation of camphene whereas others leading towards formation of monocyclic terpenes (such as dipentene). It is supposed, that prevailing route of reaction depends on type and force of acid sites of catalyst. Over weak acid sites of catalyst surface is observed mainly migration of carbon-carbon bonds with following Wagner-Meerwein rearrangement leading to formation of camphene. Over strong acid sites the basic direction of transformations is С1-С6 opening, with the subsequent formation of dipentene and monocyclic terpenes mixes [2]. The modified catalysts on a basis of bentonite (Ben) and diatomite (Dia) are investigated. Modifying diatomite and bentonite carried out implantation in their lattice of aluminium atoms from 0 AlCl3·6H20 at 450 С during 1,5 h and AlCl3·6H2О quantity is 0,7 g/g catalyst (Al/Dia, Al/Ben). Isomerization of α-pinene carried out at 1400С in the presence of 1 wt% modified Dia and Ben. Acidity of catalysts was defined by thermoprogrammed desorption of ammonia (NH3-TPD) Modified Dia and Ben have practically identical general acidity – 0,53 and 0,56 mmol/g accordingly, however are characterised various distribution of force of the acid sites. In Al/Dia prevail week-medium acid sites (0,35 mmol/g), whereas in Al/Ben prevail strong acid sites (0,34 mmol/g). At identical conversion of α-pinene (50 %) selectivity of reaction towards camphene over Al/Dia makes 50 %, whereas over Al/Ben – 37 %. The greatest selectivity to dipentene (38 %) is show Al/Ben, over Al/Dia it make 30 %. For 5 h reactions over Al/Dia and Al/Ben has reacted accordingly 93 and 53 % of α-pinene. Prevalence strong acid sites in Al/Ben directs reaction on the way of dipentene formations primary, speed of α-pinene expenditure thus decreases. Increase selectivity to camphene over Al/Dia it is possible to explain presence of a considerable quantity of week-medium acid sites

198 It is established, that in reaction of α-pinene isomerization over modified AlCl3·6H20 catalysts on basis of bentonite and diatomite the weak and medium acid cites favour to formation of camphene, whereas strong acid sites direct reaction on a way of primary dipentene formation. Possibility of use modified by aluminium diatomite like catalyst system for isomerization of α- pinene to camphene is shown.

The literature: 1.Yadav M.Kr., Chudasama C.D. Jasra R.V.//J. of Molecular Catal. A:Chemical. 2004. Vol.216, No 1. P. 51. 2. Agabekov V. E, Senkov G. M// Catalysis in the industry. 2007. №4. p.38.

SORBENT BASED ON NATURAL RAW MATERIALS

L.A. Silchenko, P.S. Golynskii Bryansk State Engineering Technological Academy [email protected]

One of perspective directions of processing of a biomass of wood cultures alongside with creation of valuable products for food and a farmaceutical industry is creation low-cost effective sorbent materials on the basis of available natural raw material. It was represented appropriate to estimate properties of a sorbent on the basis of fruits of a mountain ash ordinary from which sorbic acid for the first time has been received. The specified sorbent received on the technology providing "dredging" of extractive and biologically active substances and subsequent mechanochemical treatment of the dry waste. Sorbent was tested for availability adsorbption properties in relation to acids in dynamic conditions. As cleared solutions were investigated solutions organic acids (acetic, formic and sorbic). The specified sorbent placed in a glass column of the optimum sizes (the attitude of diameter to length of a column about 1:10), supplied by porous linings in order to prevent ablation sorbent in operations of sorption. Through a stationary layer of a sorbent passed a solution containing organic acid, having adjusted the uniform expiration of a liquid with the certain speed. Supply of a filtrate was carried out up to breakthrough of the absorbed component that located by means of the analysis on acidity with acid- base indicator. After that purified and initial solutions were analyzed for an acid content by the method of titration 0,01н sodium hydroxide at presence of phenolphthalein. After saturation of a sorbent on absorbed components material balance was counted for each experiment, allowing quantitatively to estimate results of sorption and to compare them. It is shown, that the capacity of a sorbent on the basis of mountain ash pulp makes 60 г/1 kg on acetic acid, 75г/1 kg on sorbic acid and 80г/1 kg on formic acid. In view of that the specified acids are used as preservatives (using of acetic and sorbic acids as conservations of foodstuff it is known for a long time, formic acid is used in an agriculture for conservation of green forages – for silage), the fulfilled sorbent may be is used in these objectives in an agricultural production. Regeneration of the sorbents is not provided. The testing of toxicity of filtrates lead by us after adsorption clearing of impurity of organic acids with use as the test of objects Daphnia magna and liophilized bacteria Escherichia coli has shown that filtrates do not represent danger for hydrobioorganisms and soil organisms in case of their dump to superficial reservoirs or injection under a deep-lying seam of soil.

199 BREAD TECHNOLOGY AND CANCER

V. Simac1, M. Sandric1, V. Caragia1, D. Nicolaeva2, Ju. Golovco3 1 - National Institute of Research & Development for Food Bioresources - IBA Bucharest, Interdisciplinary Research Compartment, Bucharest, Romania 2 - Scientific-Practical Institute of Horticulture, Viticulture and Food Technology, Laboratory of Food Technology, Chisinau, Moldova 3 - "SVD-GROUP" SRL, Chisinau, Moldova [email protected]

Bread and other bakery products are the most important consumed worldwide daily food products. The classical bread quality approach has been focused on the bread crumb porosity and whiteness. It has so much spread over the world that, even in our days, when nutrition science have discovered the importance of some biologically active compounds, which are missing here, most of the consumers and of the producers are looking for or producing a such type of bread. It’s normally and good consumer behavior and food production practice or not? If the bread and bakery products would be representing a little slice of our daily intake, may be the situation would not be so bad. But in most of the cases, bread and bakery products bring about 20- 30% of our daily calories. According to classical bread quality approach, to achieve the “best” crumb porosity and whiteness the producer will need the flour with lower extraction rate, the whitest as possible, besides the quality and quantity of gluten, the content of α-amylases, etc. For the same purpose it will be necessary to add some additives. As a result, the final product looks “good”, but its nutritional value is the poorest possible and even may be harmful. This is the correct explanation for some of the identified connections between white bread consumption and kidney and colorectal cancer. Different studies conducted in different countries (UK, Italy and Poland) came to the same conclusions. The fact is so clear, that for non-harmful bread even has been established a new characteristic: “non-white”, meaning any kind of bread (whole meal, brown, rye, multi-cereal, with seeds, etc), except white bread, which is now qualified as bad. While the scientific proves is evident, still remain a gap between science and production, between science and consumption preferences. To solve this situation is the role of the scientist and of the scientific dissemination. They are the people who know and who own the best means to spread this knowledge at large scale for producers, consumers and other scientists. The best way to escape cancer is to prevent it. Let than our food be our medicines, as Hypocrites has said. Besides the wheat and rye flour (even whole meal), the sensorial and nutritional characteristics may be improved by using of different kind of ingredients, which are not normally used to make bread: herbs and spices, fruits, seeds, vegetables, legumes and cereals. These materials may be used in different forms: grounded, dried, powder, meals, flour, flakes and oil. An example of new ingredients to be used in bakery is by a merging with the supercritical CO2-extraction technology. That technology extracts from natural raw materials, at low temperature, different fraction rich in biologically active substances. Normally, these fractions may be used in pharmaceutical, cosmetics or food supplements industry. But there will be some by-products, which may be very well used in bakery technology. A bilateral project “Development of CO2 - extraction technology of biologically active substances of wheat germ” was financed by Academy of Sciences of the Republic of Moldova (project No 24/RoA) and National Authority for Scientific Research of Romania (project No 417/2010) which will apply exactly this principle of utilization the extracts in some industries and the remaining by-product in bakery. With the classical methods of extraction in pharmaceutical or food industry will result some by- products, like press cakes, filter-cakes or extraction cakes, which may be used in bakery (taking in account of course the solvents content and avoiding possible toxicity). The main idea is to improve, as much as possible, the bread nutritional and sensorial characteristics by low-cost and ecological materials and methods. This should be included also in governmental

200 strategy and supported by the state in all the aspects, because bread is the strategic food in the country – it may improve or deteriorate the health of the entire population (like water for instance). Literature: 1. M. A. Sanjoaquin, P. N. Appleby, M. Thorogood, J. I. Mann and T. J. Key, "Nutrition, lifestyle and colorectal cancer incidence: a prospective investigation of 10.998 vegetarians and non-vegetarians in the United Kingdom", British Journal of Cancer (2004) 90, p.118– 121, doi: 10.1038/sj.bjc.6601441. 2. E. Bidoli, S. Franceschi, R. Talamini, S. Barra, C. L. Vecchia, "Food consumption and cancer of the colon and rectum in north-eastern Italy", International Journal of Cancer, Vol. 50, Issue 2, p. 223–229, 21 January 1992.

VEGETABLE OIL HYDROGENATION OVER PD SUPPORTED ON MESOPOROUS CARBON: CATALYST ACTIVITY ENHANCEMENT AND REACTION KINETICS MEASUREMENTS

I.L. Simakova, Yu.S. Demidova, M.N. Simonov Boreskov Institute of Catalysis, Novosibirsk, Russia [email protected]

Hydrogenation of polyunsaturated fatty acids and their triglycerides over platinum metals is an important process in the oil, fat and oleochemical industries providing a broad range of margarines, shortenings, light butters and fats free from carcinogenic Ni with lower content of trans-isomers [1]. The general purpose of this process is to increase the melting point and to improve the oxidation properties of the liquid oil. The chemistry of the hydrogenation processing of oils involves three simultaneous reactions: saturation of double bonds, geometric (cis–trans) and positional isomerizations. The quality and physical properties of the hydrogenated oil are greatly influenced by the number of double bonds and the cis–trans-isomers composition of fatty acids. The utilization of trans-fatty acids (TFA) in food consumption has been reported to be unfavorable since it strongly correlates with coronary heart diseases. As a consequence there is a growing interest in new hydrogenation processes which reduce the amount of trans fats formed. A series of studies has been reported in the literature showing that supported Pd catalysts containing low amounts of the metal are proved to be a right compromise for commercial industrial application in the oil hydroprocessing [2-8]. Ecological friendly nanosized palladium catalysts supported on mesoporous carbon Sibunit were developed to produce harmless nickel-free margarine and confectionery fat with high organoleptic quality [9]. The aim of this work is to design the Pd/C catalysts providing maximum activity for the plant oil partial hydrogenation and to evaluate Pd/C samples behavior at the laboratory scale before their further introduction into production-scale operation. The effects of support chemical pretreatment, catalyst particle size, Pd loading and the type of vegetable oil (sunflower and palm) on reaction rate and fatty acids distribution as well as on profile of solid fat content (SFC) were studied. The samples of the carbon support of 40-70 m, 70-100 m, 100-180 m, 180-250 m were wet sieved after grinding to prepare 0.1 or 1% wt. Pd/C. Part of Sibunit carbon support was activated by a treatment with 38 wt. % HCl (aqua) to purify from possible metallic impurities. Laboratory scale hydrogenations were performed in a 150 ml stainless steel autoclave (1000 rpm) at 413 K and PH2 9 bar in the absence of mass transfer limitations with automatic recording of hydrogen uptake. The catalyst/oil weight ratio was 1/100÷1/1000, the amount of substrate was 14 g. The fatty acid composition was analyzed by GC (FID, 15m х0.25mm х0.5 mm, Carbowax-DVB, 250C), while the SFC was analyzed by 1H-NMR. According to experimental kinetic data a Pd/C catalyst with optimal structural parameters affording higher activity has been developed. A comparison between Pd/C and commercially available Ni catalysts was performed. It was shown that the catalysts, containing Pd, led to lower TFA amounts and showed activity similar to commercial nickel counterparts, being not only environmentally benign but also displaying stable behavior in the

201 repeated tests (at least 10 cycles). It should be kept in mind that the palladium loading in the tested samples (1.0 wt. %) is significantly lower than the nickel one in commercial catalysts (ca. 35% of Ni and NiO) pointing out on superior intrinsic activity of palladium. Such promising results encouraged to perform pilot plant tests at the industrial plant demonstrating that similar iodine values and SFC profile can be achieved for palladium catalysts.

References [1] Patent RF 2105050. [2] V.A. Semikolenov, I.L. Simakova, G.V. Sadovnichii, Chimicheskaia promyshlennost, 3 (1996) 184-192. [3] A.F. Perez-Cadenas, M. M. P.Zieverink, F. Kapteijn, J.A. Moulijn, Carbon, 44 (2006) 173-176. [4] M.B. Fernandez, J.F. Sanchez M., G.M. Tonetto, D.E. Damiani, Chem. Eng. J. 155 (2009) 941– 949. [5] I.L. Simakova, O. Simakova, A.V. Romanenko, D.Yu. Murzin, Ind. Eng. Chem. Res. 47 (2008) 7219-7225. [6] O.A. Simakova, P.A. Simonov, A.V. Romanenko, I.L. Simakova, React. Kinet. Catal. Lett., 95 (2008) 3-12. [7] Patent RF 2318868. [8] Patent RF 2323046. [9] Patent RF 2411996.

ANALYSIS OF PALM KERNEL OIL HYDROGENATION USING PD/C: EFFECTS OF CARBON PORE STRUCTURE AND PD CONCENTRATION PROFILE

I.L. Simakova, M.N. Simonov, Yu.S. Demidova, I.P. Prosvirin Boreskov Institute of Catalysis, Novosibirsk, Russia [email protected]

Palm kernel oil (PKO) being of vegetable origin and solid at normal temperature is obtained from the kernels of the oil palm (Elaeis guineensis). PKO is different from palm oil, which is obtained from the flesh of the fruit. Increasing use of this oil in the commercial food industry throughout the world is encouraged by its low cost, high oxidative stability of the refined product when used for frying, and absence of cholesterol and trans- fatty acids. PKO is an attractive source of highly saturated fatty acid triglycerides for tire and candle production, cosmetic and pharmaceutical industries [1,2]. Currently, the process is carried out at high temperatures (180÷250oC) over toxic nickel or nickel-copper catalysts and has serious disadvantages such as contamination of products by carcinogenic Ni and inevitability of catalyst waste utilization. Earlier a batch-wise method to produce edible hydrogenated oils by sunflower oil hydrogenation in the presence of Pd/C catalyst was developed [3,4]. This work deals with development of PKO hydrogenation over Pd/C as an alternative to traditional Ni catalysts. The general reaction regularities, influence of the catalyst preparation method providing the best accessibility of active Pd sites for faster fatty acids conversion, as well as the impact of support texture and particle size on the reaction rate and fatty acids distribution were investigated. The activated carbon “Sibunit” has been chosen as a mesoporous carbonaceous support because of its high surface area, lipophility and chemical inertness in acidic and basic media [5]. Sibunit samples with varied BET surface area, pore volume and average pore size of carbon support were synthesized in IHP SB RAS (Omsk). Samples with carbon particle size of <40 μm, 40-70 μm and 70-100 μm were taken for Pd supporting. The Pd on Sibunit catalysts (denoted as called ICT-3-20 and ICT-3-23) were prepared by the techniques different in reagent feeding, developed in Boreskov Institute of Catalysis and previously utilized for catalyst preparation on a o pilot scale. Hydrogenation experiments were carried out in a batch reactor at PH2 9 bar and 195 C. Hydrogen uptake was monitored during the reaction by using a pressure controller “Sapfir”. Concentration of catalyst in the oil was 0.2 % and 0.4% in case of 1%Pd/C and Nysosel-800 202 (commercial Ni catalyst), respectively. Fatty acid composition of initial and hydrogenated PKO was analyzed by GC using a Rt-2560 (100m×0.25mm×0.2μm) column. Iodine values were calculated using fatty acids concentrations. XPS spectra of Pd/C samples were recorded on SPECS spectrometer equipped with PHOIBOS-150-MCD-9 semi-spherical analyser and FOCUS-500 X- ray monochromator (AlK, h = 1486.74 eV, 200 W). The surface elemental compositions were determined by the ratios of elemental peak areas for catalysts per se and grinded ones. Influence of the support particle size and catalyst preparation method on activity of 1wt.% Pd/C catalysts in PKO hydrogenation reaction was studied. A higher reaction rate was observed over ICT-3-23 compared to ICT -3-20, although hydrogenation of PKO to the fully saturated product in the presence of a commercial Nysosel-800 catalyst was found to be even faster. PKO conversion over ICT-3-23 catalysts increases with decreasing carbon particle size, and the highest reaction rate was obtained for fraction with a size less 40 μm. On the contrary, fast reaction rate on ICT-3-20 was achieved over a fraction with the largest particle size 70-100 m. A comparative analysis of both catalyst samples by XPS has confirmed that ICT-3-20 catalysts have a core-shell distribution of Pd along the catalyst grain. Therefore, high hydrogenation rates are related to high local concentration of palladium on the outer grain surface providing easy access for reactants and high activity of such catalysts in triglycerides hydrogenation. Carbon pore diameter seems to be an important factor among the other factors strongly affecting PKO hydrogenation rate, being the highest for the most active Pd/C catalyst despite of its relatively lower specific surface area.

[1] H.J. Dutton. Chem. Ind. 2 (1982) 9-17. [2] H. Wagner, R. Luther, T. Mang. Appl. Catal. A: General 221 (2001) 429-442. [3] Russian Pat. No. 2105050, 1996. [4] V.A. Semikolenov, I.L. Simakova, G.V. Sadovnichii, Chimicheskaia promyshlennost 3 (1996) 184. [5] A.F. Pérez-Cadenas, M.P. Zieverink, F. Kapteijn, J.A. Moulijn. Carbon 44 (2006) 173-176.

BIOMASS PROCESSING OVER GOLD CATALYSTS VIA SELECTIVE OXIDATION OF HYDROXYMATAIRESINOL (HMR) AND 5-HYDROXYMETHYLFURFURAL (HMF)

O.A. Simakova1, S. Davis2, E.V. Murzina1, S.M. Willfor1, R.J. Davis2, D.Yu. Murzin1 1 - Abo Akademi University, Department of Chemical Engineering, Turku, Finland 2 - University of Virginia, Department of Chemical Engineering, Charlottesville, USA [email protected]

Valorization of biomass-derived compounds has stimulated the development of processes performed over heterogeneous catalysts, since this approach is more appropriate for the industry. Recent expansion of research on catalysis by gold has revealed excellent activity and stability of these catalysts in the variety of reactions, in particular, selective oxidation. Investigation of gold as a heterogeneous catalyst for the processing of the biomass-derived compounds is a matter of fundamental and industrial interest. Here we are HMR reporting a study on gold catalysts application in the selective oxidation of a lignan hydroxymatairesinol (HMR) and 5-hydroxymethylfurfural (HMF), both derived from biomass feedstock. Lignans are natural phenolic compounds found in different parts of plants, HMF such as wooden parts, roots, leaves, stem, seeds, flowers, and fruits. Thus, Norway spruce (Picea abies) knots contain large amounts of lignans, where the most abundant one is hydroxymatairesinol (HMR) [1], constituting 65-85 wt. % of the total lignans and occuring in unconjugated free form [2]. Lignans or lignan derivatives, due to their antioxidative activity and UV-protection properties [3], can be applied for cosmetic and pharmaceutical uses (skin- and hair-care products), as well as color-keeping agents for textile industry, wherein the active agent is selected from the group of lignans comprising oxomatairesinol (oxoMAT), which can be obtained from HMR. The latter 203 reaction of secondary alcohol oxidative dehydrogenation over gold catalysts was performed in a semi-batch reactor at 70°C under the synthetic air flow. Reaction products were silylated and analyzed by GC. 5-hydroxymethylfurfural (HMF) is one of the many potential platform chemicals for biorenewable chemicals production [4] because it is formed by dehydration of fructose and glucose [5]. HMF can be oxidized to 2,5-furandicarboxylic acid (FDCA), which, for example, is a possible replacement monomer for terephthalic acid used to produce polyethylene terephthalate (PET). The reaction was performed using gold catalysts in the autoclave at 25 °C under the oxygen pressure of 5 bar. Obtained products were analyzed by HPLC. Gold catalysts applied in both reactions were prepared by several methods such deposition- precipitation with urea and direct ion exchange. Catalysts were characterized by TEM, XRD and XPS. Activity of Au-catalysts on different supports was found to be dependent on the support nature. Thus, in case of the selective oxidation of HMR, the most active catalyst was Au supported on alumina. At the same time, selectivity to oxoMAT was 100 % while Au on alumina, titania and silica were applied. Gold catalysts have demonstrated high activity in the synthesis of FDCA from HMF. The reaction was performed at different conditions, such as pH of the solution, pressure and the catalyst loading. These parameters were observed to determine the selectivity of the reaction to the desired FDCA. More details will be given in the presentation. [1] R. Ekman, Holzforschung 30 (1976) 79. [2] S. Willför, J. Hemming, M. Reunanen, C. Eckerman, B. Holmbom, Holzforschung 57 (2003) 27. [3] H. Korte, M. Unkila, M. Hiilovaara-Teijo, V.-M. Lehtola, M. Ahotupa, Patent WO/2004/000304 A1 (2003); T. Ahlnäs, Patent WO 2008/020112 A1 (2008). [4] J.N. Chheda, G.W. Huber, J.A. Dumesic, Angew. Chem. Int. Ed. Engl. 46 (2007) 7164. [5] J.N. Chheda, Y. Roman-Leshkov, J.A. Dumesic, Green Chem. 9 (2007) 342.

MORPHOLOGY OF THE NANOCOMPOSITES BASED ON POLYURETHANES SYNTHESISED FROM CASTOR OIL

V. Simendic1, I. Ristic1, N. Vukic1, P. Hvizdos2 1 - University of Novi Sad, Faculty of Technology, Department of materials engineering, Novi Sad, Serbia 2 - Institute of Materials Research of the Slovak Academy of Sciences, Kosice, Slovak Republic [email protected]

Castor oil is mainly contained from esters of 12-hydroxy-9-octadecanoic acid. Because of the presence of hydroxyl groups in castor oil, castor oil is suitable for urethane type reactions. Hydrogen bonding of its hydroxyl group gives a high viscosity to the oil. This work presents the preparation and Morphology of the nanocomposites based on polyurethanes synthesised from toluene diisocyanate and castor oil, with addition of TiO2 nano particles. Also, polyurethane sheets from isophorone diisocyanate and castor oil were synthesized to be compared with polurethanes synthesised from toluene diisocyanate. Different NCO/OH ratios, r, were used (1; 1.15; 0.92) for sample preparation. For nanocomposites r value was 1 and they were prepared by premixing the filler particles with the castor oil polyol before reaction in glass wassel with toluene diisocyanate at 120°C for 15 minutes. Samples were obtained in metal molds (heated in oven at 120°C for 12h). Different contents of TiO2 nano particles were added to polymer matrix (0.5; 1; and 2 wt%) for composites preparation. Morphology of obtained materials was observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). From SEM images good dispersion of nano filler in polymer matrix was noticed. AFM method demonstrated topology of nano fillers in polymer matrix and confirmed its good homogenization.

204 GREEN PROPYLENE GLYCOL CATALYTIC SYNTHESIS FROM LACTIC ACID ESTERS UNDER MILD REACTION CONDITIONS

M.N. Simonov, I.L. Simakova, T.P. Minyukova, A.A. Khassin Boreskov Institute of Catalysis, Novosibirsk, Russia [email protected]

Nowadays design of the new catalytic routes starting from platform molecules derived from renewables and different from the traditional chemical synthesis routes starting from fossil fuels is one of the key issues of sustainable development [1].Thus, commercial production of propylene glycol widely used as a solvent or a reagent in pharmaceutical and chemical industries is currently petroleum-based and involves high pressure and high temperature hydrolysis of propylene oxide produced by either chlorohydrin process or the per-oxidation process which is unfavorable from green chemistry point of view. A catalytic method starting from lactic acid obtained by fermentation of crude biomass provides an eco-friendly alternative to the petroleum-based process for 1,2-propanediol synthesis. However it is well known that catalytic hydrogenation of carboxylic acid to corresponding alcohols is a very difficult process, which requires high pressure and temperature [2]. For example, hydrogenation of lactic acid to propylene glycol over Ru-containing catalyst was carried out at 14.5 MPa and 423 K leading to noticeable lactic acid conversion and selectivity to propylene glycol [3]. Carrying out hydrogenation in a vapor phase allows lowering hydrogen pressure. Lactic acid hydrogenation in vapour-phase over 10 wt. % Cu/SiO2 catalyst leads to 7.3 % conversion and 75 % selectivity to propylene glycol at 1 bar hydrogen pressure [4]. However, several drawbacks have arisen during direct hydrogenation of lactic acid such as catalyst deactivation due to polymerization of lactic acid and formation of undesirable propionic acid. To perform the hydrogenation process more effectively carboxylic acids are usually converted into more readily reducible esters [5]. A novel method for production of glycols that can be performed under relatively mild conditions and results in high conversion of lactic acid esters and selectivity to propylene glycol was recently reported [6]. At present work we were focusing on feasibility of propylene glycol synthesis via copper catalyzed hydrogenolysis of methyl and butyl lactates under mild reaction conditions [7]. The goal is to study an effect of copper loading, an impact of alkyl substitute length and an influence of reaction conditions such as temperature, space velocity, and solvent nature in order to develop highly selective green catalytic process of propylene glycol synthesis under mild reaction condition. In optimized reaction conditions the most active catalyst with copper loading 45.5 wt. % afforded 98% neat methyl lactate conversion and selectivity to propylene glycol of 78% at 473 K. In the presence of water and methanol side reactions of hydrolysis and dehydration occur leading to selectivity drop, therefore the use of solvent should be avoided. Effect of substituent in alkyl lactate on conversion and selectivity to propylene glycol was studied. Substrate conversion and selectivity to the main products were very similar during hydrogenolysis of neat methyl and butyl lactates. Utilization of butyl lactate is preferred due to resistant of released butanol to side transformations compared to methanol providing propylene glycol selectivity of 96% at nearly full butyl lactate conversion of 99% under atmospheric hydrogen pressure at 453 K. Based on the kinetic data and identification of intermediates by GC/MS and 1H-NMR a butyl lactate hydrogenolysis routes over reduced silica-supported copper were proposed. The main reaction path involves consecutive lactate carbonyl moiety protonation and hydrogenation into hemiacetal followed by formation of thermodynamically equilibrated mixture of propylene glycol and hydroxyacetone with majority of propylene glycol whereas irreversible alkyl acrylate formation is completely suppressed.

[1] P. Gallezot, Catal. Today 2007, 121, 76–91. [2] B. Chen, et al. Appl. Catal. A 2005, 280, 17-46. [3] Z. Zhang, J.E. Jackson, D.J. Miller. Appl. Catal. A 2001, 219, 89-98. [4] R.D. Cortright, M. Sanchez-Castillo, J.A. Dumesic. Appl. Catal. B 2002, 39, 353-359. [5] A.G.M. Barrett in Comprehensive Organic Synthesis (Eds.: B.M. Trost, I. Fleming), Elsevier, Oxford, 1991, 39, p. 205 236. [6] I.L. Simakova, M.N. Simonov, M.P. Demeshkina, T.P. Minyukova, A.A. Khassin, V.N. Parmon Pat. WO 2009103682 27.08.2009. [7] M. N. Simonov, I. L. Simakova, V. N. Parmon. React. Kinet. Catal. Lett. 2009, 97, 157-162.

RESEARCH OF POSSIBILITY OF OBTAINING OF HETEROCYCLES FROM (+)-3- CARENE AND ANILINE

D.A. Skladchikov, R.R. Gataullin Institute of Organic Chemistry of the Ufa Scientific Center of the Russian Academy of Sciences, Ufa [email protected]

The natural terpens hydrocarbons extracted from vegetative raw materials, are used in chemical researches and in synthesis of a various classes of compounds. Among bicyclic natural ethylenes of this series Δ3-carene is one of easily available representatives [1]. We research possibility of application of this terpen in synthesis of heterocyclic compounds. After bromination of carene 1 reactionary compound without selection of halogenation products have been mixed with aniline at a boiling in triethylamine. In result of reaction was received a mixture of several compounds from which were isolated pure 2 and 3 with low yields. There are not unequivocal opinion about mechanism of formation of last azabicyclo[3.2.1]octenic heterocycle. We consider some variants of this transformation. This substance could be formed both as a product of double bromination of some part of carene and from the intermediate dibromide or a product of dehydrogalogenation. The composition and structure of the received samples 2 and 3 was established by the element analysis, NMR 1H-, 13C - and mass-spectroscopic methods. Orientation of substituents at asymmetric atoms of carbon in a heterocycle 3 was attributed on the basis of the suppose mechanism of natural carene bromination and the subsequent structural transformations of intermediates.

CH 3 CH H3C Br 2 H3C Br Br Br Br Br2 Br H C 3 CH 3 H3CCH3 H CCH 1 Br 3 Br 3 [O] Et N -HBr ? H 3 NH2 N CH2 H3C Br Br CH Br NH2 2 HBr N

H3C H2CCH3 CH3 H3C CH3 2, 38 % 3, 9 % 20 o 20 o []D +4 (c 1, C6H6) []D +54 (c 1, C6H6) References. [1] Volcho K.P., Rogoza L.N., Salahutdinov N.F., Tolstikov A.G. Preparativnaya khimiya terpenoidov. Vol. 1. Novosibirsk, 2005.

206 IDENTIFICATION OF NEW LIGNANS IN NORWAY SPRUCE KNOTWOOD EXTRACTS

A.I. Smeds1, I. Ceskova2, P.C. Eklund3, S.M. Willfor1 1 - Process Chemistry Centre Laboratory of Wood and Paper Chemistry Abo Akademi University Porthansgatan, Turku, Finland 2 - Faculty of Agriculture University of South Bohemia Ceske Budejovice, Czech, Republic 3 - Process Chemistry Centre Laboratory of Organic Chemistry Abo Akademi University Biskopsgatan, Turku, Finland [email protected]

Introduction. Approximately 0.5% of the dry weight of Norway spruce wood has been reported to consist of lignans, a group of phenolic compounds structurally characterized by two phenylpropane units linked together by -bonds. Lignans have attracted much attention because of their health- promoting effects. In Norway spruce, the knots (the part of the branch embedded in the stem), which constitute up to 2% of the dry mass, have an extremely high lignan content (6% -24%). 7- Hydroxymatairesinol is the dominating lignan, accounting for 65-85% of the total lignan content. Other known lignans in spruce knots are -conidendrin, secoisolarici-, larici-, pino-, and matairesinol, lignan A (7´-hydroxylariciresinol), lignan B (demethoxylated lignan A), iso- hydroxymatairesinol, and two stereoisomers of a lignan suggested to be liovil. In the present study, we aimed at identifying new lignans in knotwood of Norway spruce. Unidentified peaks in the gas chromatography-mass spectrometry (GC-MS) chromatograms of Norway spruce knotwood hydrophilic extracts have indicated that other previously unidentified lignans, which seem to be of the hydroxylated divanillyl butyrolactol type, may be found in Picea species. Experimental. Splintered, freeze-dried, and ground knotwood of Norway spruce was Soxhlet extracted with n-hexane overnight and then with ethanol overnight. 7-Hydroxymatairesinol was partly removed from the ethanol extract by potassium acetate precipitation. The extract was purified by flash chromatography, and combined flash fractions containing target lignans were further purified by preparative high-performance liquid chromatography (HPLC). Identification and quantification of individual components was performed by GC-MS and GC-FID analysis, respectively, of silylated extracts. Structural elucidation of some individual components was performed by NMR analyses. Results. 7S- and 7R-todolactol A, 7S-isoliovil, one stereoisomer of lignan A, and two stereoisomers of 9´-hydroxylariciresinol were identified by GC-MS analyses, and their structures were confirmed by NMR analyses. The configuration of lignan A seemed to be 7´S,8´R,8R,7S, and of the two stereoisomers of 9´-hydroxylariciresinol 9´R,8´R,8R,7S and 9´R,8´R,8R,7R. Additionally, lignan B was identified by GC-MS analyses. At least two other stereoisomers of lignan A and four stereoisomers of liovil, 7-hydroxylariciresinol, 7-hydroxy-divanillyl tetrahydrofuran, and 9- hydroxypinoresinol were tentatively identified on the basis of their mass spectra. The correct identities of the previously tentatively identified liovils were probably 7R-todolactol A and 7R- isoliovil. In addition to these lignans, the mass spectra of 16 more unknown minor lignans indicated the presence of 31 previously unidentified lignans in Norway spruce knotwood hydrophilic extracts. The previously unidentified lignans account altogether for approximately 7% of the dry ethanol extract weight. 7R-Todolactol A, which was the dominating of the new lignans, was found to be very unstable in aqueous solutions, forming 7R-isoliovil, one stereoisomer of 9´- hydroxylariciresinol, probably 7S-todolactol A, and, tentatively, todolactol B, 7-hydroxy-divanillyl tetrahydrofuran, and didehydro-divanillyl tetrahydrofuran.

207 CHEMICAL CHARACTERIZATION OF POLYMERIZED PRODUCTS FORMED IN THE REACTIONS OF MATAIRESINOL AND PINORESINOL WITH THE STABLE RADICAL 2,2-DIPHENYL-1-PICRYLHYDRAZYL

A.I. Smeds1, P.C. Eklund2, E. Monogioudi3, S.M. Willfor1 1 - Process Chemistry Centre Laboratory of Wood and Paper Chemistry Abo Akademi University Porthansgatan, Turku, Finland 2 - Process Chemistry Centre Laboratory of Organic Chemistry Abo Akademi University Biskopsgatan, Turku, Finland 3 - VTT Technical Research Centre of Finland, Finland [email protected]

Introduction. This study presents methods for preparation of and chemical characterization of polymers, based on renewable wood resources. More exactly, we studied the reactions of the pure lignans matairesinol (MR) and pinoresinol (Pin), isolated from wood, with the stable radical 2,2- diphenyl-1-picrylhydrazyl (DPPH). Lignans are natural polyphenols occurring especially in the knotwood of coniferous trees, and they possess a diverse spectrum of biological activity, including the promotion of human health. The study is connected to the biorefinery concept and the necessity to utilize lignin as a value-added material, since more processable lignins may be produced by co- polymerization of degraded lignin and lignans. Lignans function as simple model compounds similar to lignin units, available in large amounts as waste from the forest industry. Lignan polymers as such may also be useful in some applications. Furthermore, developing an analytical protocol for characterizing lignan polymers is important. There are indications that lignan polymers are present in wood, as several oligolignans have previously been identified in knotwood of Norway spruce and Scots pine. Experimental. MR and Pin were (separately) allowed to react with DPPH in a molar lignan–DPPH ratio of 1:2, at a concentration of 3 mg/mL in methanol. The reaction mixture was stirred in the dark at room temperature for 24 h, and then the solvent was removed in a vacuum evaporator. The reaction mixtures were fractionated using flash chromatography and gel permeation chromatography using Sephadex LH-20 gel. The polymer fractions were chemically characterized using several advanced analytical techniques. Results. Both lignans reacted very rapidly with DPPH, and the reactions were almost quantitative. The molecular weight (MW) distribution of the formed lignan dimers and polymers was determined by high-performance size-exclusion chromatography with evaporative light-scattering detection, and the compounds were characterized by HPLC-MS, pyrolysis-GC-MS, NMR, matrix-assisted laser desorption ionization time-of-flight MS, and GC-MS of monomeric and dimeric units formed after KMnO4 oxidation. The different analytical methods showed partly different pictures of the products because of the selectivity of each method. The yield of high-MW polymers was higher for Pin, and the MW distribution was also broader than for MR. Pin polymers seemed to consist mainly of hepta–hexacontalignans (MW 2.5–21.4 kDa), whereas the MR polymers were mainly penta– pentadecalignans (MW 1.8–5.3 kDa). The MR dimers contained partly methoxylated and dehydrogenated units. Both MR and Pin polymers were partly modified by demethylation, demethoxylation, and oxidation at the  position, and Pin dimers and polymers contained partly guaiacyl and vanillyl adducts. However, these modified units constituted a minor part of the products. Both MR and Pin polymers were predominantly linked to each other by 5–5´ bonds: the 5–5´:5–O–4´ ratio was approximately 87:13 for MR polymers and 92:8 for Pin polymers. Acknowledgements. The study is part of the LigniVal project in the Tekes BioRefine program. Funding from Tekes, Metso Power Oy, Oy Metsä-Botnia Ab, Stora Enso Oyj and Roal Oy is acknowledged. The work is also part of the activities at the Åbo Akademi University Process Chemistry Centre within the Finnish Centre of Excellence Programme by the Academy of Finland.

208 THE WAYS TO IMPROVE THE ELECTRO-PHYSICAL PROPERTIES OF PAPER

E.G. Smirnova1, N.M. Zhuravleva2, A.K. Hripunov3 1 - Saint-Petersburg State Forest Technical Academy n.a. S.M. Kirov, Russia 2 - Saint- Petersburg State Polytechnic University, Russiа 3 - Institute of high molecular Compounds, Russian Academy of Sciences, Saint-Petersburg, Russiа [email protected]

Obviously, the role of electrically insulating materials in the development of electrical energy industry is big because reliability and technical and economic parameters of electrotechnical equipment depend to a large extent on condition of its dielectrical system. Thereby in the whole world the special attention is given to development of the new dielectric materials as well as to improvement of the properties of the papers, traditionally used for this purposes. Paper insulating materials are high-demanded in a high-voltage cable technology, pulse capacitors. Up to now they don't have competitive synthetical analogues in a power transformer industry. However, it is well known that a paper as a dielectric has significant disadvantages, such as low electric strength and thermal stability. To improve the electro-physical properties were obtained laboratory samples of electrical insulation paper. The paper is a composite which includes cellulose – sulfate unbleached softwood EGB-brand and bacterial cellulose which is produced by bacterial culture Gluconacetobacter xylinum (CGX). Bacterial cellulose in the form of nano-gel-film (NGF CGХ) was obtained by static cultivation of the environment, using as a source of carbon waste of sugar manufacture. After CGX preparation it was added to sulfate unbleached softwood EGB-brand in number 0-10% [1]. The composite was put to several tests such as mechanical strength (σ, MPa) and short-term electric strength (E, kV/mm) before and after thermal deterioration. Thermal deterioration was made at temperature 140°С within 120 hours at easy approach of air. In process of augmentation of maintenance CGX in a paper about 0 % to 10 % mechanical strength on tearing up (σ) has increased on the average by 28 % (with 75.0 ± 1.8 МPа to 96.3 ± 2.0 МPа). After thermal deterioration value of the characteristic has obtained 60.0 ± 2.5 МPа and 86.6 ± 1.8 МPа, accordingly. In the course of thermal deterioration rate of mechanical strength of a composite were depressed, however introduction of CGX hasn't led to increasing speed of process of deterioration. Short-term electric strength (Е) has increased by 90 % (with 7.0 ± 0.8 kV/mm to 13,2 ± 0,8 kV/mm) in a reference state and remained almost invariable after thermal degradation. We have defined using the microcolorimetr the coefficient of relative lighttransmission (K, %) for assessment of sorption capacity of the composite, this capacity provide the slowdown of dielectric losses impregnated dielectrics. Comparison the coefficients of relative transmittance lighttransmission (K) previously aged in the presence of copper transformer oil and after it matures in contact with the test samples showed an increased sorption activity of the composite. So, our researches suggest the feasibility of developing technologies in manufacture dielectrics of new generation dielectrics with improved electric strength, mechanical characteristics and thermal stability.

[1]. Zhuravleva N.M., et al. Patent of Russion Federation 2010, 117599/17 Positive decision of 01.11.2010.

209 THE NEW LOW-TEMPERATURE SYNTHESIS OF FURAN DERIVATIVES FROM CARBOHYDRATE

M.A. Smirnova, V.E. Tarabanko, M.Yu. Chernyak Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia [email protected]

Hexose carbohydrates, like glucose, sucrose and fructose, are known to produce 5-hydroxymetylfurfural (5-HMF) in the acid media. 5-hydroxymethylfurfural (5-HMF), 5-bromomethylfurfural (5-BMF) and 5-chloromethylfurfural (5-CMF) are considered as promising building blocks obtainable from biomass. These substances are versatile intermediate in biofuel chemistry and polymers production [1]. The main problems of 5-HMF synthesis are humic substances formation and rehydration to levulinic acid (LA) in the conversion. Rehydration into LA can be prevented by two methods: to use the high temperature (more 2000C) [2], or to use organic solvents [3]. The effective preparative 5-HMF synthesis requires available and volatile solvent. The 5-halogenmethylfurfural production requires specific halogenation reagents or dry gaseous hydrogen halogenides [4]. In this paper the low-temperature synthesis of 5-HMF in water solutions containing isopropanol, dioxane, sodium hydrosulfate and producing 5-BMF and 5-CMF from hexose carbohydrates in two- phase system are studied. The most applicable solvent is dioxane due to its volatility, stability and absence of by-products in the process. The maximum 5-HMF yield (78 mol. %) is observed at the fructose concentration 0.06 M. The 5-HMF yield from 0.25 M fructose at 200 – 2400C (40 mol. %) [5] is 1.5 time less than in water-dioxane system. Thus the low-temperature synthesis of 5-HMF is more selective in comparison with high-temperature processes. The isopropyl ether of 5-HMF and isopropyl ester of LA are formed in water-isopropanol system. The maximum 5-HMF yield (77 mol. %) is attained at the low fructose concentration and decreased by a factor 1.5 in increasing the substrate concentration up to 0.5 M. The 0.5 M sucrose conversion 0 at 95 C in solution of 3.5 M NaHSO4 gives 16 mol. % 5-HMF without its rehydration to levulinic acid. The advantage of this method is the high purity of product, and it can be crystallized after extraction without additional purification. The new catalytic water-toluene system at the presence of potassium bromide and sulfuric acid was developed for 5-BMF synthesis. The similar two-phase system at the presence of hydrochloric acid was applied for 5-CMF production. The fructose in water-toluene system at presence of potassium bromide gives 70 – 80 mol. % 5-BMF. These product yields are attained only at the dropping of sulphuric acid during experiments. The instantaneous and very fast addition of sulphuric acid results in fructose oligomerization, jelling of reaction mixture and formation of products of polymerization and condensation. Under similar conditions the product yield from 1M sucrose is attained 20 mol. %. The 5-CMF yield is attained 70 mol. % from fructose at the ratio of water and organic phases 1:10. The increasing of phase ratio leads to significant decrease of product yield. The sucrose and glucose give 46 and 16 mol. % of 5-CMF correspondingly.

References: 1. Lichtenthaler F.W. Carb. Res. 1998. P. 69 – 89. 2. Timokhin, B.V.; Baransky, V.A. Russian Chemical Revues. 1999. Vol. 68. P. 80–93. 3. Levitin, B. M. Levulinic Acid. Properties, Production and Applications, Moscow, 1978; P. 4 - 35. 4. Newth F.H., Wiggins L.F. J. Chem. Soc. 1947. P. 396 – 398. 5. Tarabanko V.E. Chernyak, M. Yu., Smirnova M.A. Chemistry for sustainable development. 2006. Vol. 14. P. 53 – 75.

210 BIOLOGICAL PROPERTIES OF CARRAGEENANS-RED ALGAL POLYSACCHARIDES

E.V. Sokolova1, A.O. Barabanova1, L.N. Bogdanovich2, I.M. Yermak1 1 - Pacific Intstitute of Bioorganic Chemistry of FEB RAS 2 - Medical association of FEB RAS [email protected]

Red algal cell walls contain sulphated polysaccharides – carrageenans belonging to food fibers and widely used in the medical and food fields owing to their physicochemical and comprehensive biological properties. Carrageenans present soluble linear sulfated galactans, which backbone based on a repeating disaccharide sequences composed of differing 3-linked β-D-galactopyranose and 4- linked α-D-galactopyranose, which can occur as 3,6-anhydrogalactose. The structure of algal sulfated polysaccharides varies according to algal species, environmental conditions, and life stage of seaweed, and every new one is a novel compound with potential altering biological properties. Biological activities of different types of carrageenans isolated from red seaweeds Gigartinaceae and Tichocarpaceae families collected from the Pacific coast were studied. Antioxidant capacity of – kappa, lambda, kappa/iota, kappa/beta and iks- carrageenans –was assessed by means of in vitro models. The reducing capacity of the investigated carrageenans was not much expressed, and capacity of the commercial polysaccharide samples was negligible. Iks-carrageenan containing three sulphate groups per disaccharide unit and a 3,6-anhydrogalactose unit was among the most effective superoxide anion and nitric oxide scavengers, and the only polysaccharide possessing iron ion chelating capacity. Antioxidant actions of lambda-, iks-, kappa-, kappa/beta- and kappa/iota- carrageenans against reactive oxygen/nitrogen species depend on polysaccharide concentration and such fine structural characteristics as presence of hydrophobic 3,6-anhydrogalactose unit, amount and position of sulphate groups, and an oxidant agent, on which sample antioxidant action is directed. The results indicated that carrageenans possess antioxidant capacity in vitro, and this action notably depends on the structure of the polysaccharide itself than the reducing capacity of the polysaccharides. Anticoagulant and antiaggregant properties of carrageenans (lambda, iks, kappa and kappa/beta) and heparin as a positive control were examined. All the carrageenans caused increase in thrombin time compared to control (PBS) from 125% (kappa/beta-carrageenan) to 150% (lambda- carrageenan), so this kind of activity for carrageenans depended on sulphate contents, but all of them were less active than heparin (up to 235%). Carrageenans were also shown to inhibit aggregation of washed platelets with thrombin or collagen as agonists, and in case of collagen the influence of carrageenans was more expressed resulting in lowering on the average by 80% for carrageenans and 85% for heparin. If activation of washed platelets was performed with ristocetin as a cofactor for a von Willebrand factor, carrageenans elevated agglutination velocity and kappa/beta-carrageenan was the most effective sample, lambda-carrageenan had not any effect on agglutination in that instance. Examined polysaccharides were tested at a concentration of 1 mg/ml in regard to hemolysis of red blood cells, and no significant lysis was observed (less 1%). Anticoagulant and antiaggregant properties continue to be potential one for carrageenans. In vivo influence of carrageenans as food additive (“Carrageenan-DV”) composed from two carrageenan samples was also determined. The aim of that study was directed on the observation of lipid and cholesterol levels, and biomarkers of chronic inflammatory process of patients with coronary heart diseases receiving a favor therapy for a long time. Comparative analysis of those indices before and after application of “Carrageenan-DV” by patients elicited statistically significant reduce in the levels of total cholesterol and low density lipoprotein cholesterol down to normal levels, and not significant movement of high density lipid cholesterol and triacylglycerol. Employment of “Carrageenan-DV” put in significant decrease in markers of chronic inflammation: total level of white blood cells and fibrinogen, and tendency to lower the CRP level. The results of that investigation demonstrated that application of “Carrageenan-DV” as addititious food fiber source during complex therapy of patients with cardio vascular disorders contributed normalization of indices of lipid metabolism and chronic inflammatory process.

211 INTERACTION OF HYDROLYTIC LIGNIN WITH POLYACRYLONITRILE IN DIMETHYL SULFOXIDE-WATER SYSTEM

T.N. Spirina1, E.M. Kulikova1, V.Ju Elokhovsky1, E.N. Popova1, S.M. Krutov2, I.V. Sumersky2 1 - IMC RAS 2 - Saint-Petersburg State Forest Technical Academy [email protected]

An interaction of hydrolytic lignin (HLG) produced by Kirov Hydrolysis Plant with polyacrylonitrile (PAN) in dimethyl sulfoxide (DMSO)-water system in a wide temperature range has been investigated by the methods of reology and thermal analysis. The model experiments show that during a thermal processing of HLG-DMSO a partial dissolving of HLG takes a place, and its maximum conversion is observed at 2000С during 10 hours of the interaction time. A water for increasing a conversion level of HLG and NaOH as activator are used in a concentration range of 30% to 5% correspondingly. A substantial increasing of HLG conversion to an activated system of the solvents attained 70-80% of initial amound of HLG is revealed. The anomalous dependences of yield point, dynamic viscocity of the system and energy of viscous flow activation allowed to define a forming of comples solvato-aggregates of HLG-DMSO-H2O-NaOH and to offer a mechanism of HLG dissolution- destruction following with forming of the low molecular products, according to data [1,2], enclosed by the solvate shells naving a variable composition. An optimum ratio of HLG-DMSO equal to 70:30 when the most reactive intermediate compound supporting the interaction of the complex obtained with a solution of PAN and DMSO is determined. The analysis of the interpolymer interaction products in the activated DMSO-H2O system permitted not only to define a mutual interaction of these high molecular compounds but to show a modifying effect of PAN related to increasing of a general dissolution of HLG in DMSO. A probable mechanism of intermolecular interaction of HLG-DMSO and PAN-DMSO complexes is offered.

Literature 1. Alekseev S.P., Krutov S.M., Zarubin M.Ya. //Izvestia of Saint-Petersburg State Forest- Technical Academy.-1999.-Issue 7(165).-P.65-71. 2. Zarubin M.Ya., Krutov S.M.//Isvestia of Saint-Petersburg State Forest-Technical Academy.- 2008.-Issue 169. P.222-231.

VALUE ADDITION IN THE SUSTAINABLE USE OF COLOMBIAҐS BIODIVERSITY

E. Stashenko, A. Mora, J.R. Martinez, D.C. Duran, B.E. Sanabria Industrial University of Santander, Chemistry, Bucaramanga, Colombia [email protected]

Colombia is a megadiverse country with a wide variety of climates and ecosystems. The richness of its native flora and its relatively few studies, are a motivation to investigate its botanical and eco- agricultural as well as chemical aspects. The secondary metabolites of aromatic plants and their medicinal use are an important field of study. The Colombian equinoxial aromatic flora is formed by introduced Mediterranean plants (rosemary, sage, minths, thyme, basils, fennel, dill), aromatic and condimentary Asian plants (anise, lemongrass, vetiver, ylang-ylang, ginger, cinnamon, curcuma), plants from Africa (geraniums) or Australia (eucalyptus). The systematic study of native aromatic plants began rather recently. Many of these plants belong to the Labiatae, Verbenacea, Piperaceae, Myrtaceae, Laureaceae, and Asteraceae families. The database of Colombian aromatic resources has implied vegetal material recollection, its botanical identification, the use of various extraction techniques (solvent extraction, microwave-assisted hydrodistillation, static and dynamic headspace, solid-phase microextraction), followed by physicochemical and detailed chemical secondary metabolite characterization (GC, GC-MS, HPLC, LC-MS). In the previous 5 years, the

212 study of ca. 800 aromatic plant accessions produced 400 different essential oils, 40% of which showed antibacterial, antifungal, or antiviral activities. Within the guidelines of the biotrade, a new family of final products (aromatizers, insect repellent, massage oil, antibacterial gel, mouth wash, hand soap) has been developed, to take advantage of the biological activity of certain essential oils (Lippia alba, Lippia origanoides, Turnera diffusa, Cymbopogon nardus, Cananga odorata, Eucalyptus globulus, Cymbopogon martinii, other) in a sustainable manner. This is a basis for the development of the value chain of the natural ingredients industry, devoted to the sustainable use of Colombia´s biodiversity.

THE MULTIPLE ROLE OF EXTRACTION AND SEPARATION TECHNIQUES IN THE STUDY OF TROPICAL VEGETAL BIODIVERSITY AND ITS VALUE-ADDED PRODUCTS

E.E. Stashenko, G. Arias, M.P. Cala, C.A. Ruiz, D. Caballero, D.C. Duran, J.R. Martinez Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Biodiversity studies include not only the macroscopic aspects of the large number of plant species, but also their secondary metabolites. To study molecular diversity, intertwined with plant biodiversity, the use of different isolation techniques (steam distillation, hydrodistillation, simultaneous distillation-extraction, supercritical fluid extraction, solid-phase microextraction, solvent extraction), LC, GC, CE, and other separation techniques is necessary for a thorough secondary metabolites description and complex mixture characterization. The circadian rhythm of VOC emission in Sansevieria trifasciata, Brugmansia suaveolens and Cananga odorata flowers is an excellent example of the application of HS-SPME-GC with different detection systems. The search for natural antioxidants, e.g., flavonoids in tropical aromatic plants of the Verbenaceae family, is another illustration of the potential of LC-MS and GC-MS techniques. A deeper level of biodiversity is appreciated in the discovery of plants of the same botanical, but with different secondary metabolite profiles. Chemotype distinction based on the chromatographic characterization of their secondary metabolites is illustrated with the use of GC/MS analysis in the identification of Lippia species (Verbenaceae family) chemotypes. The determination of monoterpenoid enantiomers in these oils is used as an example of another level at which molecular diversity can be scrutinized with chiral separation techniques. The detailed characterization of complex mixtures, such as essential oils, e.g., from Swinglea glutinosa, is possible using comprehensive chromatography (GCxGC-TOFMS).

CHROMATOGRAPHIC ANALYSIS OF POLYPHENOLS OBTAINED FROM LIPPIA AROMATIC PLANTS BY MEANS OF SOLVENT AND SUPERCRITICAL CO2 EXTRACTIONS

E.E. Stashenko, M.P. Cala, J.R. Martinez Center for Chromatography and Mass Spectrometry, Industrial University of Santander, Bucaramanga, Colombia [email protected]

Supercritical fluid (CO2) extraction (SFE) was compared with solvent (water-methanol) extraction for the isolation of flavonoids from stems and leaves of 9 different Lippia (Verbenaceae family) aromatic species. Vegetal material from three Lippia origanoides chemotypes (carvacrol-, thymol-, and phellandrene-rich chemotypes), two Lippia alba chemotypes (carvone- and citral-rich chemotypes), Lippia citriodora, Lippia americana, Lippia graveolens, and Lippia micromera, were obtained from an experimental garden. Extracts were obtained with and without previous hydrolysis in order to detect the potential existence of the glycosidic forms of the extracted flavonoids. An HPLC (Agilent Technologies 1200, DAD, Zorbax C-18 column) method was developed for the simultaneous determination of 11 polyphenols in these extracts. SFE isolated solely pinocembrin and narigenin from the three L. origanoides chemotypes, with yields that varied around 20% with

213 the hydrolysis step. Solvent extracts had a more varied composition which additionally included apigenin, quercetin and luteolin. Solvent extraction afforded higher overall flavonoid yields from all species than SFE. Confirmation of flavonoid identifications were made by LC-TOF-MS.

ETHANOL PRODUCTION FROM ENZYMATICALLY PRETREATED RICE STRAW BY THERMOTOLERANT YEAST CELLS

N. Stepanov1, E. Efremenko1, S. Varfolomeev1, T. Tran Dinh2, T. Nguyen Dinh2, S. Do Trung2, T. Nguyen Ngoc2, D. Nguyen Thi2 1 - N.M. Emanuel Institute of Biochemical physics, RAS, Moscow, Russia 2 - Institute of chemistry, VAST, Hanoi, Vet Nam [email protected]

Cellulose present in plant biomass is a rich source of renewable raw material which can be converted into glucose under action of cellulases. Glucose can be used for ethanol production as biofuel. It was shown, that usage of complex with cellulases possessing different hydrolytic activity is the most effective way, providing deep destruction of raw material components with high yield of monosaccharides. The rice straw was used as the main object of investigation in this work. The hydrolysis was carried out at рН 5.0, 50оС for 48 h. In this process the cellulose-containing complex secreted by immobilized cells of filamentous fungi Aspergillus terreus was used. Twelve yeast strains were screened for glucose fermentation in rice hydrolyzates over the temperature of 45oC. All cells were immobilized into polyvinyl alcohol cryogel.

Тable 1.Ethanol concentration obtained after 24 h of fermentation of rice straw

Strain Ethaol, g/l Yield, % Kluyveromyces marxianus Y-18 4,55 44,5 Cryptococcus albidus Y -19 7,17 70,2 Candida maltosa Y -194 5,15 50,4 Trichosporon beigelii Y -253 3,64 35,6 Torulopsis sp. Y -276 3,64 35,6 Schizosaccharomyces pombe Y-285 3,64 35,6 Candida maltosa Y -317 3,64 35,6 Candida tropicalis Y -451 3,64 35,6 Hansenula polymorpha Y- 1345 4,05 39,6 Candida sp 7158. 9,50 93,0 Sasccharomyces cerevisiae T 2 7,37 72,1 S. cerevisiae V 7028 9,30 91,0

High efficiency of conversion of enzymatic hydrolyzates of rice straw to ethanol (up to 90 % of yield of last product) were shown by 2 strains of S. cerevisiae T2 and Candida sp 7058.

214 SIMULTANEOUS SACCHARIFICATION AND FERMENTATION PROCESS OF ETHANOL PRODUCTION FROM PRETREATED WITH IONIC LIQUIDS CELLULOSIC MATERIALS

N. Stepanov1, D. Gudkov2, O. Maslova2, E. Efremenko1, S. Varfolomeev1 1 - The N.M. Emanuel Institute of Biochemical physics, RAS, Moscow, Russia, The M.V. Lomonosov Moscow State University, Moscow, Russia 2 - The M.V. Lomonosov Moscow State University, Moscow, Russia [email protected]

The use of renewable biomass to produce biofuels is one of the main directions of development of modern energetic industry. The focus of the technologies for producing biofuels today is attend to finding the most effective ways of organizing production - unification process steps, involving preprocessing of raw materials and obtaining monosaccharides, as well as the stage of their conversion to ethanol as main product. The process of simultaneous saccharification and fermentation (SSF) of raw materials allows to combine the enzymatic hydrolysis of raw material with the conversion of obtained sugars to ethanol in the same reactor at the same time. In such biocatalytic system achieved overall shift of the chemical balance toward the formation of the final product, thus increasing the degree of hydrolysis of the substrate and increase the productivity of the whole process. To provide complete enzymatic hydrolysis of cellulose-containing raw materials, their pretreatment with salts of organic or inorganic acids with organic bases (ionic liquids), providing the amorphization of the crystalline part of cellulose molecules, was made. The procedure enabled obtaining of substrate characterizing by more accessibility for hydrolysis. The literature data showed that ionic liquids are toxic for many microorganisms. To increase their resistance, the preference was given to the use of cells in immobilized form. Thus, the investigation of ethanol production from cellulose-containing materials pretreated by ionic liquids during SSF process under action of yeast cells Saccharomyces cerevisiae immobilized into polyvinyl alcohol cryogel was a main target of with work. The complex of cellulases (endo- and exoglucanases, -glucosidase) produced by immobilized cells of filamentous fungi Aspergillus terreus was applied in this research. The wheat straw pretreated with ionic liquid such as 1-allyl-3-methylimidazolium chloride was used as a substrate. It was revealed, that metabolic activity of the immobilized cells did not reduce when residual concentrations of ionic liquid in fermented media was lower then 5%. The yield of ethanol was 90% from theoretical level, and it was 10% higher as compared to result obtained in process with separate but consecutive saccahrification and fermentation of wheat straw.

CELLULOSE CONTAINING MATERIALS AS A SOURCE FOR BUTANOL PRODUCTION BY IMMOBILIZED CELLS CLOSTRIDIUM ACETOBUTYLICUM

N. Stepanov, O. Senko, O. Maslova, E. Efremenko, S. Varfolomeev The M.V. Lomonosov Moscow State University, Moscow, Russia [email protected]

At present time high enough oil prices, depletion of fossil fuels and environmental problems associated with increasing volume of agricultural and wood wastes provide an increasing interest to alternative types of fuels such as biobutanol, which is the main product formed during the acetone- butanol-ethanol (ABE) fermentation catalyzed by bacteria Clostridium acetobutylicum. Production of butanol from renewable non-food sources such as cellulose agricultural and wood wastes is a perspective process. To realize this process a heterogeneous biocatalyst on a base of bacterial cells C. acetobutylicum immobilized into polyvinyl alcohol was developed.

215 Immobilization of bacterial cells can reduce the inhibitory effect of high concentrations of target products on the bacterial cells, enables continuous operation of immobilized cells and simplifies separation of cultural medium containing products of ABE-fermentation. The various hydrolyzed pine samples were used as substrates in this work for biobutanol production with immobilized cells. For comparison, a control ABE-fermentation was carried out using free cells and same pine hydrolizates. The ABE process with the participation of the immobilized biocatalyst was performed in a mini reactor in which the ratio between volumes of liquid medium and gas phase was 2.0. Analysis of the cultural liquid after 72 h of the action of the biocatalyst based on immobilized Clostridium acetobutylicum cells showed that the medium contained 0.9 g/l acetone, 2.5 g/l butanol, 0.2 g/l ethanol. The concentration of butanol accumulated in the cultural medium with immobilized cells for same period of time was 2.5 times higher than that in the medium with free cells. Thus, it was found that immobilized cells C. acetobutyricum can be efficiently used for production of commercially important product such as butanol from cellulose containing agricultural wastes.

STRUCTURE AND PROPERTIES OF RAPESEED OIL AND DIETHANOLAMINE POLYOL AND POLYURETHANE ON THEIR BASE

U. Stirna, A. Fridrihsone, M. Misane, B. Lazdina, D. Vilsone Latvan State Institute of Wood Chemistry, Riga, Latvia [email protected]

Natural oil-derived polyols have been considered as an alternative for petroleum-based polyols for making polyurethane (PU). To obtain polyurethane materials from vegetable oil, hydroxyl groups are necessary for the reactions with isocyanate groups that result in urethane linkages. Unfortunately, there are no hydroxyl groups in rapeseed oil (RO) triacylglycerol structures of saturated and unsaturated fatty acids; hence, there is a need to chemically introduce hydroxyl groups onto RO triacylglycerols. RO polyols were synthesized by reacting vegetable oil with diethanolamine (DEA) at a molar ratio of 1:2.9 M at three temperatures – 130º C, 140º C and 160º C. At these temperatures, NH groups’ conversion degree reached 77%, 74% and 72%, respectively. This is explained by the fact that both trans-amidization and trans-esterification processes progressed in parallel during the RO diethanolamide synthesis. These results indicate that there is equilibrium between higher fatty acid diethanolamides and amine group containing compounds. The course of RO amidization was investigated also using FTIR spectroscopy data. The relative intensity of C=O groups decreases at -1 -1 1739 cm / 2923 cm , which is characteristic of H-free ester groups, while the C=O absorption intensity at 1620 cm1/ 2923 cm-1, characteristic of tertiary amide, increases. The results confirm that the NH group conversion degree reaches 77 % for the synthesis at 130º C. The NH group conversion degree is expected to be similar also for the synthesis at 140º C and 160º C. The structure of polyols was analyzed using 1H-NMR and 13C-NMR spectra. The NH number of the obtained diethanolamides decreases, when they are stored at room temperature for a long time. For RO diethanolamides, the NH number decreases from 29 to 8 mg KOH/g during a 6-month period. The decreasing of the NH number indicated the equilibrium between diethanolamide and amine group containing compounds. After storage, RO diethanolamide was reheated to obtain a variation in NH number values. The results show that the NH number increases to 22.26 and 31 mg KOH/g at 130º C, 140º C and 160º C, respectively. The Hildebrand solubility parameter δ was calculated by the Fedors’ group contribution method. For RO, δ is 8.94 (cal/cm3)1/2. Also the solubility parameter of unsaturated and saturated fatty acid radicals, attached to glycerol (the vertical carbon chain), was calculated. PU films were obtained from RO polyol, which was synthesized from RO/DEA, increasing the DEA molar ratio 2.1 to 3, and hexamethylene diisocyanate HDI. The results show that, with increasing molar ratio, the PU films’ tensile strength σt, Young’s modulus (E) and glass transition temperature (Tg) increase, while their elongation at break decreases. 216 The obtained PU can be characterized as polymers with a dimensional structure, containing C12-C22 side chains 30.6 to 35.7% by weight, where C12-C22 are unsaturated and saturated fatty acid radicals.

DIMINISHING CALCIUM-INDUCED AGGREGATION OF COLLOIDAL EMULSIONS IN TMP SUSPENSIONS BY ADDITION OF GALACTOGLUCOMANNANS

A. Strand, A. Sundberg, L. Vahasalo Abo Akademi University, Process Chemistry Centre, c/o Laboratory of Wood and Paper Chemistry, Turku, Finland [email protected]

Steric stabilisation of an oil-in-water emulsion by water-soluble galactoglucomannans (GGM) against calcium-induced aggregation was assessed. The emulsion used was composed of lipophilic extractives from Norway spruce, i.e. a mixture of resin acids, fatty acids, steryl esters and triglycerides. The colloidal stability of the emulsion was determined as such as well as in the presence of peroxide-bleached thermomechanical pulp (p-bl. TMP) towards CaCl2. The experiments were performed with and without added GGM at pH 5 and pH 8. The main goal of this study was to determine if steric stabilisation of oil-in-water emulsions by GGM against electrolyte- induced aggregation is dependent on pH, and affected by the presence of fibres. Emulsions were mixed at different consistencies of p-bl. TMP and 0-10 mM CaCl2 was added. The suspensions were centrifuged to remove fibres, fines and aggregates of colloidal droplets. The concentration of extractives was determined in the supernatant by gas chromatographic analysis, and was compared to emulsions without added CaCl2, which had been subjected to the same experimental procedure. The emulsion had low affinity to p-bl. TMP in the absence of CaCl2. At pH 5, even low CaCl2- concentrations caused extensive aggregation of the emulsion in suspensions of p-bl. TMP. At pH 8, a higher concentration of CaCl2 was required for aggregation of the emulsion than at pH 5. The mechanisms behind the loss of colloidal stability were most likely aggregation of colloidal droplets, due to compression of their electrostatic double layer, followed by retention of the aggregates by wood fibres and fines. The steric stabilisation by GGM was close to complete against 0-10 mM of CaCl2, at both pH 5 and pH 8, in absence of p-bl. TMP. When GGM was added, 51% of the emulsion was stable against 3 mM of CaCl2 in a suspension of 1% p-bl. TMP at pH 5, while the corresponding value without added GGM was only 2%. The results indicated that GGM increased the colloidal stability of the emulsion against calcium-induced aggregation, also in the presence of p-bl. TMP. About 83% of the emulsion was stable in a suspension of 0.25% p-bl. TMP against 3 mM of CaCl2 at pH 5, while 51% of the emulsion was stable in a suspension of 1% p-bl. TMP; hence the consistency of p-bl. TMP was an important factor behind the aggregation of the colloidal droplets in the presence of GGM. The results showed that oil-in-water emulsions can be stabilised against calcium-induced aggregation by water-soluble GGM, both at pH 5 and pH 8. The added GGM stabilised the emulsion against electrolyte-induced aggregation also in the presence of fibre surfaces, although not completely. These results imply that GGM could possibly function as a stabiliser of emulsions in a wide variety of applications, at both acidic and slightly alkaline conditions, in the absence or presence of fibres or other particles.

217 THE METHOD OF CARBON NANOTUBES OBTAINING FROM PRODUCTS OF PINE SAWDUST PYROLYSIS

D.A. Strizhakov, A.P. Solntsev, V.E. Agabekov, N.I. Sazon, V.I. Korbut The Institute of new materials chemistry of NAS of Belarus, Minsk, Belarus [email protected]

The method of gas-phase chemical deposition is the most widespread way of carbon nanotubes obtaining (CNT). Initial raw materials for CNT synthesis are hydrocarbons (methane, propane, propylene, benzene). Belarus is a country which is not possessing considerable fuel and energy resources. In this connection, in the given communication possibility of application the synthesis- gas received by high-temperature oxidation of a wood biomass by oxygen of air as carboncontaining source gases was shown. It is established by method of a gas chromatography, that the basic carbon-containing component of synthesis-gas received at temperature of 800 оС and the expense of air of 0,2 l/mines is carbon monoxide (31 wt. %..). Methane and carbon dioxide also contains in a small amounts (3,5 wt. %) (1,2 wt.. %) respectively. о Disproportionation of synthesis-gas was realized at temperature of 600 С on the Ni/MgO/Y2O3 catalyst received by thermal decomposition of nickel nitrate, magnesium nitrate, ittrium oxide and о glicine at 650 С. The proposed method allows to receive multilayered carbon nanotubes (MCNT) with external diameters from 18 to 55 nanometers. The length of separate tubes reaches 2 microns. For the MWCNTs obtained is characteristic constant diameter of the tube along its entire length, suggesting the stability of conditions for its growth. Obviously, the diameter of the tubes is determined by the characteristic size of the active crystallization centers of the catalyst (Ni/MgO/Y2O3), as evidenced by located at the ends of the tubes in Fig. 1a dark, as in Fig. 1b bright rounded formations (particles of nickel).

Figure. 1 – (а) TEM and (b) SEM microphotographs of MCNT obtained.

SORPTION OF METAL IONS TO SPRUCE BARK

P. Su1, K. Granholm1, A. Pranovich2, L. Harju1, B. Holmbom2, A. Ivaska1 1 - Laboratory of Analytical Chemistry, Process Chemistry Centre, Abo Akademi University, Turku, Abo, Finland 2 - Laboratory of Wood and Paper Chemistry, Process Chemistry Centre, Abo Akademi University, Turku, Abo, Finland [email protected]

In this study spruce is used as a material for removal of metal ions from aqueous solution. The sorption-desorption of metal ions to bark was studied with four different metal ion mixtures by using a column chromatographic method. Inner bark and outer bark of spruce were studied

218 separately. The equilibrium times of metal sorption to bark were investigated in a batch experiment. It was found that the different metal ions exhibit different sorption affinities to bark. The sorption capacity of bark was found to depend on what metal ions were present in the mixtures studied. This was due to competition of the different metal ions to the binding sites in bark. The mechanism of metal sorption to bark is the ion-exchange reaction, mainly by the complexation of metal ions with the binding sites. The affinity of metal ions to spruce bark showed the following order: Fe3+ > Pb2+ > Cd2+ > Zn2+ > Ni2+ > Ca2+ > Ba2+ > Sr2+ > Mn2+ > Mg2+ >> K+ ≈ Na+ ≈ Li+ In our previous papers, sorption of metal ions to different types of kraft pulp and wood particles has been studied. Similar affinity orders were obtained for all types of materials applied, except for Ca ions. Calcium ions show stronger sorption affinity than barium ions to bark. The affinity order for calcium and barium ions to pulp and wood particles is reverse. The sorption of metal ions is mainly attributed to the functional groups, e.g. carboxyl and phenolic hydroxyl groups, in bark. Their concentrations and protonation constants were determined by a potentiometric acid-base titration. It was found the concentration of phenolic hydroxyl groups was higher in bark than that in pulp and wood particles.

COMPOSITION AND BINDING PROPERTIES OF ACETIC ACID LIGNINS FROM WHEAT STRAW

I.G. Sudakova1, N.V. Garyntseva1, A.V. Petrov1, A. Celzard2, B.N. Kuznetsov1 1 - Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia 2 - Nansy University, ENSTIB, Epinol, France [email protected]

At present the development of modern ecology safe composite materials on the basis of available and inexpensive binding agents with low toxicity is a very important task. Some example of the use for producing composite materials with improved characteristics the non-toxic binding agents on the base of wastes of plant raw materials processing are available in literature [1, 2]. The most large-tonnage waste materials of pulp and hydrolysis plants are industrial lignins. Oxidative delignification of lignocellulosic raw materials (wood, straw, ets.) in the medium “acetic acid – hydrogen peroxide – water – sulfuric acid catalyst” makes possible to obtain high-quality cellulosic products [1]. Acetic acid lignins produced by oxidative delignification have lower molecular mass and higher reaction ability as compared to hydrolytic lignin. In this study the composition and binding properties of acetic acid lignins obtained at oxidative delignification of different types of plant biomass (softwood, hard wood, wheat straw) were compared. Air dry sawdust (fraction < 2,5 mm) of different types of wood species: larch wood (Larix sibirica), abies wood (Abies sibirica), aspen wood (Populus tremula), birch wood (Betula pendula) and wheat straw were used as the initial raw materials. Acetic acid lignins obtained from wood and wheat straw are amorphous fine-dispersed powders which colour varies from light brown to dark brown. They have melting point 175–180 °C and low solubility in water and organic solvents. Their yields from initial raw material are near 9.0–9.5 % wt. Some data about chemical composition of acetic acid lignins are presented in table. Table. Elemental composition of acetic acid lignins and concentration of oxygen-containing functional groups (% wt.) Lignin С H О -COOH -С=О -ОНphen. -ОНaliph. Abies 61.2 5.1 33.0 3.2 3.8 2.6 0.12 Aspen 62.7 5.4 31.4 2.3 3.2 3.4 2.1 Birch 62.8 5.1 31.9 2.4 4.3 3.0 0.2 Wheat straw 61.8 5.4 29.7 2.03 1.7 2.9 1.6 According to obtained results the acetic acid lignins have high concentration of reactive oxygen- containing functional groups. It was suggested to use acetic acid lignins as low-toxic binding agents

219 for production of wood panel materials with good strength characteristics. The influence of lignin nature, its content in lignin/wood blend and conditions of pressing on the bending strength and water-resistance of obtained wood panel materials was studied. Optimal technological parameters for manufacture of wood panel materials were found; lignin content near 40 % wt., pressing temperature 160–165 °C, pressure 10–13 MPa. Chemical modification of blend lignin/wood with 0.5 % solution of sulfuric acid at 85 °C before pressing increases by 2.5–3 times the water resistance of obtained wood panel materials. Results of the accomplished study show that acetic acid lignin – side products of cellulose obtaining by oxidative delignification of wood and straw can be used as low-toxic binding agents in production of wood panel materials. 1. Kuznetsov B. N., Taraban’ko V. E., Kuznetsova S. A. New catalytic methods for obtaining cellulose and other chemical products from vegetable biomass. Kinetics and Catalysis. 2008. V. 49. N4. P. 517-526.

MOLECULAR SPECTRA OF LIQUORS AS METHOD OF STUDYING DELIGNIFICATION PROCESS

D.А. Sukhov1, О.Yu. Derkacheva1, H. Pakkanen2, R. Alen2 1 - St.Petersburg State Technological University of Plant Polymers 2 - University of Jyvaskyla [email protected]

In the cooking process lignin and other components go into cook liquor from wood chips. Composition of cook liquor dependes on pulping condition and can be source of value information about delignification process course and about state of pulps [1]. Due to some objective difficulties, pulp liquors studies by FTIR-spectroscopy were not very intense. Nevertheless in the articles [2-4] were revealed good correlations between intensities of absorbance bands of alkali lignins at 1118 and 1487 cm-1 and lignin concentration in solution and in pulp. The aim of the work was to get and to analyse IR-spectra of dry samples of aspen kraft cook liquors. Value of Н-factor for these laboratory cooks changed in limits 4–1010, minimal value of Kappa number for final pulp was 13.5. Feature of this work was the use of hardwood lignins spectral model [5] to identify the absorption bands of alkali lignin from complex spectra of liquors. As result of analysis of liqours molecular spectra there was established that on the fast dissolving lignin stage (at H-factor value range lower 200) the lignin absorbance bands changed with different rate. As an example, the band intensity of with maximum at 1498 cm-1 increased in 9 times, the bands at 1229 и 1117 cm-1 increased in 5.5 and 3.3 times, respectively. At H-factor value above 200, intensities of these bands changed a little. The correlations were revealed between intensities of some lignin bands in liqours spectra and contain of residual lignin in the pulps evaluated after our spectral data and Kappa number ones. Spectral liqour parameters had good relationships with value of pulp yield. Mathematical treatment of the obtained spectra allowed to discuss the absorbance bands of other liqour non-lignin components. So in the spectra of liquors isolated on the initial cook stage at the H- factor values lower than 200, strong intensity changes were found for the bands with maxima at 783 and 1335 cm-1, connected with formic acid presence, and two bands with maxima at 652 and 625 cm-1 which are appeared as result of vibrations of molecules of acetic acid, and sodium carbonate band at 881 cm-1. It is worth noting in the delignification condition at the H-factor values above 200, the intensities of these bands changed only slightly. The analysis of molecular spectra of dried liqours allowed to reveal two stage of delignification process: first stage – with intensive changes of cook liqour spectral characteristics and next stage - with insignificant changes of intensities discussed above bands. 1. Nepenin Yu.N. Cellulose technology, 2nd Rus. Ed., v. 2. Production of kraft cellulose, М., 1990. 2. Patt R., Faix O., Welker U. Das Papier 41: V7 (1987) 3. Faix O., Patt R., Beinhoff O. Das Papier 41: 657(1987)

220 4. Michell A.J. Kappa number determination in kraft pulping by FTIR spectroscopic measurements on spent liquors. April 1990 Tappi Journal pp.235-236. 5. Sukhov D.А., Derkacheva O.Yu., Fedorov A.V. Stability of spectral models of lignin and carbohydrates in lignocellulosics. Proceedings of international conference “Physic and chemistry of lignin”, – Archangelsk, 3-6 July 2005. p 177-180.

THE COMPOSITION OF CO2-EXTRACT OF ECHINOPS RITRO

Ye.M. Suleimen1, S. Machmudah2, M.Yu. Ishmuratova3, M. Sasaki2, S.B. Rahmadieva1, M. Goto2 1 - L.N. Gumilyov Eurasian National University, Astana, Kazakhstan 2 - Kumamoto University, Japan 3 - Zhezkazgan Botanic Garden, Kazakhstan [email protected]

Alkaloids [1-2], sesquiterpene acids and triterpenes [3], flavanoids [4-6], n-alkanes [7] and lipids [8] were isolated from Echinops ritro (Asteraceae) before. Crude extracts and thiophenes of E. ritro have termiticidal activity against Coptotermes formosanus [9]. The dichloromethane extract of the radix of E. ritro and thiophenes from it has antifungal activities using a broth microdilution assay against plant pathogens Colletotrichum acutatum, C. fragariae, C. gloeosporioides, Botrytis cinerea, Fusarium oxysporum, Phomopsis viticola, and P. obscurans [10]. The essential oils from the fresh inflorescences of E. ritro were analyzed by GC and GC/MS. The oil of E. ritro showed (E)-2-hexenal (21,4%), 1,8-cineole (16,3%) and p-cymene (12,2%) as the major constituents [11]. In our study we investigated by GC/MS method a composition of CO2-extract of E. ritro, which was collected in Kazakhstan, Pavlodar region., near Toraigyr lake (Bayanauyl) in the beginning of August, 2007 (flowering). Supercritical Fluid Extraction (SCFE) parameters: Extraction was carried out at a pressure of 15 МPa, flow rate of CO2 - 3 ml/min and temperature of extractor - 40 ºС. The yield of extract is 1,01%. The obtained fractions were dissolved in 1 ml of ethanol, cooled overnight at -20 ºС and analyzed by GC/MS. GC/MS: System: Hewlett Packard GCD system. Column: an Innowax FSC (60 m x 0.25 mm id.). Temperatures: Injection port: 250 ˚C. Column: at 60 ˚C for 10 min and programmed to 220 ˚C at a rate of 4 ˚C/min, and then held isothermal for 10 min. Carrier gas: Helium, with 1mL/min. Split Ratio: 50 : 1. Electron Energy: 70 eV Mass-range: m/z 35-425. Library: Wiley GC/MS Library. It has been found, that the tetradecanoic acid (32.4%), phytone (7.3%), hexadecanoic acid methyl ester (4.5%) and diisobutyl phthalate (2,9%) were found as main components.

The authors thank the Matsumae International Foundation for financial support.

1. Savin K., Tucakov J., Lukic P., Acta Pharmaceutica Jugoslavica (1974), 4(2), 123-8. 2. Doepke W., Fritsch G., Pharmazie (1969), 24(12), 782. 3. Ulubelen A., Kurucu S., Fitoterapia (1991), 62(3), 280. 4. Mahadyan F., Qadsi M.B. Daneshkade-ye Darusazi (1977), (March), 31-4. 5. Chevrier M., Raynaud J., Bull. des Travaux de la Societe de Pharm.de Lyon (1973), 17(2), 72-8. 6. Chevrier M., Fitoterapia (1976), 47(3), 115-17. 7. Chevrier M., Abdel G.M., Bull. des Travaux de la Societe de Pharm. de Lyon (1974), 18(2), 58- 65. 8. Chevrier M., Abdel G.M., Raynaud J., Pharmazie (1975), 30(6), 389-90. 9. Tellez M.R., Kobaisy M., Osbrink W.L., et all, Phytotoxic, antifungal, antialgal, and antiinsect activity of components from selected plants of Kazakhstan and Greece (2004), AGFD-018. 10. Fokialakis N., Cantrell C.L., et all, J. Agric.and Food Chem. (2006), 54(5), 1651-1655. 11. Papadopoulou P., Couladis M., Tzakou O., J. Ess. Oil Res. (2006), 18(3), 242-243.

221 ENERGY-DISPERSIVE XRF ANALYSIS OF THE HYDROLYSIS LIGNINS

I.V. Sumersky1, A.S. Zemlianikina2, I.V. Gribkov1, M.M. Ravizkiy1, Ju.N. Sazanov3, S.M. Krutov1, M.Ja Zarubin1 1 - Saint-Petersburg State Forest Technical Academy 2 - "Analit" 3 - IMC RAS [email protected]

In this work results of a study of elemental composition, located in the dumps Hydrolysis Plant in Archangel -city using energy-dispersive XRF are represented. The samples for the investigation were taken from different levels of industrial damp area of Hydrolysis Plant in Archangelsk (one of them from the suface of the bulk of the dump, the others – from the depth 0.5 m -1.5 m). Elementary of the samples were mesured with EDX-800HS (Shimadzu). Elementary of hydrolytic lignin in the range of its depth are presented in the Table 1. The date were obtained for the samples of hydrolytic lignin taken from the surface and upper layers of the bulk in the bulk of industrial dump (sample №1, Table 1) and from the different depth – till 0.5 m (sample 2, Table 1) and till 1.5 m ( sample №3, Table 1).

Table 1. Elementary of hydrolytic lignin from different levels of the bulk in industrial dupm area of Hydrolytic Plant in Archangelsk of Russian Federation. Yield, % Composition Sample №1 Sample №2 Sample №3 SO3 9,35 18,35 3,69 Fe2O3 2,95 2,59 3,40 K2O 0,71 0,27 0,77 CaO 6,56 8,51 5,60 TiO2 0,35 0,58 0,89 CuO 0,28 0,19 0,17 SiO2 14,80 4,46 20,46

The samples of hydrolytic lignin from the depth (~1 m. and more deeper) comprised less amount of the sulphur than samples from the upper levels (from the suface till ~1 m.). Probably, hydrolytic lignin in the bulk of the industrial dump lose sulphuric acid under weather condition. The changing in amount of others substences are nearly the same in all levels. The contents of iron, titan, potassium change in negligible quantity in different levels. Their amounts slightly increse in the depth. The calcium is destributed similar to the sulphur (the most amount in the samples from the depth about 0.5 m, in the deeper levels its amount decreeses), but changing of the calcium in content is negligble. Therefore, the investigation confirmes that the method can be applied for investigation of elementary of hydrolytic lignin from industrial digester. The changing in amount of S, Fe, Ca depends from depth of storage of hudrolytic lignin in the bulk of the industrial dump.

Reference 1. Materials of VI th Russia conference on XRF analysis. On October, 5-10th, Krasnodar, 2008. 2. http://www.bruker.ru 3. Lomako I.D., etc. J. of Applied Spectroscopy, 2000. 4. Barilo S.N., etc. Superconductivity: physics, chemistry, technics, 1991г. 5. Shadrov V. G, etc. the Surface, 1998г.

222 CONTROLLING SOLUBILITY OF RESIN AND FATTY ACIDS IN WATER BY ADJUSTING PH AND ELECTROLYTE CONCENTRATION

A.C. Sundberg, A. Strand, L. Vahasalo, D. Macneil, B. Holmbom Abo Akademi University, Process Chemistry Centre, c/o Laboratory of Wood and Paper Chemistry, Turku, Abo, Finland [email protected]

The solubility of resin and fatty acids (RFAs) in water, i.e. the phase distribution between the water phase and the colloidal or aggregated phase, is very dependent on the structure of the RFAs, pH and the electrolyte concentration. The solubility of the RFAs is essential for possible isolation/fractionation, efficient pitch control in papermaking, pulp washing processes, and the removal of pitch from chips prior to mechanical pulping. The main goal of this work was to determine the solubility of different resin and fatty acids as a function of pH and electrolytes. An emulsion of wood pitch in water was prepared so as to have similar properties as the pitch found in process water at a mechanical pulp mill. The pH was adjusted (3-11) and the emulsion was heated to 50°C. 10 ml of the emulsion was filtered through a nylon syringe filter with pore openings of 0.2 μm. The concentration of the RFAs in the filtrate was determined by gas chromatography and compared to the concentration in the original pitch emulsion. The electrolyte concentration was also adjusted to 10 and 30 mM NaCl, or to 1 and 10 mM CaCl2 prior to the tests. At pH 3 or below, all RFAs were attached to the colloidal pitch and no RFAs were found in the water phase. When increasing the pH, the RFAs were gradually dissociated and released from the colloidal droplets. In this paper, we use the term pKlw for the pH at which 50% of the component was found in the lipophilic, colloidal phase (l), and 50% was in the water phase (w). The rate of dissolution from the colloidal phase to the water phase and vice versa was very fast after changes in pH. The resin acids were released at a lower pH than the fatty acids. Dehydroabietic acid was soluble in water at the lowest pH of all RFAs, with a pKlw of about 5.3. This was most probably due to the aromatic ring in dehydroabietic acid, which is a strong electron-withdrawing group and unique for the resin acids studied. No significant difference was seen between the other resin acids: their pKlw- values were all between 6.7-7.2. The phase distribution of fatty acids was very dependent on chain length, number of double bonds, and composition of the RFAs in the emulsion. A shorter chain length and more double bonds decreased the pKlw. The pKlw of oleic acid was 9.5, linoleic acid 8.2 and pinolenic acid 7.3. Only very few saturated fatty acids, those with 20 or more carbon atoms, were found in the water phase even at pH 11. + 2+ Addition of Na or Ca increased the pKlw-values of all RFAs. Resin acids and especially fatty acids formed insoluble aggregates in the presence of Ca2+, and were not dissolved even at pH 11. A process water containing pitch is a complex mixture of many components. By carefully controlling the pH and electrolyte concentration e.g. during filtration, isolation/fractionation of individual RFAs might be possible. All RFAs are in the colloidal phase at pH 3, implying that water-soluble components (polysaccharides, salt etc.) then could be removed by filtration. Dehydroabietic acid is dissolved at the lowest pH of all studied pitch components and could be isolated from a pitch emulsion at pH 5, especially after addition of Ca2+. Control of pH is also important during washing and pitch control. Resin acids and unsaturated, short chain fatty acids are more efficiently removed from pulp or chips at neutral or alkaline than at acidic conditions. After pulp washing at alkaline conditions, the pH should be adjusted back to 5 and fixation aids added for efficient pitch control. Furthermore, mixtures of fatty and resin acids are also efficient surface- active agents, even in hard, Ca2+-rich waters, and can be used as detergents, emulsifiers and flotation agents.

223 THE COLZA OIL BASED BIOFUEL DEVELOPMENT

E.D. Tanygina1, N.S. Lipatova2, I.V. Tchemerkin1 1 - Tambov State University named after G.R. Derzhavin 2 - Tambov State Technical University [email protected]

At the present time the alternative energy sources research is the urgent problem nearly all over the world. One of the solutions is the colza oil and methanol based biofuel synthesis. The latter is rather toxic and the special leave for work is required, what makes use of methanol difficult. The methanol substitution for the ethanol by the biofuel synthesis will make it more available and environmentally safe. The objects of the following study are the colza oil and ethanol based biofuel producing in presence of different catalysts research, the optimum set of the the colza oil and ethanol based biofuel synthesis conditions (temperature, the catalyst’s character and content, reaction mix composition etc.) estimation, the colza oil and ethanol based biofuel quantitative composition and its physicochemical characteristics study, such as ash content, coking, limit of inflammability. The study singularity lies along the biofuel synthesis raw produce availability to the direct producers e.g. farmers, the usable catalysts character, the processing method conditions. The processing method is based on the fine organic synthesis of the compound based on the mono-, di- and triglycerides. The final product quality depends on the homogeneous distribution of the ethanol and catalyst to the vegetable oil volume, beforehand flooded to the apparatus. Therefore the basic requirements are the reactants’ homogenization and the liquid reaction mix temperature invariability in the course of time in the apparatus volume.

The biofuel synthesis laboratory plant The diesel fuel physicochemical characteristics (biofuel’s analog)

Coking, % - 0,20

Ash content, % - 0,01

Limit of inflammability, °С - 62

The synthesis were carried out by the mix (volumetric content: refined colza oil : ethanol, 3 : 1) hashing within 3 hours at 60 оС in presence of different catalysts. The ethanol were dehydrated beforehand with the zeolite. At the synthesis finishing the reaction mix was settled down within twenty-four hours for the layers differentiation. The upper layer was removed, rinsed out with water for ethanol and glycerine disposal. Next the biofuel was dried for water disposal. Then the biofuel physicochemical characteristics were estimated. It is shown, that the biofuel’s coking and ash content correspond to the diesel fuel’s state standard specifications. Without rinsing out with water the biofuel samples were characterized by low limit of inflammability about 25 °С.

PROCESSING OF HARDWOOD AND SOFTWOOD INTO THE FINE CHEMICALS

V.E. Tarabanko, K.L. Kaygorodov Institute of Chemistry and Chemical Technology, SB RAS, Krasnoyarsk, Russia [email protected]

Main wood components, lignin and cellulose, is known to be processed into the fine chemicals. They are levulinic (4-ketopentanoic) acid and 5-hydroxymethylfurfural, obtained by the acid- catalyzed cellulose conversion, vanillin (4-hydroxy-3-methoxybenzaldehyde) and syringaldehyde

224 (4-hydroxy-3,5-dimethoxybenzaldehyde), which are produced by the catalytic oxidation of softwood and hardwood lignins, correspondingly. The schemes of wood treatment into these products are suggested [1, 2]. They include the catalytic oxidation of wood lignins into the aldehydes followed by the hydrolysis of cellulose residue into levulinic acid. The aim of this report is to discuss the scientific basics of technology of producing the above-listed products from wood or wastes of wood processing. This problem was studied during a half of century, but many questions in this field do not have satisfied solutions. The questions are listed below: 1. What kinds of raw materials are the most efficient to produce the products listed? 2. Are there any possibilities to decrease the alkali consumption in a step of lignin oxidation into vanillin and syringaldehyde? 3. How to regenerate catalysts of the oxidation and hydrolysis processes? 4. What are the mass transfer conditions, which are necessary for selective lignin oxidation? 5. What kinds of the recovering, separation and purification methods are the most efficient? 6. What are the market perspectives of the processes suggested? The answer on the first questions is primarily determined by the list of products obtained. To produce vanillin without byproducts the fermented lignins of softwood may be the most available. Such lignins are formed as the wastes in the modern technologies of softwood conversion into biobutanol. The new ways to decrease the alkali consumption in a step of lignin oxidation into vanillin and syringaldehyde are found. They were found on the base of mechanism of lignin oxidation into the aldehydes, which was suggested earlier [3]. Finally, conversion of, for example, aspen wood permits to produce up to (based on the wood) 2 wt. % of vanillin, 4 wt. % of syringaldehyde, 10 wt. % of levulinic acid, and other products [4]. Taking into account approximate prices of these products (10, 25 and 10 US$ per kilogram, correspondingly) processing 1 tone of the wood gives the products of US$ 2200 cost, and this value exceeds the cost of cellulose produced from the same wood by a factor of 5 and more.

References

1. Tarabanko V.E., Ivanchenko N.M., Koropachinskaya N.V., Kuznetsov B.N. Chemistry for Sustainable Development, 1996, No 4-5, p. 405-417. 2. Tarabanko V.E., Koropachinskaya N.V. Chem. of Plant Raw Materials (Russia), 2003, No 1, p. 5-25. 3. Tarabanko V.E., Petukhov D.V., Selutin G.E. Kinetics and Catalysis, 2004, vol. 45, No 4, p. 603-611. 4. Tarabanko V.E. e.a. Ru Pat. 2059599, 2059600, 2059601, 2065434, 2072980, 2119427.

COMPOSITE MATERIALS FROM THE WOOD WASTE

A.T. Teleshev, G.Z. Kaziev, M.P. Koroteev, K.I. Bykov, E.E. Nifant’ev Moscow pedagogical state university, chemical faculty [email protected]

Contemporary materials should be of high specific strength, efficiency, impact resistance, low density, manufacturability. These requirements are largely responsible natural wood composite. However, not all tree species and the tree is optimized for use in industrial production. The creation of artificial composite materials based on different breeds and wood waste, whose properties are close to the native properties of technically important wood is a challenge. The paper deals with issues related to technology and the properties of matrix composite materials obtained through a variety of wood waste. The technology is based on the method of mechano-chemical transformation of wood waste in the process of dispersion and dispersion of the amplifying processing component.

225 Used in industrial waste wood of Siberian larch, birch, Siberian cedar. As a reinforcing component in the manufacture of models of composite materials was investigated synthetic latex of polyvinyl acetate, urethane rubber. Dispersion of wood waste was carried out using the rotary-pulsation apparatus for liquor equal to 15 and number of cavitation  1. The results of the granulometric composition of the resulting wood pulp indicate that the dispersion leads to an exponential distribution of solid fractions ranging from <0.5 to 10 microns. Probable size of the particles is less than 0.5 microns in number average size of 2.4 microns. According to microscopy, the original timber, detecting cellular elements ordered in the longitudinal direction of the barrel, when dispersed and loses its native structure also tends to the organization of secondary structure, characterized by a pronounced roundness of the structural elements that reach a size of 30-45 microns. From the wood of the Siberian larch after dispersion by the method of forming a band with a force of 1.5 kg/cm2, followed by exposure of the samples during the day at 605 оС (to a residual moisture content 15%), samples and technical pressure-treated wood, characterized by mechanical strength of 45-50 kg/cm2. Using the reinforcing component, such as polyvinyl acetate latex (2-5%) by dispersing the wood enhances the strength of the samples pressure-treated wood is 3-4 times while maintaining the conditions of molding.

DEGRADATION AND STABILISATION OF CARBOHYDRATES IN ALKALINE PULPING CONDITIONS IN CONNECTION WITH ACIDIC PRE-HYDROLYSIS: MODEL STUDY

L. Testova, H. Sixta Department of Forest Products Technology, Aalto University School of Chemical Technology, Espoo, Finland [email protected]

Biorefinery concept pursues different pathways of complete utilisation of biomass in most efficient and environmentally friendly way. While in conventional biomass processing industries cellulosic part of carbohydrates has always been given much attention, potential of hemicelluloses has quite often been overlooked. Particularly, hardwood hemicelluloses mainly comprised of 4-O- methylglucuronoxylan are an available raw material for biochemicals, food additives and biofuels. In pulp production, the isolation of hemicelluloses could be implemented as a separate stage prior or subsequent to alkaline cooking. Among the possible isolation techniques pre-hydrolysis (both autocatalysed and acid-catalysed) is being widely investigated nowadays. Unfortunately, implementation of this process is hindered by numerous challenges and problems. One of the major undesired reactions in acidic conditions is hydrolytic depolymerization of cellulose while its actual yield remains unchanged. Cleavage of glycosidic bonds leads to dramatic decrease in cellulose DP and the formation of new reducing end groups. After autohydrolysis, the residual polysaccharide fraction is very susceptible towards peeling off reactions in subsequent alkaline cooking, which in turn results in substantial pulp yield loss. While the decrease in the degree of polymerisation in pre-hydrolysis is irreversible, stabilisation of cellulose reducing end-groups against alkaline peeling could decelerate further degradation to a certain extent. Previous studies on the stabilisation of wood carbohydrates in conventional alkaline pulping in order to obtain increased overall pulp yield were quite successful [1]. In the preliminary dilute acid pre-hydrolysis experiments on cotton linters, significant decrease of cellulose intrinsic viscosity was observed with relatively low yield loss. Subsequent alkaline treatment was accompanied by moderate decrease in viscosity, but significant yield loss of approximately 20%. It was also demonstrated that sodium borohydride, anthraquinone and anthraquinone monosulfonate applied in-situ in the alkaline pulping liquor are capable of preserving cellulose yield considerably. In this paper degradation kinetics of carbohydrates in alkaline conditions was studied on the model cellulose substrate – cotton linters. Based on the preliminary stabilisation trials alkaline degradation time-series experiments were carried out utilising different stabilisation techniques. Resulting samples were analysed in order to monitor cellulose depolymerisation and conversion of functional

226 groups attributed to degradation and stabilisation. Suggested analytical methods included intrinsic viscosity, quantification of carbonyl groups by BCA assay colorimetric method [2] and carboxyl groups by methylene blue adsorption [3] and molar mass distribution by size exclusion chromatography. References 1. Copur, Y.; Tozluoglu, A. A comparison of kraft, PS, kraft-AQ and kraft-NaBH4 pulps of Brutia pine. Bioresource Technology (2008), 99(5), 909-913. 2. Kongruang, S.; Han, M.J.; Breton, C.I.G.; Penner, M.H. Quantitative analysis of cellulose - reducing ends. Applied Biochemistry and Biotechnology (2004), 113-116, 213-231. 3. Fras, L.; Stana-Kleinschek, K.; Ribitsch, V.; Sfiligoj-Smole, M.; Kreze, T. Quantitative determination of carboxyl groups in cellulose by complexometric titration. Lenzinger Berichte (2002), 81, 80-88.

ACID-BASE APPROACH TO THE SYNTHESIS OF POTENTIAL DRUGS ON BASE OF COTTONSEED PIGMENT - GOSSYPOL

K.Z. Tilyabaev, A.M. Yuldashev, B.T. Ibragimov Institute of Bioorganic Chemistry of AS RUz, Laboratory of Physicochemical Research Methods, Tashkent, Uzbekistan [email protected]

Gossypol, 2,2'-bis(8-formyl-1,6,7-trihydroxyl-5-isopropyl-3-methylnaphtalene), is a specific cottonseed pigment. Antitumor and antiviral properties displayed by gossypol allow for its consideration as a potential drug. However, pharmacological studies have shown some disadvantages preventing its use as an effective drug, in particular, marked toxicity at optimal therapeutic doses, cumulating properties, insolubility in water, and pain at the injection sites. Numerous studies suggest that gossypol’s toxicity is reduced while its therapeutic effects are retained by modification of gossypol’s reactive aldehyde groups. Therefore, many different primary amines have been reacted with gossypol’s aldehydes to give gossypol Schiff’s bases (also termed gossypol imine derivatives), and this condensation reaction is undoubtedly the reaction most often applied to the gossypol molecule. An enormous number of gossypol Schiff’s base derivatives have been prepared for physiological studies and this class of gossypol derivatives seems to be the most promising for drug discovery. That is why their effective synthesis is of a high interest. Gossypol’s reaction with primary amines can be considered as acid-base interaction. It is known that amines are organic bases; therefore, reacting with them, gossypol acts as an acid. The following graph represents a strong linear relationship between reaction yields (%) of 13 gossypol aryl-imines and reverse Kb (basicity constant) values of corresponding amines used for the reaction with gossypol under the same conditions.

227

Graph. Reaction yield (%) of gossypol aryl-imines vs. reverse Kb of amine

The high correlation (-0.9789) found strongly suggests that the smaller is the value of reverse Kb, the higher is the yield of gossypol bis-aryl-imine. It also indirectly supports the fact that gossypol mono-imines well-known to exhibit higher physiological effects than those of their bis-analogs, can be prepared with higher yields by reaction with amines having extremely large reverse Kb values, as it has been found for mono-(o-nitrophenylimino)-gossypol obtained with 94% yield by reaction of gossypol with o-nitroaniline in a molar ratio of 1:2.

VARIABILITY OF CONTENT ECDYSTERONE IN LEAVES RHAPONTICUM CARTHAMOIDES DURING SEASON OF VEGETATION

N.P. Timofeev CF BIO (Research-Production Enterprises), Koryazhma, Russia [email protected]

Introduction. Rhaponticum carthamoides (Willd.) Iljin (Leuzea carthamoides DC.) – perennial, frigostable species from family Asteraceae. R. carthamoides and drugs on its basis were included in the State pharmacopoeia and the Register of medications of many states. The species is alien from high-mountainous region an alpestrine girdle (1200-2700 m above sea-level); it is characterized by duration of life cycle, indiscriminateness to conditions of soil fertility. Specificity of the secondary metabolism is accompanied by biosynthesis phytoecdysteroids, being the basic which major a component is ecdysterone (over 90 % of individual share). Problem of the production technology of vegetative medicinal raw materials from ecdysteroid synthesising plants is extreme unevenness of distribution ecdysterone on various organs (Dinan et al., 2001; Phytoecdysteroids, 2003). It was caused by that producing of organic substance (ecdysteroids) and accumulation of the secondary metabolites is rather difficult depended from growth processes (Shain, 2005). Proceeding from necessity of standardizing of medicinal raw materials R. carthamoides for active substances, we studied accumulation and variability content of the ecdysterone during the season of vegetation. Object and methods of researches. The district of researches is located in the southeast of the Arkhangelsk region of Russia, in the European-West-Siberian taiga-timber bioclimatic range. Dynamics of the content ecdysterone studied at adults generative plants of 6-10th year of life.

228 Various fractions of leaves organs, based on the terms of regrowth and development phases served as objects of studying. Samples selected from 20-25 plants (on 2 sheets from each plant). Concentration ecdysterone in the exsiccate was researched with a method of high-performance liquid chromatography (=242 nm), with computer data processing according a method of the intrinsic standard (Punegov and Savinovskaya, 2002). Results. 1. The beginning of vegetation of plants started in some days after slope of the snow cover (in the end of April-beginning of May) and proceeds before transferring of daily average temperature in the autumn through 0 °С (in late October). Appearance of new young growing leaves, their growing and necrosis is not timed for certain phases of development, they function during all vegetation period, replacing each other in time. Development and formation of leaves germs occurring at different times from different propagules leads up to simultaneous accumulation in above-ground sphere of fractions of the growing, young, adult, old and died off leaves. 2. Dynamic of the content ecdysterone in separate elements and phytomass fractions is combined with process of formation of propagules at which there is a redistribution biologically active substances – from old and dying in favor of growing and developing organs. Therefore the maximum concentration ecdysterone as a part of vegetative propagules are characteristic for the youngest on physiological age fractions. 3. Values of variability of concentration ecdysterone during vegetation in young leaves organs compound 2 times - 0.55-0.28%. In adult leaves of vegetative propagules, in 10 days after the regrowth beginning, the content ecdysterone is makes 0.38%. In 30 days of vegetation, during intensive growth of propagules, concentration ecdysterone drops to 0.27 %, and in 60 days - to 0.17 %. Fall to the minimum values (0.11-0.12 %) in July-August coincides with droughty environmental conditions, in the autumn season concentration increases slightly and in September compounds 0.14-0.15 %. 4. Generally the concentration of ecdysterone in adult leaves during active vegetation variate in 3 times (0.38-0.12 %). In old leaves level fall ecdysterone is practically rectilinear, also does not depend neither on a development phase, nor from calendar terms of development of plants - it decreasing consistently during a growing period in 7-8 times - from 0.15 % to 0.02 %. Absolute levels of ecdysterone in leaves R. carthamoides vary as 0.70-0.01 %.

RESEARCHES ON MANAGED BIOLOGICAL SYNTHESIS ECDYSTEROIDS AND BIOTECHNOLOGICAL PROCESS OF MANUFACTURE OF MEDICINAL RAW MATERIALS FROM LEUZEA CARTHAMOIDES AND SERRATULA CORONATA

N.P. Timofeev CF BIO (Research-Production Enterprises), Koryazhma, Russia [email protected]

The medicinal raw materials of plants Rhaponticum carthamoides and Serratula coronata, containing phytoecdysteroids, were used in medicine for the decision of a wide range of problems for conservation of health of the person, including for treatment and preventive maintenance of cardiovascular and oncological diseases, increase of acclimatization of an organism to action of unfavorable and harmful factors of inhabitancy. Proceeding from necessity of revealing of factors, growth-regulating, development and the maximum efficiency ecdysteroids synthesising (Es) plants with the enriched content of target materials and high biological activity in medicinal raw materials, the wide complex of scientific researches in following directions is actual: 1. Studying of laws of ability to live of Es-plants in ontogenesis, features of formation by them endomyccorhiza; topology, growth and development of symbiotic structures in annual cycle, them is also a microanatomic structure. 2. Dynamic communications between development endomyccorhiza in an annual cycle and growth of above-ground members of Es-plants during vegetation were investigated.

229 3. Response of Es-plants (chemical composition, number, growth and development of propagules, parametres of efficiency and phytomass) on soil nutrition intensification was revealed. 4. Influence agrochemical and cultivation technology factors (entering different types of organic and mineral fertilizers, an intensification of alienation of biomass, humidity into a root layer of populations) on magnitude of biosynthesis and qualitative compound phytoecdysteroids were positioned. Works were made during 2008-2009 years for scientific Grants RFFI № 08-04-98840. By results of researches it was positioned that life activity Es-plants (R. carthamoides, R. scariosum, Serratula coronata) in an ontogenesis it was intimately connected to symbiotic relations with fungus from genus Glomus (Glomeraceae: Glomeromycota). Age stages of development of a mycorhiza in an annual cycle, variability of parametres of vegetative frames, and also the key moments allowing a plant to supervise fungus and natural factors, managing were in detail considered by a plant. The hypothesis was put forward, that through the mechanisms underlying ecological-biochemical interactions VAM-mycorhiza and Es-plants, it is possible to manage efficiency, biosynthesis and accumulation phytoecdysteroids in members of plants - controlling biological, technological or agrochemical methods efficacy of microbiological-vegetative plants mutual relations. Strong negative reaction R. carthamoides was experimentally proved on entering of centre and high doses of organic fertilizers as readily available power supplies. Ability of plants to a reproduction drops in 2-4 times, efficiency - to 1.7 times, biosynthesis phytoecdysteroids - from 3-5 to 10 times. At use of small doses of mineral fertilizers level decrease phytoecdysteroids in medicinal raw materials was insignificant (on 7-12 %). Qualitative compound phytoecdysteroids and containing them low activity ecdysteroids it was bound to formation of reproductive propagules and their development during vegetation. It was revealed that qualitative structure phytoecdysteroids and enrichment their individual substances was connected with formation of reproductive propagules and intensity of their development during vegetation. Therefore at plants of the generative season the balance of compound phytoecdysteroids can be changed through influence ecological or anthropogenic factors. Acknowledgments. The work was done on a partial financial support granted by the Russian Fond for Fundamental Investigations (RFFI) and the administration of the Archangelsk region.

ADAPTATION OF RHAPONTICUM CARTHAMOIDES TO EDAPHIC FACTORS (HEAT, LENGTH OF DAY AND GROWING SEASON), BASED ON PRODUCTIVITY AND ABILITY TO SYNTHESIZE ECDYSTERONE

N.P. Timofeev1, P.W. Kowalski2, J. Krywuc2 1 - CF BIO (Research-Production Enterprises), Koryazhma, Russia 2 - FITOSTAR, Gdynia, Polska [email protected]

1. Object and methods of researches. Proceeding from necessity of an establishment of influence of natural and climatic factors on ability to live of medicinal plants Rhaponticum carthamoides (Leuzea, maral root), species comparative study in 6 agropopulations cultivated in Poland and Russia was made. The medicinal raw materials are designed for reception ecdysterone containing pharmpreparations, drugs and fodder additives. 2. Within 5 years indexes of development of 2 populations in Central Poland (Bygdoshch, agrofirm "Fitostar") compared to parametres of 4 agropopulations grown in the European North (Russia, the Arkhangelsk region). Investigated the soil factors influencing density of species, formation of propagules and phytomass accumulation on years of life in an ontogenesis; studied ability to biosynthesis ecdysterone during vegetation (HPLC-method). 3. For both climatic zones relatives are a soil type (sod-podzolic), level of its fertility, the content of nutrients and moisture parametres. Differences was concluded in smaller duration of a frostless season, and provision of heat during a season of vegetation and length of light day. In the European North the sum of temperatures above +5 … 10 C less on 30-40 %, and above 15 C – on 50-60 %.

230 The growing season is shorter for 2 months (175 against 235 days), a frostless season – on 50 % (105 days against 150).The length of light day, on the contrary, is more (16-20 hours against 14-16). 4. Results. It is assigned, that processes of growth and development of propagules R. carthamoides in two different climatic regions are identical – a median number of propagules, their height, width of blades are identical to the same age states of an ontogenesis. Development to a blooming phase occupies in Poland 56-61 day, fructification of 71-77 days. Heat disadvantage in the European North is compensated by larger duration of light day - blooming comes through 44-51, fructification through 66-72 (77) days. The average density of sowings (number of plants per acre) within 4th years of life also is identical. In the conditions of Poland it is close to value in the European North: for 3rd year of life 31 against 23-32 thousand plants of/hectares, for 4th year - 21 against 19-25 thousand plants. Productivity of agropopulations, irrespective of geographical region and characteristics of soils, has compounded for 3rd year of life about 500 kg/hectares. For 4th year of life, during a blooming phase in June, efficiency was enlarged to 700-800 kg/hectare, and in July (in a fruiting stage) has reached about 1000 kg/hectare. In further, after the introduction into the generative season, for 5-6th year of life in the conditions of the European North there is a doubling-trebling of magnitude of phytomass - to 2000-3000 kg/hectare, for 6-7th years – to 5000-8500 kg/hectare for above-ground parts and 3400- 6500 kg/hectare for underground parts. In an ontogenesis the contents ecdysterone in adult leaves has compounded accordingly: 0.04 and 0.06 % at juvenile plants for 1st year; 0.18 % and 0.17-0.22 % at virginitive plants for 3rd year. For 5th year at generative plants during a phase of a regrowth the contents ecdysterone in both climatic zones also was to relatives of 0.52 % and 0.53 %. The content ecdysteroids in leaves of plants depended on a development phase. The maximum concentrations ecdysterone (0,4-0,5 %) in all populations were observed in the early spring after a regrowth. During a phase blossom fading the content ecdysterone decreased in 1,5 times. After blooming of plants has dropped in 2 times, and after fructification the difference in concentration ecdysterone at young and old leaves has compounded 6 times. Conclusions. Thus formation productivity and biosynthesis ecdysterone heating support of area of cultivation has no crucial importance. In the conditions of a cold climate of the European North development R. carthamoides in an ontogenesis to similarly that in the conditions of a warm climate of the central Poland, but with alteration for 1 month later.

FINE STRUCTURE OF PAPERMAKING FIBRES AND ITS PRACTICAL ASPECTS

A. Treimanis1, M. Laka2, L. Vikele2, S. Chernyavskaya2, M. Skute2 1 - Latvian Academy of Sciences, Riga, Latvia 2 - LS Institute of Wood Chemistry, Cellulose Department, Riga, Latvia [email protected]

The development of the research equipment and methods, and the further improvement of the technologies are boosting the studies on the micro- and nanostructure of papermaking fibres and cellulose particles. This paper focuses on the localization of the residual components in the chemical pulp fibre walls and the properties of nano/micro particles from wood and cellulose. The beating and grinding processes are binding these two topics together. The localization of residual wood components in pulp fibres was investigated mainly by using hydromechanical peeling of the fibres’ surface layers by the prolonged mixing of the fibres’ water- ethanol suspension in a laboratory disintegrator. This method has been continuously extended and modernized at the Latvian State Institute of Wood Chemistry, Riga, during several years. The advantage of the method is the possibility to separate and isolate the surface layers in quantities which are sufficient for certain analytical procedures. In spite of the developed network of micro- and submicropores, the final localization of residual wood cell components (lignin, hemicelluloses) is uneven across the fibre wall. The content of lignin and heteroaromatic compounds (furanoids/furan polymers) as well as oxypolysaccharides is determined to be higher in the surface

231 fibre wall fraction. Fluorescence labeling and GPC-MALLS fractionation show that the molecular weight distribution of the fibre surface material differs significantly from that of the bulk fibre. The hydromechanical peeling of the fibre surface layers is performed in a disintegrator with blunt mixer blades. When using sharper blades, it is possible to produce pulp fibres with nano/micro fibrillar and spheroidal cellulose particles attached to the fibre wall as well as loose ones. They form a gel-like structure. The addition of this material in the quantities of 5-20% by weight gives considerable boost of paper handsheet’s strength properties. Nano/micro particles of cellulose and wood were obtained also by using a traditional approach, namely, acid hydrolysis and grinding at a high shear stress. In this case, the thermocatalytic method was applied with small quantities of weak hydrochloric acid and sequential treatment in a ball mill. TEM Microscopy data show that nanocellulose (NC) particles exist in nanofibrillated (40-70 nm) and spherical (50 nm) form. Also much smaller particles are observed. Still a part of the particles constitutes aggregates. The separation of the particles was not performed because it would not be an economically attractive process in practical applications. The experimental data show that the addition of nano/micro particles promotes the improvement of both strength and surface properties of the handsheets.

ANTIBACTERIAL DRUGS AS ENVIRONMENTAL POLLUTANTS

R.E. Trifonov, A.D. Goryachikh, E.A. Popova, V.A. Ostrovskii St.-Petersburg State Institute of Technology (Technical University) [email protected]

A study of Pharmaceuticals and Personal Care Products (PPCPs) as danger environmental pollutants is a high-priority subject for different kinds of ecological and chemical sciences. The trace levels of such compounds are constantly detected in aquatic biota of Arctic regions. Among others, different anti-infective pharmaceuticals represent a cause for concern because of their potential contribution to the spread of anti-infective resistance in bacteria and other negative effects on environment and human health. Several classes of these compounds (e.g., antibiotics: -lactams, tetracyclines, macrolides; synthetic antimicrobals: sulfonamides, quinolones etc.) which are widely using in different kinds of human activity may be considered as the danger pollutants. One of the important problems in this area is a studying of degradation and chemical transformation processes of the PPCPs pollutants. On one hand these reactions is the main way to get the harmful substances from the environment. However, on another hand, in some cases high-toxic compounds may be formed in this manner. The knowledge on mechanism and velocity of the degradation processes allows to determined content and time of life-cycle of the compounds and their metabolites in biota. These investigations lie in a sphere of competence of organic chemistry, analytical chemistry and ecological chemistry and require the participations of various experts. Researches from different universities and scientific institutes may take part in these investigations.

THE CHEMICAL TREATMENT OF TEXTILE FIBRIOUS WASTES AND TO OBTAIN CARBOXIMETHILCELLULOSE ON THE BASES OF THEM

S.M. Turobjonov, M.M. Murodov, E.A. Egamberdiyev Tashkent chemical technology institute [email protected]

It is known that there is a great demand for cellulose and its products in our republic nowadays. At present cellulose is being made from cotton wool. But its being expensive causes the cellulose and also products which are making on the basis of cotton wool are becoming expensive. To settle above matters, to put into operation manufacturing of cellulose on the bases of various annual and perennial plants which kept cellulose in their structure, to widen the source of local raw materials which are necessary for manufacturing cellulose on the basis of not only cotton wool but

232 also on the bases of different raw materials above-mentioned are becoming one of the today’s active objects. In this field some work is being done to implement different research and their results in the industry scale. Besides, textile fibrous wastes are considered the base of raw materials of manufacturing cellulose and its products. During the research some samples were taken from the fibrous wastes of different textiles and their properties were studied. As the result of research studied fibrous wastes were separated into 3 kinds, that’s to say marks (A-1, B-2, C-3) and the process of chemical treatment were carried out. During the process of chemical treatment some difficulties such as: various uncleanness in the structure of fibers, fibers dyed with colouring agents which possess various complex structures, different pigments, and the modifications of artificial fibers were occurred. As the result, the quality indices of taken fibrous raw materials were defined and obtaining potentialities of cellulose ether – carboximethilcellulose on the bases of textile fibrous wastes which possess different polymerization degrees have been studied. The qualty indices of carboximethilcellulose obtained on the bases of samples textile fibrous wastes which possess different polymerization degrees as the result of chemical process (mercerization process 10 0С, prepare process 70-80 0С)

Quality indices of CMC А-1.DP В-1.DP С-1.DP ТS -88. 3000 1200 1300 2-12: 2005 PD of CMC 1500 770 710 350-700 Exchanging degree, % 0,85 0,86 0,84 not less than 0,80 The amount of main substance, % 52,8 51,7 52,1 not less than 47 Solubility of CMC which 99,5 99,3 99,4 not less than 97,0 possesses dry structure in water,% рН indices 8 8 9 10-11 Anhydrous index of mixture, 4 4.1 3.8 5 sm3⁄30 min. DP – degree of polymerization TS – technical specification It may be observed, it has been defined that different shown quality indices of CMC obtained on the bases of textile fibrous wastes meet technical terms demands.

OIL MILL PLANTS WASTE USED AS THE ANTICORROSIVE COATINGS FOR THE STEEL ATMOSPHERIC CORROSION PROTECTION

A.A. Uryadnikov, E.D. Tanygina, N.A. Smolin, L.E. Tsygankova Tambov State University named after G.R. Derzhavin Tambov, Russia [email protected]

The present study suggests to use the anticorrosive coatings based on the colza oil (CO) with oil mill waste admixtures. The waste 1 contains higher carboxylic acids and the waste 2 is the higher carboxylic acids and phospholipids (Ph) mix. The study singularity is caused by the mineral oils’ high costs and toxicity, which are common used in the same way for the machinery conservation. Their substitution by the widespread renewable natural product allows to avoid the grounds pollution and to reduce the conservation costs. The corrosion (0,5 M NaCl solution within 14 days) and the full-scale in the urban atmosphere conditions tests of the carbon steel under the protective coatings were carried out. The tests’ results were compared to the same of the coatings based on the colza oil with the synthetic carboxylic acids vat residues (SCAVR) or phospholipids admixtures.

233 The compositions’ except of the CO with SCAVR mix protective action does not exceed 40 % in the salt solution. This effect is caused by the surface-active to the steel surface chloride-ions. The 15 and 20 wt. % SCAVR admix increases the compositions’ coatings thickness (h) sharply which protective action (Z) reach correspondingly 77 and 98 %. The SCAVR are low toxic and can be used as the anticorrosive admix, but at the present time they are not produced practically in Russia. Therefore it is proposed to substitute them by the similar oil mill plants waste. The CO and Waste 1or Waste 2 compositions protective actions are comparable the same of the compositions contained SCAVR or phospholipids (Table). The phospholipids at the same time are very valuable product and the colza oil’s itself price is high enough at the present time. The waste admix to basis-solvent (CO) allows to decrease the conservations costs. CO supplies with the metal surface hydrophobization and the admixed surfactants due their adsorption allow to decrease the carbon steel corrosion rate. Table The studied compositions protective action after 3 month full-scale Composition Coating thickness, μm Z, % CO 31 96 Phospholipids 122 99 Waste 1 31 95 Waste 2 36 96 CO + Waste 1, 20% 28 97 CO + Waste 2, 20% 30 97 CO + SCAVR, 20 % 686 99

The potentiostatic polarization measurements of the carbon steel under the protective coatings have shown, that the studied CO and Waste 1or Waste 2 compositions shift the corrosion potential to the anodic area.

PRODUCTS COMPLEX WASTE PROCESSING OF ABIES SIBIRICA

V.M. Ushanova The Siberian State Technological Univercity, Krasnoyarsk, Russia [email protected]

During Abies sibirica harvesting and processing the waste (wood greenery (WG) and bark) is generated. The waste is possible to use for getting different products in demand, which are contain bioactive substance (BAS). Complex WG and bark processing give the possibility for more complete use it for economic and ecological goals. Complex WG processing of Abies sibirica provide for its chemical and biological processing, that make it possible for increase yield and assortment of valuable products, which contain BAS. Different variants of processing the waste of abies possible depend on delivered objects. Ii is possible significantly increase yield of extractive substance by using the sequential extraction. For example, yield of extractive substance compose from 25 % and WG of abies – 33 % if we use the sequential extraction of bark by liquid carbon dioxide, water and ethyl spirit. After processing WG of abies (1,5 tonnage) by hot steam we got 23-25 kg of essential oil, 258-260 kg of residue, 497-500 kg florent water. Residue used for getting coniferous aqueous and coniferous salt extracts. Residue of WG extract by aqueous solution of ethyl spirit. We got 229-340 kg of spirit extract which contains 32-42 % of extractive substances. The extract cooled and settled in the course of 12 hours. Refrigerated extract filtered with the separation of waxy substances, evaporated for getting coniferous paste (130 kg). Paste, which we got from WG of abies after distillation of essential oil, satisfy the requirements of State Standart Specification 21802-76. Coniferous paste can use as bioactive additive in cosmetic products and in feed for domestic animals. After

234 extrication by ethyl spirit solid residue dried out, powdered and made from it vitamin flour (350 kg). Fresh WG of abies (7 kg) powdered and extracted (on the first stage) by liquid carbon dioxide. Yield of the product made up 3,2 % (from mass а.d.s.). Dry solid residue (on the second stage) extracted by solution of ethyl spirit. Yield of the product was 24,4 % (from mass а.d.s.). After distillation of solid residue of WG of abies as original WG extracted (on the first stage) by liquid СО2 and solution of ethyl spirit (on the second stage). Yield СО2-extract was 3,5 %, spirit extract – 17,0 %. During the processing of WG of abies with use of such methods get products which contains BAS. Used extra gent go through the regeneration. Engineered method of processing of residuals of barking without their prior sorting [Patent. 2238307] aloud to get bioactive products from them which are carbon dioxide, spirit and aqueous extract containing different BAS. Processing of abies bark [Patent. 2067977] provide for getting carbon dioxid extract and maltol. On the base of carried out researches was exhaust regulations for produce of carbon dioxide extracts and specification for СО2–extracts, spirit and aqueous extract rrom WG and bark of Abies sibirica. Bioproducts for protection of plants, feed products or biocompost were getting from original WG, bark and waste of barking and its post-extractive residues. In case of impossible realization some methods carried out briquetting of bark for further using as a fuel.

FRACTIONATION AND CHEMICAL CONVERSION OF LIGNOCELLULOSICS FOR THE PRODUCTION OF LIQUID TRANSPORTATION FUELS IN A FOREST BIOREFINERY

A. Van Heiningen Aalto University, Department of Forest Products Technology, Espoo, Finland and University of Maine, Department of Chemical and Biological Engineering, Orono, USA [email protected]

Lignocellulosics are considered as feed stock for transportation fuels and chemicals because they address two pressing global issues; climate change and “peak oil”. The collection and processing of wood at centralized facilities is already practiced by the forest products industry. Therefore, the production of renewable and carbon-neutral biofuels and chemicals besides traditional products such as paper, tissue, board and wood products presents a great opportunity to the forest products industry. Since the market for transportation fuels is an order of magnitude larger than the pulp market, these new products will have a lower price than pulp. Therefore at the present time the new products should be produced from the non-cellulose part of the wood chips or from additional biomass. To minimize capital and operating cost, the scale of the lignocellulosic biomass conversion should be maximized and closely integrated with pulp production. Also the biomass fractionation process must be omnivorous process and simple in order to minimize operating and capital costs.

Different fractionation processes and chemical conversion processes will be compared. Special attention will be given to the SO2-Ethanol-Water (SEW) fractionation process which fractionates lignocellulosics into hemicellulose sugars, degraded cellulose and sulfonated lignin. Subsequent fermentation of the hydrolyzed carbohydrates into butanol using Clostridia bacteria will be described. An integrated process diagram will be presented.

235 FIREPROOF WOOD LAYERED PLASTICS

V.V. Vasilyev, V.V. Bystrova, A.M. Sokolova Saint-Petersburg State Forest Technical Academy, Saint-Petersburg, Russia [email protected]

Wood layered plastic of mark FТО-3 is used in warmed building deck. Its heating up to temperature 50-60C is carried out at the expense of an electroconducting layer, located in the middle part of the plastic. Application of wood materials in buildings construction is connected with danger of their ignition. Plastic fireproof has been increased by an impregnation of wood veneer by flame retardants, containing nitrogen and phosphorus atoms: ammonium phosphates and Amidophosphate of mark KM, which obtained by condensation ortho-phosphoric acid and carbamide. Birch veneer in the thickness 1.5 mm and humidity 80-90% was treated by flame retardants water solutions in concentration of 35%. After drying the phenol-formaldehyde resin of mark SFZh-3014 in quantity 20% was applied on the veneer. Plastic in the thickness 5.5 mm was pressed at the temperature 120С under the pressure 10 MPa, and specific time of exposure at the maximum pressure 5 minutes/mm. Fire test was estimated on weight loss in «a fire pipe» at exposure time of the sample in a torch flame during 150 s. Properties of the obtained plastics are shown in the Table.

Table. Properties of wood layered plastics with the various content of flame retardants.

Flame Content of Density, Strength, МPa Weight retardant flame kg/m3 at a bend at a chopping loss, retardant, % after boiling % Control - 1140 194 2,74 80,3 (NH4)2HPO4 10 1290 206 2,83 68,5 20 1100 173 2,72 19,8 25 1220 184 2,57 23,4 30 1230 161 1,72 16,3 35 1250 175 0,81 15,8 NH4H2PO4 20 1160 198 2,70 23,2 30 1210 177 1,88 18,1 КМ 10 1270 272 3,14 9,6 20 1320 212 2,95 7,9 25 1290 208 2,68 6,0 30 1320 170 1,94 5,4

Plastic, made of veneer impregnated by composition KM, has the maximum durability and fireproof in a comparison with the plastics containing ammonium phosphates. Advantage of the amidophosphate KM is possibility to prepare solutions with concentrations 50-55 % at 20С, while the maximum concentration of salts solutions is 26-40 %. The optimum content of conposition KM in a range from 20 to 30 % from weight of absolutely dry wood for different groups of materials combustibility in accord with «SNiP 21-01-97» should be defined during special investigations in the certificated laboratories.

236 EXTRACTIVE COMPOUNDS OF BETULA PENDULA ROTH TWIGS PHLOEM

D.N. Vedernikov, V.I. Roshchin Saint-Petersburg Forest Technical Academy [email protected]

Birch twigs were divided by wood (70,6%), inner bark (16,2%) and outer bark (13,2%). Inner bark was extracted successively with petroleum ether (PE) and diethyl ether (DE). PE extract was separated into neutral substances (NC) and "free" acids. DE extract was divided into neutral substances (NC), "strong" and "weak" acids. PE extract (0,58% of the inner bark) contained 0,44% NC and 0,14% "free" acids. NC was separated by column chromatography on silica. Chlorophyll derivatives, hydrocarbons, trimethylpentadekanon, esters of fatty acids and lupeol, phytol, β- sitosterol, stigmastanol, octakosanol, betulaprenols, tri-, di-, monoglycerides, lupeol, β-sitosterol, stigmastanol, 5β, 6α, 8β-trihydroxycaryolane, 7α-dihydroxysitosterol, 7β-dihydroxysitosterol, 7- oxositosterol have been identified by methods of chromate-mass-spectrometry, NMR1H spectroscopy and infrared spectroscopy. C27H56 prevails among hydrocarbons. The quantity of “odd” alkanes is approximately equal “even”. For example: C27H56-25,3%; C26H54-15,1; C28H58-14,9. Palmitic (58%) and stearic acid (10%) dominate as part of the free acids of PE. Palmitic ( 35%), nonandioic ( 20%), unsaturated acids: oleic (8%) and linoleic (2%) are included in composition of triglycerides. Methyl ether of betulinic acid acetate (30% of NC), betulin (10%), oleanol (1%), 3β, 20-lupan-diol (2%), monoglycerides (30%) have been identified in NC of DE. 4- (4-Hydroxyphenyl)butan-2-ol (rhododendrol) is passed over from DE extract in aqueous solutions of NaOH and NaHCO3 during exraction of acids. Octanoic, heptandioic, hexandioic, nonandioic (50%), rhododendrol as part of the "strong" acids of DE. Rhododendrol (33% of acids), fatty acid, acetate, oleanolic acid (6%), oleanolic acid acetate (8%) have been identified as part of the "weak" acid of DE extract.

THE CARRIER FROM INNER BIRCH BARK FOR PROTEIN SUBSTANCES IMMOBILIZITION

E.V. Veprikova, S.A. Kuznetsova, B.N. Kuznetsov Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia [email protected]

Porous materials from wood wastes have prospects for the use as the carriers for ferments and microorganisms immobilization. The important property defining the possibility to use carriers for biocatalysts immobilization is their ability to adsorb substances of protein nature, for example – at gelatin. The possibility to use sorbent, obtained from the inner birch bark as a carrier for protein catalysts was studied in the present work. Sorbent was obtained by the treatment of inner birch bark with 2 % NaOH solution [1]. The influence of background electrolytes, pH and temperature on gelatin sorption was investigated. It was established that electrostatic interaction of gelatin with sorbent surface prevents the sorption in acid and alkaline solutions. The increase of gelatin sorbtion in presence NaCl, KCl, CaCl2 and + + MgCl2 is due to a screen of these interactions. The positive effect Na and K on gelatin sorption is observed in pH range from 2,0 to 7,5. Gelatin sorption practically doesn’t depend on these ions nature. The influence of Ca2+ and Mg2+ become apparent only at pH 3,1. The maximal increase of gelatin sorption is observed in solution containing 0,9 % NaCl, 0,2 % CaCl2 and 0,2 % MgCl2 at pH 4,5. The equilibrium is reached during 1,5 – 2 h in this solution. To reach sorption equilibrium at рН 2,0 and 7,5 it is required 7,5 and 2,5 h accordingly. The values of equilibrium sorption at different pH are presented in table 1.

237 Table. The equilibrium sorption of gelatin at different pH (electrolytes concentration is 0,9 % NaCl, 0,2 % CaCl2 and 0,2 % MgCl2) Sorption of gelatin, mg/g рН Temperature, оС * Gelatin concentration in solution, g/l ** 22 37 0,6 6,0 30,0 2,0 18,1 23,5 4,1 18,1 18,5 3,1 26,7 31,6 9,2 26,7 38,2 4,5 62,5 78,15 31,4 62,5 82,8 7,5 43,5 46,2 19,9 43,5 49,2 * Gelatin sorption from 0,6 % solution, ** sorption at 22 оС.

The increasing of temperature to 37 оС results in rising of gelatin sorption at different pH (table 1). Time to reach equilibrium is also reduced to 2 h in alkaline and to 2,5 h in acid solutions. The maximal sorption of gelatin is observed at рН 4,5 and temperature 37 °С. Table confirm that the sorbent from inner birch bark is characterized by good sorption capacity for gelatin in wide ranges its concentrations in model solution. The results of the gelatin sorption studies show the possibility to use sorbent, obtained from inner birch bark as carrier for ferments and microorganisms.

1. Patent RU 2311954. Enterosorbent and a method for preparation thereof / Kuznetsova S.A., Shchipko M.L., Kuznetsov B.N. et al. – published 10.12.2007, Bull. № 34.

NEW RECEIVED COMPOUNDS BASED ON NATURAL ALIZARIN

N.A. Vereschagin, D.Y. Korulkin al-Farabi Kazakh National University [email protected]

Many researchers are striving to create new, more effective medicines. And for this they use the methods of modification or directed synthesis of various substances. To create a highly active compounds are used as the basis of various forms of natural compounds. For the retrofit, we used the anthraquinone skeleton, to which was attached amino acids of different natures. The search for new biological activity and enhance their own were compared with the activity of the initial anthraquinone and associated amino acids. We obtained the following compounds: ОН

ОН + О О О О

H2N О ОН О HN ОН ОН ОН HN

ОН

О О ОН О 1,2-dioxiantraquinone Glutamic 1,2-N-diglutamilantraquinone (alizarin) acid ОН ОН О О + О О О О ОН ОН HN ОН ОН HN H N 2 ОН

О ОН О О О 1,2-dioxiantraquinone Aspartic 1,2-N-diasparticilantraquinone (alizarin) acid

238 + OH H2N O O O OH

О ОН O HN ОН OH HN

О O 1,2-dioxiantraquinone Phenylalanin 1,2-N-diphenylalaninilantraquinone (alizarin) O OH

OH + H2N OH O O OH О ОН HN ОН O HN OH

О OH O 1,2-dioxiantraquinone Tyrosine 1,2-N-dityrosinilanthraquinone (alizarin)

At this moment we are searching biological activity and further modification in order to obtain antiviral drugs.

LIGNINS HYDROGENATION

Yu.T. Vigranenko, V.M. Ushakov Saint-Petersburg State Forest Technical Academy, Saint-Petersburg, Russia [email protected]

Lignins hydrogenation permits to avoid paper yellowing and importantly improves its quality. 4- propylphenol, 1,2-dimethoxy-4-propylbenzene, sinape and cumarine alcohols were tested as lignins model compounds. Heterogeneous catalysts – platinum on aluminium oxide and nickel on coal, homogeneous catalysts – carbonyl complexes of cobalt were tested. Benzene nucleus is o hydrogenased under t=400 – 500 C, PH2 = 10,0 – 15,0 MPa, if heterogeneous catalysts are used. Products hydrogenation yields equal 30 – 40 % , as initial substrates conversion is low. C=C bonds o is hydrogenased under t=130 – 180 C, PCO+H2 =20,0 – 30,0 MPa and hydroformylation parallel reaction occurs, if homogeneous catalysts are used [ catalysts precursors ,Со2(СО)8 Co2(CO)6(РR3)2, R=alkyl or aryl, cobaltcarbonylpyridine complex KPK ]. Homogeneous catalysts are inactive in benzene nucleus hydrogenation reaction. Products hydrogenation and hydroformylation yields are 20 – 30% , as initial substrates conversion is smaller 40% . Cobalt catalysts reactions hydrogenation and hydroformylation are decomposed and desactivated, if temperature arised above 180o C. Yield products these reactions is decrease,

OPTIMIZATION OF ENZYMATIC AND BIOMIMETIC CONVERSION OF UNSATURATED FATTY ACIDS INTO HYDROPEROXIDES: AN EFFICIENT APPROACH TO VALUABLE OLEOCHEMICALS

J.J. Villaverde1, S.A.O. Santos1, N. Loureiro1, M.M.Q. Simoes2, M.R.M. Domingues2, A.J.D. Silvestre1 1 - CICECO, Department of Chemistry, University of Aveiro, Aveiro, Portugal 2 - QOPNA, Department of Chemistry, University of Aveiro, Aveiro, Portugal [email protected]

Vegetable oils and fatty acids, due to their natural abundance and inherent functionality, are nowadays seen as important raw materials for the production of biofuelsa but also of chemicals through modifications involving both the carboxylic group or the double bonds, in the carbon chain

239 leading to materials with wide applications in paints, adhesives, polymers and coatings, among others products.b The mid-chain functionalization/cleavage of unsaturated fatty acids is one of the most attractive routes for the development on new applications for these compounds. This approach is particularly attractive considering that some natural mid-chain functionalized fatty acids like ricinoleic acid, obtained from castor oil are produced in limited amounts, and very high priced. Apart from chemical approaches, this mid-chain functionalization can be accomplished with the aid of biotechnological tools. O In this communication we report some OH results in the enzymatic (via lipoxygenases) Several hydroperoxide isomers and biomimetic conversion of unsaturated OOH O fatty acids into hydroperoxide derivatives. ······· · ····· These intermediates can then be converted · · · · · · · · · · · OH C14 C8 into ricinoleic acid analogs (Figure 1), which are useful synthons, for example for Ricinoleic acid analogs the synthesis of aliphatic polyesters.c Also a OH O general description of the study, from the ······· · ····· · · · · · · · · setup of adequate analytical methodologies, · · · OH C14 C8 optimization of enzymatic and biomimetic systems to maximize hydroperoxides production and their conversion into useful POLYMERS derivatives will be presented Figure 1. Formation of polymers from linoleic acid by biomimetic and enzymatic systems

Acknowledgements ERA-NOEL: “Novel enzyme tools for production of functional oleochemicals from unsaturated lipids” ERA-IB/BIO/0001/2008.

References 1. Kamm, B.; Gruber, P.R.; Kamm, M. Biorefineries – Industrial Processes and Products; WILEY-VCH, 2006. 2. Belgacem, M.N.; Gandini, A. Monomers, Polymers and Composites from Renewable Resources; Elsevier, 2008. 3. Sousa, A.F.; Gandini, A.; Silvestre, A.J.D.; Pascoal Neto, C. Synthesis and Characterization of Novel Biopolyesters from Suberin and Model Comonomers. ChemSusChem, 2008, 1, 1020–1025.

NEW MODIFYING MULTIFUNCTIONAL ADDITIVES ON THE MALEINISED COLOPHONY FOR TIRE AND RUBBER INDUSTRY

D.S. Vladykina, K.P. Kolnogorov, S.A. Lamotkin Belarusian state technological university, Minsk, Republic of Belarus [email protected]

Primarily, the tire production presupposes the maintenance of sustained fixation in the rubber system in the process of tire usage, the melioration of tires themselves, the improvement of physical-mechanical and dynamic characteristics of the rubber. To find reliable and stable bond strength in the brass metal cord rubber system is very important for developing new tire rubber formulations. The use of special modifying additives, i.e. adhesion’s promoters, is the most widespread means to create a sustained bond between the rubber and the metal cord.

240 It is known that due to its chemical composition peculiarities the colophony is a significant raw materials source of the modifying additives. The work’s aim was to produce new modifying additives on the maleinised colophony for tire and rubber industry. In the process, there were received individual as well as mixed amide salts of metals of variable valency and zinc maleopimaric acid, received on the basis of the maleinised colophony. The effect of the obtained by modifying additives on the kinetics of vulcanization of the unfilled rubber compounds was studied. The effect of modifying additives on the plastic-elastic unfilled and filled rubber compounds properties. There were conducted experimental researches studying the influence of the received modifiers on the rubber physical-mechanical indicators characterizing their strength properties. There was studied the influence of the modifiers on the resistance to the rubber thermal aging. There was researched the influence of the modifiers on the rubber adhesion properties to the brass metal cord. There were defined the dynamic characteristics of carcass rubber received by using the modifying additives. It was found out that the best complex of the physical-mechanical and dynamic properties and the strength to a thermal-oxidative influence are typical of the rubber containing the cobalt amide salt dosated 1.0 part by weight, taken as modifying additives. The strongest adhesion bond of the brass metal cord to the rubber is observed when using the cobalt amide salt dosated 1.0 part by weight and the nickel-zinc amide salt dosated 1.5 parts by weight. The received modifiers of the rubber-metal cord adhesion bond strength are at the level of traditionally used foreign modifiers, and in some indicators the former excel the latter, for example, in characterizing the rubber physical-mechanical indicators, especially after thermal aging.

ESSENTIAL OILS OF VARIOUS VIEWS OF SPRUCES, AS A SOURCE OF BIOLOGICALLY ACTIVE SUBSTANCES

D.S. Vladykina, S.A. Lamotkin, E.D. Skakovskij Belarusian state technological university, Minsk, Republic of Belarus [email protected]

Salvaging of foliage allows without involving in a turn of new forest areas essentially to raise commodity output discharge. It can serve as raw materials for development of valuable chemical combinations, medical drugs, the fodder and other products, which cost much above the wood. The augmentation of assortment of yields from the needle of a conifer can be obtained at the expense of fuller use of extractives of raw materials. Among coniferous woods for logging industry the main are: pine ordinary, fir Siberian, views of spruces and larches. In Belarus the most widespread are pine ordinary and spruce ordinary, which requirements of a forest husbandry since they incompletely use potential fertility of bedrock and climatic resources for wood cultivation cannot be to the full satisfied. At the same time natural settings of Belarus are favorable for growth of major number of views coniferous trees a temperate zone of the Earth. Introduction of woody plants can solve a problem of rising of efficiency of forests and optimisation of environment, allows to involve new plants with the best, than at indigenous views, biological and economic properties. The aim of my work is to investigate essential oils of various kinds of spruces, as raw materials for reception various biologically active substances. As objects 20-25 summer trees of 4 views of spruces (Picea) have been chosen and samples of needle are collected: 1. P. glauca (Moench) Voss. (white spruce), 2. P. pungens Coerulea (colorado spruce), 3. P. mariana (black spruce), 4 P. abies (L.) Karst (common spruce). The foliages were collected in winter months when composition of essential oil is stabilized, on the trial area of free from the industrial targets, 70 km had apart from a city.

241 Essential oils from the samples were obtained by hydrodistillation, which quantitative yield to define volumetrically. Samples were analyzed by a gas chromatography method on a chromatograph «the Crystal 5000.1», supplied with a flame ionization detector. The spectroscopy method 1Н and 13С NMR was also used to the analysis of essential oils. Record of spectrums of NMR was made on spectrometer AVANCE-500 (Germany) with working frequencies for kerns 1Н- 500 MHz and for kerns 13С-125 MHz. The obtained under investigation results have shown, that alien views it is more productive on essential oil. So the essential oil content for 100g a.d.s.. compounded 1.98; 0.66; 2.64; and 0.20 % accordingly. Moreover, the content of separate fractions in explored essential oils was also examined. Apparently, in essential oils alien views above the content of sesquiterpenes and oxygen- containing fractions. As a part of essential oils 44 components have been identified. As results from the presented data, qualitative composition of explored essential oils remained to stationary values while the quantitative content of separate components essentially varied depending on a spruce view. In explored samples of essential oils the content of limonene for a common spruce above in 2-3 times. However, the others are characterized by higher content of santene, myrcene, Δ3-carene. The most considerable differences are found for bornyl acetate. The oxygen-containing fraction of essential oils alien views on 75-85 % is presented by the above mentioned component, that practically in 2 times above the content of this ingredient for a common spruce. It can be seen that the white spruce deserves the greatest attention, for which content of such components as bornyl acetate (40 % of mass. from the total content), α-ilagene (0,2 %), γ-muurolene (1 %), α-muurolene (0,5 %), γ- cadinene (0,75 %) and δ-cadinene (2,7 %) reach the maximal value. Besides, the total content of the sesquiterpene fraction, involve biologically active substances, reaches 8.15 %. The presented data permit recommended the black spruce as raw materials for essential oil reception for Republic terrains, in connection with its high content in foliage and similarity terpene composition with a common spruce.

NEW CNS-ACTIVE COMPOUNDS SYNTHESIZED FROM MONOTERPENOIDS

K.P. Volcho, I.V. Il’ina, O.V. Ardashov, A.V. Pavlova, T.G. Tolstikova, N.F. Salakhutdinov Novosibirsk Institute of Organic Chemistry, Novosibirsk, Russia [email protected]

Starting from accessible monoterpenoids with pinane, carane and para-menthane frameworks a large set of new compounds has been synthesized. Most of the compounds are the products of interaction of monoterpenoids with aldehydes; some of them possess new skeletons not found in literature. The structure of the products depends strongly on small changes in the structure of both starting terpenoids and aldehydes. Structures of some synthesized compounds are drawn below.

242 OH O OH Cl OH OH O O OH O OMe OMe 2 OH 1 3 OH 4 O OH H O O MeO H OMe HO O OH 5 6 OH

Many of the synthesized compounds possess various CNS-activities. For example compounds 1 and 2 manifest promising antiparkinsonian activity; compounds 3-5 possess analgesic activity; compound 1 has high antiepileptic activity. The deciding influence of the absolute configuration of the tested compounds on theirs activities was shown.

The authors are grateful to the Presidium of RAS (program 24.8) and Russian Foundation for Basic Research (grants 10-03-00230a and 11-03-00010a) for financial support.

WATER SORPTION ISOTHERMS OF EUCALYPTUS KRAFT LIGNIN AND COMPOSITES

N. Volkova1, V. Ibrahim1, L. Wadso2, R. Hatti-Kaul1 1 - Biotechnology, Lund University, Sweden 2 - Building Materials, Lund University, Sweden [email protected]

The water vapour isotherms provide the valuable data for characterization of different types of materials. It is known that biodegradation changes the properties of wood and its components [1]. In our work we used a Eucalyptus Kraft lignin as an initial material, which had been treated by Laccase from Galerina sp. HC1 [2] for the modification of lignin. Activated lignin was reacted with branched polyethylenimine and a polysaccharide, respectively, to produce composites 1 and 2. Sorption-desorption isotherms were obtained for these samples by using dynamic vapour sorption (DVS) instrument (Surface Measuring Systems, London, UK). Some of experimental sorption isotherms are presented in a figure below.

243

Experimental results were treated by BET model for water activities up to aw=0.4 in order to calculate monolayer capacity and surface area of samples. GAB model equation had been applied to isotherms for the total range of water activities studied (0-0.95) with a very good agreement between experimental and calculated curves (R=0.999).

References 1. Chirkova J., Andersons B. and Andersone I. “Study of the structure of wood-related biopolymers by sorption methods”, Bioresources, 4(3), 2007, 1044-1057. 2. Ibrahim V, Mendoza L, Mamo G, Hatti-Kaul R. 2011. Blue laccase from Galerina sp.: Properties and potential for Kraft lignin demethylation. Proc Biochem 46: 379-385.

MORPHOMETRIC PECULIARITIES AND AGE STRUCTURE OF POPULATIONS OF RHODODENDRON (ERICACEAE)

O.S. Vologdina Botanical-Garden Institute FEBRAS, Vladivostok, Russia [email protected]

The comparative analysis of supply of Rhododendron dauricum, R. mucronulatum and R. sichotense are based on author data gathered in other parts south Russian Far East. R. dauricum is ecologically plastic species which colonized the territory of Siberia and Far East. The single-head species, R. sichotense is endemic the mountains of Sichote-Alin. For another rhododendron, R. mucronulatum is growing in south and west Prymorsky region. They prefer rocky substrates near mountain summits. Their morphological similarity is not obvious, they are more like each other than they are to any other taxon in Rhododendron. Minimal level of almost all the investigated parameters of R. dauricum, R. mucronulatum and R. sichotense has been noted for the biotope being under the intensive anthropogenic load. The plants from the studied populations realized strategy of more viable progeny formation under the unfavorable influence of environmental factors even in spite of week development of vegetative organs. The populations age structure of populations of rhododendrons with predominance of the plants being in generative state reflects the result of fluctuation of the population structure connected with the action of abiotic and human factors. The limiting human factor is the fire. The influence of environmental factors on populations of rhododendrons was determined by their

244 relative living condition. The frequency of violations in the growth of shoots decreases with increasing distance from the city of Vladivostok (in Prymorsky region). The plants from the studied populations realized strategy of more quantity seeds and more viable progeny formation under the unfavorable influence of environmental factors even in spite of week development of vegetative organs. More wide spread type of the populations age structure of Rhododendron with predominance of the plants being in generative state. In this investigation distribution pattern, ecology, endemism of R. dauricum, R. mucronulatum and R. sichotense in Russian Far East are described.

BIOLOGICAL ACTIVITY OF SAVORY ESSENTIAL OIL IN IN VIVO EXPERIMENTS

A.K. Vorobyova, E.S. Alinkina, L.D. Fatkullina, T.A. Misharina, M.B. Terenina, V.N. Erohin, E.B. Burlakova Emanuel Institute of Biochemical Physics RAS [email protected]

Among natural antioxidants which are of plant origin the important role play essential oils (EO) composed of volatile constituents, extracted from different parts of aromatic plants. In the model experiments the antioxidant properties of many essential oils was shown (Misharina et al., 2009). However there is much less work on estimation of biological activity of EO in vivo. The capacity of thymol, carvacrol and eugenol derivatives was reported to be able to decrease consequences of oxidative stress (Danesi et al., 2008). The superoxide dismutase and glutathione peroxidase from the liver of rats fed thymol or thyme EO with feed were remarkably higher than in control group, and total antioxidant status of rats was higher by 61-71% compared with control (Youdim, Deans, 2000). Essential oils of thyme and savory are of the main components with similar composition, so we believed that the savory EO, which has successfully cultivated in central Russia, will also have biological activity. The aim of the present work is to study the in vivo effect of the antioxidant action of savory EO (Satureja hortensis L.), added with drinking water (1.5 mg/ml) or with feed (2.5 mg/g). The influence of EO on the lifespan of AKR mice with spontaneous leucоsis and some indicators of oxidative stress in these animals were estimated. It was found that savory EO regardless of the method of administration provided significant antileukemic action, increasing the value of latent stage of the disease. There was the difference in starting dates of animal deaths: the control group, it began after 120 days of life, and in the experiment - after 200-250 days. Average life span of mice compared with the control increased by 47 days (20%) when using the EO with drinking water and for 52 days (35%) - with food. Hence, prolonged intake of savory EO at small doses has a preventive effect, recessing the dates of leukosogenesis and mass animal mortality. For a more detailed study of the effect of savory EO on the state of the mice organism some markers of oxidative stress were investigated on 120 (at the end of the latent period) and 180 (at the stage of intensive leukosogenesis) days of the animals life. It was found that the ingestion of savory EO reduced the hemolysis level and MDA amount in erythrocytes of experimental animals, altering the structural state of their membranes, and stabilize the level of saturated and polyunsaturated fatty acids in the liver cells of animals, although the changes found were within the physiological norm. Intake of EO increased oxidative stability of polyunsaturated fatty acids, i.e., improved antioxidant status of mice. These results suggest a promising use of essential oils of aromatic plants containing antioxidants (in particular, savory) in small doses for therapeutic and prophylactic purposes. And because plants containing essential oils are natural components of natural ecosystems, an enrichment of the artificial human environment will positively impact on certain functional systems of the body.

245 THE PROPERTIES OF POLYURETHANE NANOCOMPOSITES BASED ON CASTOR OIL AS POLYOL COMPONENT

N. Vukic1, I. Ristic1, V. Simendic1, S. Cakic2, I. Krakovsky3, J. Budinski Simendic1 1 - University of Novi Sad, Faculty of Technology, Department of Material Engineering, Novi Sad, Serbia 2 - University of Nis, Faculty of Technology, Department of Material Engineering, Leskovac, Serbia 3 - Charles University Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics, Prague, Czech Republic [email protected]

Castor oil is obtaining by extraction of castor oil seeds from plant with botanical name Ricinus communis. Approximately 90% of its fatty acid content is ricinoleic acid. Due to presence of hydroxyl groups this oil is suitable for polyurethanes preparation, as polyol component. The goal of this work was to investigate the influence of titanium (IV) oxide nanoparticles on the properties of castor oil based polyurethanes. For nanocomposites r value was 1 and they were prepared by premixing the filler particles with the castor oil polyol before reaction in glass wassel with toluene diisocyanate. Polyurethane formation was confirmed by ATR-FT-IR by detection of the urethane −1 band at 1515 cm . Glass transition temperatures (Tg) determined by DSC method of oil based polyurethanes were in range from 13 to 0°C. Dynamic mechanical measurements were performed on a DMA Tritec 2000 (Triton Technology Ltd.) in temperature range from 50°C to 100°C at five different frequencies f (0.31 Hz; 1 Hz; 3.1 Hz; 10 Hz; 31 Hz). It was concluded that addition of nanofiller to samples with the stoichiometric ratio (r=1) influenced decrease of Tg.

CARBOHYDRATES CONTAINING SORBENTS FOR DETERMINATION OF TOXIC METALS

A.V. Vurasko, A.V. Koltasheva, T.I. Maslakova, I.G. Pervova, B.N. Driker, E.V. Mertin Urals state forest engineering university, Ekaterinburg, Russia [email protected]

Now Wood Chemistry is developing successfully direction to create high-performance and relatively inexpensive adsorbents made of agriculture vegetation wastes for both solution environmental problems of industrial regions and quality control of natural objects. The report systematizes information about the development of express analysis system with visual detection (test reagents), which combine the sorption concentration of trace toxic elements and their determination on the matrix surface with hetarylformazanes. As the sorption material was used composition of cellulose received by oxidation-organosolvent method from the husk and straw of rice and oats. The influence of porous structure on adsorption properties of new sorbents was studied. Thus, the cellulose containing supports (CCS) obtained from rice and oats husk are superior in absorbing and sorption properties, swelling ability and water retention of CCS derived from the straw. In addition, due to high content of carboxyl groups (89,8%) immobilized formazanes hold firmly on the CCS from the husk and in contact with aqueous solutions of metal salts form colored complex compounds. The possibility of test determination in wastewater and natural waters mercury (II) and lead (II) using 1-(p-carboxyphenyl)-3-methyl-5-(4,6-diphenylpirimidinyl)formazan on CCS from rice husk was shown. The lower limit of determine concentrations of mercury (II) and lead (II) is 1.5 mg/l. However, since the cellulose from husk consists of short fibers, its low strength characteristics make difficult the use of the sorbent as a support. To improve the strength characteristics the composition has been made on the basis of cellulose obtained from rice husk and oat straw, which stands in the composition as a reinforcing material. It is optimal following percentage - 50% (of total mass) of cellulose from rice husk and 50% cellulose from oat straw. But noted that the immobilized formazane groups are held weakly on these matrices, which causes wash away them by flow of the analyte.

246 At the same time CCS with different strength characteristics can be imposed on each other in the flow cell, in this case due to simultaneous adsorption on every support disc 2-3 elements can be concentrated and then each of them determined by reaction with a suitable organic reagent on a solid phase. The possibility of test determination of mercury (II) and copper (II) in wastewater and natural waters with 1-(p-carboxyphenyl)- and 1-phenyl-3-methyl-5-(4,6-diphenylpirimidinyl) formazans on CCS from rice husk and oat straw was shown. The limit of determine concentrations of mercury (II) is 0.6 mg/l, of copper (II) - 0,5 mg/l. Developed techniques were used to monitor natural waters and snow cover in Ekaterinburg. Accuracy of the procedure is confirmed by atomic absorption method and the "introduced-found". Thus, studies show that by varying of cellulose composition the carbohydrate sorbents can be obtained with certain characteristics for specific practical purposes.

Research work was supported by a grant RFBR №11-03-00181-a.

SPRUCE GALACTOGLUCOMANNANS — NON-CELLULOSIC HETEROPOLYSACCHARIDES WITH TREMENDOUS POTENTIAL FOR NEW APPLICATION AREAS

S.M. Willfor, B.R. Holmbom, A.V. Pranovich Еbo Akademi University, Laboratory of Wood and Paper Chemistry [email protected]

The research on recovery, valorisation, and efficient utilisation of polymeric hemicelluloses, more exactly O-acetyl-galactoglucomannans (GGM), from spruce wood can still be considered rather innovative, the burst in research intensity having started less than 10 years ago. This paper will give a comprehensive view of some of the most interesting results and possible application areas of spruce GGM. In our approach, we are mainly interested in an intact, close-to-native, heteropolysaccharide that still contains most acetyl groups, which are important for a proper water-solubility and ease of handling. Hence, we aim at understanding the extraction, purification, and recovery of GGM on a molecular level to be able to optimise the yield of desired end-products. Both isolation from process waters in the pulping industry and hot-water extraction directly of wood have potential for producing large amounts of polymeric, water-soluble GGM. Although polymeric GGM is in focus, we also have an interest in selective polymer chain cleavage and utilisation of oligomers and monomers as, for example, platform chemicals, building blocks for new polymer materials, bioactive substances, and specialty sugars. Furthermore, selected chemical functionalization alone or in combination with enzymatic treatments has enabled us to introduce exiting properties to the GGM. One great challenge in modification of GGM is that most methods for functionalization have been developed for cellulose, starch, and other non-wood polysaccharides, and hence these methods seldom can be applied without alterations to GGM. Native or functionalised GGMs have then been tested and evaluated in application areas such as, emulsion stabilisation, paper, coating, biodegradable films, microencapsulation of aromas, and so on. Understanding the physico-chemical properties of GGM and the development of suitable analytical techniques have been necessary along the way and will also be discussed and illustrated by a few examples. Sample preparation before analysis is often a limiting factor for thorough chemical characterisation. Most modifications introduce changes in solubility, which makes, for example, molar mass determinations challenging. Following the success of introduction of new functional groups to GGM is also challenging, especially at low DS (degree of substitution) values. To conclude, we want to emphasize that spruce O-acetyl-galactoglucomannans are a valuable source of water-soluble natural polymers with a huge potential for use in renewable materials and as specialty and bioactive chemicals.

247 MOLECULAR COMPLEXATION OF IVY AND LICORICE SAPONINS WITH SILDENAFIL CITRATE

L.A. Yakovishin1, V.I. Grishkovets2, D.Yu. Belash1, I.R. Yarovoy1, E.N. Korzh1, Yu.P. Kopytov3 1 - Sevastopol National Technical University, Sevastopol, Ukraine 2 - V.I. Vernadsky Taurida National University, Simferopol, Ukraine 3 - Branch Campus in Sevastopol, M.V. Lomonosov Moscow State University, Sevastopol, Ukraine [email protected]

Today the complexation of triterpene saponins with biologically active compounds is of great interest because it represents a method for creating low-dose drugs. This approach has already been examined for glycyrrhizic acid, the principal triterpene glycoside of licorice roots. Monoammonium glycyrrhizate (glycyrram) is used as anti-inflammatory and antiallergenic drug. We examined some of the most common triterpene glycosides of plants from the family Araliaceae Juss. as promising complexants. These included the glycosides -hederin (hederagenin 3-О--L- rhamnopyranosyl-(12)-О--L-arabinopyranoside) and hederacoside C (hederagenin 3-О--L- rhamnopyranosyl-(12)-О--L-arabinopyranosyl-28-О--L-rhamnopyranosyl-(14)-О--D- glucopyranosyl-(16)-О--D-glucopyranoside). They were discovered in different species of genus Hedera. Triterpene saponins -hederin and hederacoside C are the components of the cough medicines hedelix, prospan, pektolvan Hedera helix and others. We prepared complexes of -hederin, hederacoside C, and glycyrram with sildenafil citrate. Sildenafil citrate (viagra) is one of the most widespread drugs for treating erectile-dysfunction today. The composition of the complexes was determined by method of isomolar series. IR and UV spectroscopy confirmed that intermolecular interactions exist between saponins and sildenafil citrate. We examined the effects of -hederin, hederacoside C, glycyrram, sildenafil citrate, and their complexes on the fish Poecilia reticulata (Poeciliidae).

DESIGN OF CATALYTIC PROCESSES FOR BIOFUELS PRODUCTION

V.A. Yakovlev1, M.V. Bykova1, A.A. Smirnov2, V.O. Dundich1, V.N. Parmon1 1 - Boreskov Institute of Catalysis 2 - Novosibirsk state university [email protected]

Today, fossil fuels such as coal, oil, and natural gas provide more than three quarters of the world’s energy. However at present renewable feedstock attracts attention due to increasing of fossil fuels cost and its graceful irretrievable consumption. At that, now the technologies level of biomass processing into engine fuels is lower than oil-refinery industry. This is a main reason of higher prime cost of bio-fuels production. Bioethanol and biodiesel are produced from food raw materials. Bio-fuels competition with food sector plays negative role for bioenergetics progress. So, for biofuels production increasing scientific society has to not only improve present biotechnologies, but develop new biomass processing technologies with widening of renewable feedstock list, including wood and agricultural waste. The new catalytic technologies of biomass processing should play a key role in the bioenergetics evolution. In Boreskov Institute of Catalysis the intensive investigations are carried out in the field of biodiesel production in the presence of heterogeneous catalysts, high-cetane fuels production from biodiesel and plant oils directly, upgrading of bio-oil – product of wood flash pyrolysis, production of bio- syn-gas and carbonaceous materials. The specificity of the work is development of new effective catalysts, adjusted to renewable feedstock. The one of developed technology is based on conjugated catalytic processes of transetherification and mild hydrocracking.

248 Main features of developed technology are: 1). biofuel production of two types; 2). biodiesel and green diesel; 3). varying of biodiesel and green diesel yields depending needs; 4). optimization of hydrogen consumption; 5). energy-supply of both stages via burning of gaseous products, produced on 2nd step. The bio-oil, which is a product of flash pyrolysis of grinded wood, is another perspective feedstock for the petrol production. However bio-oil cannot substitute traditional gasoline and diesel in the internal-combustion engines on its own owing to their lower operational properties. The main reason is the high oxygen content in above mentioned bio-fuels. Bioethanol and biodiesel can be used as the additive to gasoline and diesel correspondingly while bio-oil requires catalytic elimination of oxygen from it and simultaneous saturation by hydrogen. It should be pointed out that one cannot use traditional hydrocracking catalysts for oil-refinery at hydrotreatment of bio-fuels because of low sulfur content in original feedstock. The main reason of these phenomena is reduction of the sulfided Co- or Ni- containing active center to the metal state, followed by coke formation and the catalyst deactivation. When so, sulfur is removed from the catalysts and the target products are contaminated by sulfur. Thus, the objective of the present investigation is to develop non-sulfided catalysts for upgraded bio-fuels production. The obtained upgraded products can be used as additives to fossil crude-oil in the standard oil-refining. Catalytic process development is carried out within FP6 BIOCOUP project.

INVESTIGATIN OF MORPHOLOGICAL COMPOSITION OF SOLID DOMESTIC WASTES OF SAINT-PETERSBURG IN 2001-2009

D.S. Yakshilov1, A.V. Musatov2, O.V. Ischenko1, A.A. Ageeva1, E.V. Karelina1, V.N. Mochna1, A.V. Garabadjiu1, G.V. Kozlov1 1 - Saint-Petersburg state institute of technology (technical university), St-Petersburg 2 - Branch of the Federal State Unitary Enterprise, St. Petersburg [email protected]

Average annual fraction composition of banked solid domestic wastes (SDW) is presented in the table. Denomination of the Content in wt%. by year fraction 2001 2002 2003 2004 2005 2006 2008 2009 Paper and cardboard 22,1 20,6 19,6 15,6 15,9 15 18,5 15,6 Food wastes 30,9 35,8 34,2 29,8 29,4 27,3 25,8 28,7 Wood 3,1 1,8 2,2 1,4 4,6 6,2 2,8 6,1 Textile 5,5 6 5,5 8,8 6,7 7 7,5 7,1 Leather and rubber 1,0 1,9 1,5 1,8 2,2 2,2 2,2 1,0 Plastics 12,4 11,2 11,2 11,3 13,7 13,6 18,7 12,6 Bone 1,6 1,7 1,6 2,5 0,4 0,9 1,3 0,6 Ferrous metal 3,2 2,4 2,9 3,4 3,9 3,1 0,6 2,5 Non-ferrous metal 0,3 0,1 0,1 0,1 0 0 0,1 0 Glass 10,2 10 11,9 13,3 11,5 11,9 13 10,1 Stones 2,7 1,1 1,1 2,5 1,8 1,8 2,5 1,5 Other material - - - - 2,3 2,6 3,9 5,7 Siftings 7,0 7,4 8,2 9,5 7,6 8,4 3,1 8,5 The total 100 100 100 100 100 100 100 100

The main components of MSW St. Petersburg are food waste, paper, polymers, glass. Humidity of 50-57% solid waste, organic matter 61,0-62,1%, density 164-150 kg / cubic meter.

249 EFFECT OF INITIAL TEMPERATURE ON THE SELF-HEATING SOLID WASTE DURING COMPOSTING IN A DRUM REACTOR

Based on many years of observations drawn diagram allows to determine the duration of delay is a mechanized composting process in the reactor drum. Chart allows you to schedule the performance of factories mechanized processing MSW.

Note - the temperature inside the shop does not fall below +5 °.

PHYSICAL AND THERMAL PROPERTIES OF POLYURETHANE BINDERS ON TALL AND SEED OILS BASE

V. Yakushin, U. Stirna, M. Misane, I. Sevastyanova, D. Vilsone Latvian State Institute of Wood Chemistry, Riga, Latvia [email protected]

In recent years, interest for tall and seed oils as a renewable raw materials for polymer synthesis, increased dramatically. It is known variety of synthesis methods [1] of reactive products based on fatty acids which are basic component of mentioned oils. Among them, several syntheses of fatty acids amides and polyamide-urethanes [2] take prominent place. These studies usually tend to investigate in detail the properties of specific polyurethanes without comparison with properties of similar polyurethanes based on amides or esters of other oils.

250 The present work deals with comparison of the properties of polyamide-urethanes, based on tall, rapeseed, sunflower and castor oils amides with properties of polyester-urethanes, based on similar esters of the same oils. In case of polyurethanes based on tall oil polyols was also made an estimation of rosin acids content influence. To prepare fatty acids amides of mentioned oils diethanolamine was used in synthesis of polyols at 140 °C. To prepare esters of the same acids was used triethanolamine in synthesis at 175 °C. Synthesis continued to achieve a desired acid (amide) number of polyol. Molar ratio of fatty acids and amine was varied. Polyurethanes in the form of free films (ASTM D 4708-99) were prepared based on the synthesized polyols and polyisocyanate Voratec SD 100 (functionality 2.7). Chemical structure of polyols and polyurethanes was revealed by IR-spectroscopy. Gas Pycnometer AccuPyc 1340 (Micrometrics Instrument Corporation) was used for measuring density of obtained polyurethanes. Density of all investigated polyester-urethanes was higher than density of the similar polyamide-urethanes, sintezed from the same oils. Density of all the polyurethanes increased with increasing of hydroxyl groups’ content in the polyol. The glass transition temperature of polyurethanes was determinated by DSC 851e (METTLER TOLEDO). Glass transition temperature of polyurethanes slightly increased with hydroxyl groups’ content growth in the polyol. Glass transition temperature of polyester-urethanes based on tall and castor oil was lower than of similar polyamide-urethanes. Moreover, it slightly decreased with increasing of rosin acids content in tall oil. Glass transition temperature of polyester-urethanes based on rapeseed and sunflower oils are slightly higher than of similar polyamide-urethanes. Thermal stability of polyurethanes was studied by TGA/SDTA 851e (METTLER TOLEDO) in air atmosphere at the heating rate of 10 °C/minute. The initial decomposition temperature (the temperature of 5% weight loss) of polyester-urethanes was higher than the decomposition temperature of polyamide-urethanes. Growth of hydroxyl groups' content in polyol caused slight decrease of polymers’ initial decomposition temperature. The char yield at 600 °С also was higher for polyester-urethanes. Several other parameters used to characterize the thermal stability of polymers (temperature of 10% weight loss, first maximum polymer decomposition temperature, second maximum polymer decomposition temperature, char yield at 700 °С) changed in similar way. Water absorption (ISO 62:2008) of investigated polyamide-urethanes was less, than water absorption of similar polyester-urethanes. For all polyurethanes, it decreased with increasing of hydroxyl groups’ content in the polyol. In case of polyurethanes based on tall oil polyols water absorption also decreased with increasing of rosin acids content.

REFERENCES 1. F. Seniha Güner, Yusuf Yağci, A. Tuncer Erciyes. Polymers from triglyceride oils. Prog. Polym. Sci., 31, p.633–670 (2006). 2. Suman Yadav, Fahmina Zafar, Abul Hasnat, Sharif Ahmad. Poly (urethane fatty amide) resin from linseed oil—A renewable resource. Progress in Organic Coatings, 64, p. 27–32 (2009).

NEW ANALGESIC DRUGS BASED ON HYDROXYETHYL STARCH SOLUTIONS

N.K. Yurkshtovich1, A.V. Ivaniutsina1, S.A. Beliaev2, N.Y. Shevchuk1, V.N. Gapanovich3 1 - Institution of General and Inorganic Chemistry of the National Academy of Sciences of Belarus 2 - The Research Institute for Physical Chemical Problems of the Belarusian State University 3 - UE "LOTIOS" [email protected]

The development of durable action drug forms which are able to produce therapeutic concentration of active drug in human body and to maintain it during long periods of time is of great interest nowadays. The most acceptable polymers for injection durable action drugs are biodegradable

251 modified natural polysaccharides which macromolecules don’t contain any structural moiety that is capable to exert toxic effect on human body. The aim of this work was to investigate the processes of interaction of non-steroid anti- inflammatory drugs and hydroxyethyl starch in water solutions and to determine the influence of molecular mass and concentration of polymer and viscosity of the solution on the release kinetics of active drug to the simulated biological liquids and also to develop the composition of analgesic injection durable action drug form. As a therapeutical substances ketorolac trometamine, paracetamol and analgene being well known to possess analgesic, anti-inflammatory and febrifuge actions were chosen. Hydroxyethyl starch with molecular mass range from 130 to 450 kDa was used as a cross-linking agent providing durable analgesic action of therapeutic substance due to high viscosity of solutions and dosated distribution of therapeutic substance in spatial grid. The results obtained of the study of release kinetics of ketorolac tromethemine, paracetamol and analgene from hydroxyethyl starch solutions with concentration of polymer ranging from 3,0 to 10,0 wt.% to the physiological solution were the evidence of the pore-diffusion type of desorption kinetics, i.e. the limiting stage of sorbate transportation from the polymer solution phase to physiological solution was diffusion in polymer and the determining factor was the properties of the polymer. This fact was confirmed by the calculating of the effective diffusion coefficient (Deff) describing polymers and their solutions permeability and characterizing diffusion properties of the solutions containing hydroxyethyl starch. The introduction of hydroxyethyl starch to the solutions of ketorolac trometamine, paracetamol and analgene was shown to reduce the values of Deff in 1.52, 1.14 and 1.48 times respectively comparing to initial drugs’ solutions.

Fig.1 Kinetic release (F) curves of ketorolac trometamine and hydroxyethyl starch solutions depending on time (t1/2), where: 1 – 0.0 wt.%, 2 – 3,0 wt.%, 3 – 6,0 wt.%, 4 – 10,0 wt.% polymer concentration. Based on the conducted study a new composition of analgesic injection durable action drug containing non-steroid anti-inflammatory drug, HES and additives having optimal effect of durable action was developed.

A NEW ANTICANCER DRUG BASED ON POLYSACCHARIDE PHOSPHATES

T.L. Yurkshtovich, V.A. Alinovskaya, P.M. Bychkovsky, N.V. Golub, A.A. Kladiev, R.I. Kosterova, S.A. Beliaev The establishment of the Belarusian State University, "Research Institute of Physico-Chemical Problems" [email protected]

The purpose of this work is the creation of intraperitoneally systems with prolonged-release of prospidinume providing increasing its therapeutic activity.

252 Prospidinum is an alkylating antineoplastic agent and has been used for the treatment of different types of cancer, such as larynx cancer, skin reticulosis, bladder cancer and other. The phosphate starch and dextran as a carriers of immobilized prospidinum efficiency is due to the fact that they are non-toxic, biocompatible and biodegradable materials and have their own anti-tumor activity. The comparison of the sorption of the prospidinum by samples of the phosphate starch and dextran with different content of phosphate groups and the swelling degree was studied. These studies were carried out depending on the solution concentration, pH and time of the sorption process. It was istablished that Na-form phosphate dextran (PD) with swelling value (160 - 180 g/g) is the optimal polymer bearer for prolonged form of prospidinum. Prospidinum derivatives with PD and phosphate starch (PS) in H-form which contain a therapeutic dose of the drug in the hydrogel collapse in water. Under in vitro and in vivo conditions the comparative evaluation of antitumor effect of polymer- form prospidinum with different weight ratio polymer : prospidinum was carried out. It was found that the insertion of prospidinum into phosphate polysaccharides leads to halving of IC50 values (numerically equal the concentration that causes 50% inhibition of cell proliferation). That is the cytostatic activity of the drug in the form of a hydrogel is higher than the original cytostatic. The differences of antitumor activity of drugs with different mass ratio prospidin: phosphate polysaccharide = 1: 1 – 5 were not found. In vivo preclinical studies of white rats with implanted sarcoma M-1, sarcoma Jensen and hepatoma Seidel have shown, that the system with controlled release of prospidinum provides substantial cytostatic antitumor activity increase in comparison with original form and prolonged therapeutic action.

HYDROGELS BASED ON POLYSACCHARIDE PHOSPHATES AS DRUGS CARRIERS

T.L. Yurkshtovich, N.V. Golub, N.K. Yurkshtovich, V.A. Alinovskaya, R.I. Kosterova, P.M. Bychkovsky The establishment of the Belarusian State University "Research Institute of Physico-Chemical Problems" [email protected]

Medical-biological characteristics of polysaccharide phosphates (low toxicity, biogegradable) open a possibility to use its in medicine as drug carriers, absorbable surgical sutures. The ability of phosphorylated starch and dextran to forming hydrogels is promising for producing systems with controlled release of drugs. The purpose of the research was to prepare phosphate of starch and dextran by reaction of polysaccharides with a phosphoric acid in molten urea under vacuum, to study their structure, physicochemical and medicobiological properties. In this work the degree of substitution of phosphate (DSP) and carbamide groups (DSC) controlled by the molar ratio of polysaccharide: phosphoric acid: urea, the reaction temperature, pressure, and time. As a result, a series phosphate of starch and dextran in form of hydrogels with DSP 0,30 -1,10 and DSC 0,20-0,92 have been prepared. In general, with a given phosphorus content in the products of phosphorylation, values of their yield in the form of gel-fraction are increasing when lowering concentration of water in the reaction mixture. Polysaccharide phosphates were analyzed by infrared spectroscopy, scanning electron microscopy, viscometry, potentiometric titration, elemental analysis, gravimetric method. The chemical structure of the polysaccharide derivatives was determined by means NMR31P spectroscopy as well as by method of potentiometric titration. Besides dibasic and monobasic monophosphate groups, diphosphate groups were formed under the reaction conditions used. It was established that the formation of hydrogels is mainly due to the presence of monobasic mono-and diesters, which leads to intermolecular cross-links. It was shown, that received hydrogels (yield - more than 92%) are characterized of high values of the swelling degree (2000 – 18820 %) and have exchange capacity 1,1 – 6,0 mg-eqv/g.

253 It was established that polysaccharide phosphates belong to a class of low-toxic substances, and their LD50 is about 5000 mg/ kg. The evaluation of antitumoral activity of all polysaccharide phosphates in vitro and in vivo was conducting by experts of N.N. were conducting by experts of Respublican Scentific and Practical Center for Oncology and Meddical Radiology of N. N. Alexandrov. The antitumor activity in vitro of phosphate dextran and starch was evaluated on culture of tumor cells Hella. On the basis of the coefficients of antitumor action it was shown that cytostatic activity of starch and dextran phosphates have dose-dependent nature. At the fixed concentration of polysaccharide phosphates the ability to inhibit of tumor cell proliferation is increasing with increasing content of phosphate groups. In vivo studies was shown, that dextran and starch phosphates inhibited growth of the experimentally-induced tumors in rats (sarcoma M1, Jensen sarcoma, hepatoma Seidel).

NEW METHOD FOR SYNTHESIS OF SUCCINIC ACID DERIVATIVES

D.N. Zakusilo, O.S. Yuzikhin Saint-Petersburg State Forest-Technical Academy [email protected]

Derivates of 2,3-bis(arylmethyl) succinic acid are an important kind of lignans, as many of them either have a significant biological activity or are the key precursors for the synthesis of other biologically active compounds [1]. The anhydrides of (R,R)-2,3-bis(arylmethyl) acids play a special role into this group since they are the key intermediates for the synthesis of such compounds. Specifically (±)-matairesinol and (±)-secoisolariciresinol, showing anticancer activity, were synthesized through the intermediate formation of anhydride of the (R,R)-(2,3-(4-hydroxy-3- methoxy)-dibenzylsuccinic acid [2], a series of compounds against HIV-1 integrase was obtained from 3,4-dimethoxy derivative [3], 3,4-bis[(4-hydroxyphenyl)methyl]-dihydro-2(3H)-furanone with high luteolytic activity was prepared from anhydride of 2,3-bis-(4-hydroxyphenyl)succinic acid [4]. All described in the literature methods for the synthesis of these anhydrides either include lots of steps [2] or produce the target products in low yields [5]. We suggest the new method for the synthesis of substituted succinic acid anhydrides included just two steps.

o O O 10% Pd/C, 50 C, Methanol, O O COOH + COOH O R H2 excess , 7bar, 1ml/min PbO2-CF3COOH-CH2Cl2 . H H -e O R R R R O R

Ia,b,c + . I a,b,c IIa,b,c IIIa,b,c R = 2-F (a), 4-F (b), 4-MeO (c)

At the first stage arylsubstituted cinnamic acids (Ia,b,c) were oxidised with PbO2 in system CF3COOH-CH2Cl2 to corresponding bislactones (IIa,b,c) [6]. The used oxidising system allowed not only to receive these compounds with high degree of conversion (50–90 %), but also gave the possibility to oxidaze the cinnamic acids with electron-withdrawing substitutents in an aromatic ring. Obtained bislactones were then reduced by 10 % Pd/C (Methanol, H2 excess, 7 bar, 1 ml/min) by flow-type hydrogenation on H-Cube instrument (Thales Nano, Hungary). It is necessary to notice that the anhydride is formed at once during the hydrogenation and don’t need an addition cyclization step of 2,3-diarylmethylsuccinic acids. The yields of target products (IIIa,b,c) were above 90%, and average reaction time for such reduction were 10 min.

1. Geoffrey D. Brown and Ho-Fai Wong. Total synthesis of (±) maculalactone A, maculalactone B and maculalactone C and determination of the absolute configuration of natural (+) maculalactone A by assymmetric synthesis // Tetrahedron, 2004, Vol. 60, N 25, pp. 5439–5451.

254 2. Fuqiang Zhu, Wenling Li, Qian Wang, Zijie HouRegioselective Oxidative Coupling Approach to the Synthesis of (±)-Matairesinol and (±)-Secoisolariciresinol // Synlett, 2006, N 11, pp. 1780–1782. 3. Ryan A. Reinke and coll. Dicaffeoyltartaric Acid Analogues Inhibit Human Immunodeficiency Virus Tipe 1 (HIV-1) Integrace and HIV-1 Replication at Nontoxic Concentrations // J. Med. Chem., 2002, Vol. 45, N 17, pp. 3669–3683. 4. Neelima and A. P. Bhaduri. Syntheses of 3,4-Bis[(m- or p-substituted-phenyl)methyl]- dihydro-2(3H)-furanones & 2,3- Bis(m- or p-substituted-benzyl)-butane-1,4-diols // Indian Journal of Chemistry, 1984, Vol. 23B, N 3, pp. 209-217. 5. Yoko Takei, Kenji Mori and Masanao Matsui. Synthesis of dl-Matairesinol Dimethyl Ether Dehydrodimethylconidendrin and Dehydrodimethylretrodendrin from Ferulic Acid // Agr. Biol. Chem., 1973, Vol. 37, N 3, pp. 637–641. 6. O.S.Yuzikhin, A.V.Vasil’ev, A.P.Rudenko. Oxidation of aromatic compounds: VIII. Oxidative dehydrodimerization of cinnamic acid derivatives in the system CF3COOH- CH2Cl2-PbO2 // Russian Journal of Organic Chemistry. 2000. Vol. 36, N 12. pp. 1743 – 1753.

DESIGN OF DOUBLE ACTION DRUGS

N.S. Zefirov Moscow State University [email protected]

DEVELOPMENT OF ALTERNATIVE ENERGY IN STEPPE ZONE OF UKRAINE

T.Y. Zhavoronkova, I.N. Ostapko, O.M. Shevchuk Botanical Garden, National Academy of Sciences of Ukraine [email protected]

Ukraine belongs to the countries experiencing power shortage (internal resources cover demands in energy carriers only to 53%, import amounts 75% of the necessary volume of the natural gas and 85% of the crude oil and oil products), therefore the production of fuel out of renewable resources is very important (Geletukha and others, 2005; Rakhmetov, 2007). Nowadays due to biomass (mostly wood fuel) Ukraine covers nearly 0.5% of demand in primary energy carriers (~1 mln t u.p.). Biomass (without the share, used by other economy sectors) can provide nearly 17-20 mln t u.p./year or 8-10% of general demand in primary energy. The use of such quantity of biomass is equal to increase of domestic production of fuel to 20% (Geletukha and others, 2005; Rybalka, 2006; Kaletnik, 2008). A number of scientists of Ukraine studied the world and national trends of bioenergetics development, to define economic aspects of the use of crops of agriculture and other raw materials while producing different types of biofuel in Ukraine, to define problems of bioenergy production and perspectives of national biofuel industry formation (Shchokin and others, 2001; Grabov and others, 2002, 2003; Dubrovin, 2004; Geletukha and others, 2005, 2006; Dolinskii and others, 2005; Marchenko, 2006; Gavrik, 2007; Zerkalov, 2007; Rybalka, 2007; Kaletnik, 2008; Melnik and others, 2008).

255 Ground-climatic conditions in the majority of regions of Ukraine are favourable for cropping with the high level of energy storage of biomass during their growth. But so far the priority energy crops for biofuel production have not been defined. One of the most prospective type of biofuel is the biodiesel fuel on the basis of rapeseed oil. The South-East of Ukraine (Donetsk oblast, Luhansk oblast) is situated in the area of forb-sheep’s fescue feather-grass steppe and characterized by severely continental climate with severe temperature variation with little amount of precipitations. The kinds of Brassicaceae species, which are in the list of prospective species for biofuel production, endure very bad the sequence of thaws, ice crust, sharp temperature reduction, that is why during no-snow winters, charactertistic of the region, they, as a rule, freeze out. Besides, Brassica napus var. oleifera DC, is to be grown with watering in conditions of dry climate of the South-East of Ukraine. To solve the problem of biofuel in the region it is necessary to find specialized plants species with high level of oil, which will be able to produce guaranteed crops of biomass and seeds for biofuel production. In Donetsk Botanical Garden, National Academy of Sciences of Ukraine, in order to define and research species, prospective for biofuel production in conditions of Ukraine in 2008 the collection of technical crops, which includes 142 examples, 64 species and 47 kinds of 47 genera and 15 families has been created. The research of 37 species, 25 kinds and 3 hybrids of energy plants of 26 genera and 10 families makes it possible to ground the availability of the use for biodiesel production under conditions of dry steppe such species, as Silybum marianum (L.) Gaertn., Carthamus tinctorius L. (as alternative Brassica napus var. оleifera DC. f. annua Metzg.,) і Oenothera biennis L. (as alternative Brassica napus var. oleifera DC f. biennis Metzg.),which are characterized by high adaptation to growth in conditions of dry steppe, high seed productivity (13.65; 15.65 and 33.82 centner/ha respectively) and high amount of oil (30, 32 and 31%), and also sustainability to pests and diseases.

SYNTHESIS OF ETHYL ETHERS 4-(3-ALKALOID(AMINO)-2,5-DIOXO-2,3,4,5- TETRAHYDRO-1Н-PYRROLYL)BENZOIC ACID

T.S. Zhivotova, A.H. Zhakina, M.Y. Kurapova Institute of Organic synthesis and Coal Chemistry of Republic Kazakhstan [email protected]

Substitution derivates 4-aminobenzoic acids and their ethers, being synthetic analogues of natural connections, are of interest as potential biologically active materials with a various spectrum of action. With the purpose of reception of new biologically active derivatives 4-aminobenzoic acids, containing in the structure it is padding pyrrolydonen a cycle and fragments of biogenic secondary amines – morpholine and piperidine and alkaloids – anabasine and cytisine, we carry out synthesis of ethyl ethers 4-(3-alkaloid(amino)-2,5-dioxo-2,3,4,5-tetrahydro-1Н-pyrrolyl)benzoic acid (1-4) interaction of ethyl ether 4-aminobenzoic acids with furan-2,5-dione with the subsequent nucleophilic addition of amines under the following schema: O

C2H5OOC NH2 + O C2H5OOC NHCOCH=CHCOOH

O (A)

O O N +TsOH HN C H OOC N C2H5OOC N 2 5

O O (B) (1-4)

256 N HN = ON(1); N (2); N (3) ; N (4) N O

At interaction equimolar quantities of ethyl ether 4-aminobenzoic acids and furan-2,5-dione in the environment of acetone at ambient temperature it is formed 4-(4-ethoxycarbonyl)phenylamino-4- oxobut-2-enoic acid (A) with a yield of 91%. At heating (A) at presence of 4- methylbenzenesulphonic acid at a mix of dimethylformamide – toluene occurs ring formation to formation ethyl-4-(2,5-dioxo-2,5-dihydro-1Н-pyrrolyl)benzoate (B) with a yield of 93%. At action on (B) equimolar quantities of secondary amino in dioxane at 70-90 0С there is a formation of ethyl ethers 4-(3-alkaloid(amino)-2,5-dioxo-2,3,4,5-tetrahydro-1Н-pyrrolyl)benzoic acid (1-4) to a yield of 65-80%. Yields of connections (1-4) depend on electron-donating properties of substituents and from conformational hardness of cycles in molecules initial alkaloids and secondary amines. Connections (1-4) represent powdery substances well soluble in organic solvents, but not water soluble. The structure and composition of the received connections (1-4) are proved by data IR-, NMR 1Н- spectroscopy, the element analysis.

A NEW CATALYTIC PROCESS OF PRODUCTION OF ANTHRAQUINONE CATALYST FOR DELIGNIFICATION OF WOOD

E.G. Zhizhina, V.F. Odyakov, L.L. Gogin Boreskov Institute of Catalysis, SB RAS [email protected]

Catalysis by heteropoly (HP) compounds is an intensively developed direction of catalysis. The Mo-V-P HP acids (HPA, H3+хPMo12-хVхO40) hold a prominent place among HPA because their reduced forms (НmHPA) are able to be oxidized with O2. Thus, HPA are reversibly oxidants. We have shown that organic compounds of different classes can be oxidized with high selectivity (90- 99%) in the presence of the HPA solutions [1]. Catalytic processes of oxidation of substrates (Su) are combined from two stages (1)+(2) proceeding in different reactors. The target reaction (1) usually proceeds at 40-70C. The catalyst regeneration (2) goes at t > 140С and O2 pressure. m m m /2 Su + /2 H2O + HPA  /2 SuO + НmHPA (1) m m НmHPA + /4 O2  HPA + /2 H2O (2) The HPA solutions have bifunctional (oxidative and acidic) properties. It permits us to use them as bifunctional catalysts in the process of anthraquinone (AQ) production [2]. Acylation of benzene by phthalic anhydride according Friedel-Krafts reaction followed by cyclization of ortho-benzoylbenzoic acid is the main industrial process of AQ preparation. However, a problem of excessive acid catalysts utilization exists in this process. In another industrial process based on 1,3-butadiene addition to 1,4-naphthoquinone, concentrated alkalies, high boiling organic solvents, and strong inorganic oxidants are used. A growing demand for AQ and its derivatives cannot be supplied with archaic technologies of their manufacture. We have developed a new one-pot process of AQ production in the presence of the HPA solution in 1,3-butadiene atmosphere [1]. AQ can be produced from hydroquinone (HQ) by scheme (3)+(4) or 1,4-naphthoquinone (NQ) by scheme (4) at 80С and P=1 at. In that, we have joined the acid- catalytic reaction of diene synthesis with oxidation of adducts into one technological stage. Our new process is pollution-free owing to ability of the HPA solution to repeatedly regeneration.

OH O O O

HPA HPA HPA (3) + + -2e, -2H + -4e, -4H HQ BQ NQ O O O OH 257

O O O O

HPA HPA HPA (4) + + -2e, -2H+ -2e, -2H

O O O O NQ THA DHA AQ In the mild conditions, a mixture of AQ and its partly hydrogenated derivatives, 1,4,4a,9a- tetrahydro-9,10-anthraquinone (THA) and 1,4-dihydro-9,10-anthtaquinone (DHA), is generated in processes (3)+(4). The AQ yield from NQ in scheme (4) reaches 60%, and it is equal to 20% from HQ in scheme (3)+(4). It is important that reactions (3)+(4) proceed without organic solvent. The mixture of slightly soluble AQ+THA+DHA is practically quantitatively separated from the HPA solution by filtration. Studies in Siberian Scientific-Research Institute of Wood and Pull-and-Paper Industry (Bratsk, Russia) have shown that the AQ+THA+DHA mixture is the effective catalyst for delignification of wood.

References: [1] E.G. Zhizhina,V.F. Odyakov, M.V. Simonova. Kinetika i Kataliz. 2008. V. 49. No. 6. P. 814. [2] E.G. Zhizhina, M.V. Simonova, V.V. Russkikh. Kataliz v Promyshlennosti. 2005. No. 1. P. 12.

STUDYING BIOLOGICALLY ACTIVE COMPOUNDS OF FRUIT PLANTS IN NORTHERN KAZAKHSTAN

S.E. Zhumabaeva Kokshetau state university, biology department, Kokshetau, Kazakhstan [email protected]

In forest and forest-steppe zones of Northern Kazakhstan wild-growing plants are spread: cherry (Cerasus fruticosa (Pall.) G. Woron.), strawberry (Fragaria viridis L., F. vesca L.), raspberry (Rubus saxatilis L., R. idaeus L.), black currant (Ribus nigrum L.), bird cherry (Padus racemosa L.), brier (Rosa spinosissima L., R. cinnamomea L.), etc., relict species: cranberry (Oxycoccus palustris Pers.), bilberry (Vaccinium myrtillus L.). Here are grown up some introduced species of fruit plants: shadberry (Amelanchier rotundifolia), a bird cherry (Padus virginiana), cherry (Cerasus nomentosa (Thunb.) Wall.) and Cerasus besseyi Bailey). The biologically active substances, among them phenolic compounds, present in fruits of wild- growing plants in the definite quantitative correlation. They have various physiological effect on a human body. Fruits of the listed species of plants are widely used in food and in national medicine. However, the balanced combinations of chemical substances can change in the selection course. It quite often leads to loss of nutritious and medical properties of a plant product. Phenolic compounds of investigated fruits consist of flavonoids and phenolcarbonic acids. Flavonols are the glycosides of quercetin and caempferol. The quercetin glycosides are rutin, hyperin, avicularin, quercitrin; the derivatives of caempferol: caempferol-3-rutinoside and caempferol-7-glicoside. In fruits of species raspberry (Rubus saxatilis) flavonols aren't found out. Flavans in fruits are presented free catechins: (+)catechin, (-)epicatechin, epicatechingallat, condensed catechins and proanthocyanidins. The greatest amount of free and condensed catechins is defined in fruits of a cherry Cerasus besseyi, the least – in fruits of a raspberry (Rubus saxatilis). Among phenolcarbonic acids in fruits contain chlorogenic (caffeic-chinnic) and para-coumaric- quinnic acids. Cherries (Cerasus fruticosa and C. besseyi) are rich in these substances. The least quantity of phenolcarbonic acids is in fruits of Rubus saxatilis. It is known, that the listed phenolic substances possess a broadwide pharmacologic and therapeutic properties. Such phytochemicals as rutin, quercitrin, catechins, proanthocyanidins have anti- angiogenic and antisclerotic effect. They inhibit free-radical reactions.

258 Phenolcarbonic acids and condensed catechins influence on the work of a liver and a gastroenteric path. Proanthocyanidins and catechins of various condensation degree have antioxidant, radioprotective, antitumor, anticancer action, protective effects against chronic diseases. Flavonoids (+)catechin and (-)catechin have high activity in vitro against a human immunodeficiency virus (HIV). These data explain a great interest of scientists to biologically active polyphenols and to searches of potential sources of these substances in wild-growing and cultural plants. In leaves of the studied plants is revealed 12 green and yellow pigments: chlorophyll a and chlorophyll b, β-carotin, xanthophylls – neoxantin, violaxantin, anteroxantin, lutein, seaxantin and several no identified carotinoids. The leaves of Rubus saxatilis often are damaged by fungi infection. Comparison of such leaves and healthy leaves has shown that in the infected leaves the maintenance seaxantin and lutein is raised. Thus, the fruit plants are a potential sources of biologically active phytochemicals as nutrients and medicinal drugs.

STUDY OF ANTITUMOR AND ANTIOXIDANT ACTIVITY EXTRACT OF FENUGREEK IN EXPERIMENTAL ANIMALS

V.V. Zhylenko1, S.P. Zaletok2, L.I. Ostapchenko1 1 - Taras Shevchenko Kyiv National University of Kyiv, Kyiv, Ukraine 2 - R.E. Kavetsky Institute of Experimental Pathology, Oncology and Radiobiology NAS of Ukraine, Kyiv, Ukraine [email protected]

Proper nutrition is known to play an important role in cancer prevention. Numerous epidemiological studies have shown that a diet high in fruits and vegetables is associated with reduced risk of most cancers. Different plant polyphenols appear to have anticarcinogenic and antitumor effects. Fenugreek (Trigonella foenum graecum L.) is one of the plants with a rich variety of biologically active substances and is used, not only, as a spice in cooking but sometimes for treating some diseases. The aim: to study antitumor effect of the Fenugreek and its influence on some indices of antioxidant system in tumor-bearing animals. Materials and methods. Experiments were carried out on the mature CDF1 female mice with intraperitoneally grafted ascites L1210 lymphoid leukemia and P388 lymphocytic leukemia, mature C57Bl/6 female mice with intramuscularly grafted Ca755 mammary carcinoma and non-inbred female rats with subcutaneously grafted Walker W-256 mammary carcinosarcoma. The first group (control) obtained standard mash and the second group (experimental) obtained the mix of Fenugreek extract powder (250 mg/kg of body mass) and standard mash. Animals were administerd with the extract from the day of tumor grafting up to sacrifice. Antioxidant activity of fenugreek extract was evaluated by the level of malone dialdehyde (MDA) in liver and the level of diene conjugates (DC) in blood plasma. Antitumor activity was evaluated by the index of tumor growth inhibition. Results. It was shown that the consumption of fenugreek extract led to significant (48%) inhibition of Ca755 carcinoma growth and some less (25%) – for L1210 leukemia, versus the control animals. At the same time, antitumor effect was not educed in animals with W256 carcinosarcoma and with P388 lymphocytic leukemia. It was found that level of MDA and DC in all tumor-bearing animals was higher than in corresponding intact animals. Intake of fenugreek extract decreased these indices in all groups of animals. The greatest decrease of MDA level was observed in animals with L1210 lymphoid leukemia and Ca755 mammary carcinoma (55% and 37%, respectively), in animals with lymphocytic leukemia P388 level of MDA was decreased by 27%, and in animals with mammary carcinosarcoma W256 was decreased, but the difference versus control animals were unreliable. Conclusions. Thus, these results show that further study of anticancer and antioxidant properties of extract fenugreek can be prospective for practical oncology.

259 EVALUATION OF EUGENOL ANTIOXIDANT PROPERTIES AND ITS CONTENT IN SPICES USING CYCLIC VOLTAMMETRY

G.K. Ziyatdinova, E.R. Giniyatova, H.C. Budnikov Department of Analytical Chemistry, Kazan (Volga Region) Federal University, Russia [email protected]

Eugenol (2-methoxy-4-(2-propenyl) phenol) is the principle chemical constituent of clove oil (Eugenia aromatica) and has been used for decades in dentistry for its analgesic properties. H3CO

HO This substance has been displayed anti-inflammatory and anti-bacterial activities as well as other pharmacological properties such as neuroprotective, anticancer, anti-ischemic, antihistaminic and anti-anaphylactic effects. Eugenol acts as an antioxidant and is widely used as preservative additive in foodstuff and cosmetics. Therefore, eugenol is of interest for the evaluation of its antioxidant properties. Antioxidant effect of eugenol as for all phenolic compounds is caused by ability to easy oxidation. This behavior allows to use electrochemical methods in particular voltammetry for evaluation of eugenol antioxidant properties and its quantitative determination in different samples. Cyclic voltammetry of eugenol has shown one irreversible oxidation step with half-wave potential of +0.6 V in presence of 0.1 М Triton X100 in 0.1 М LiClO4 in 10 % ethanol. The oxidation potential characterizes the reducing power (antioxidant properties) of eugenol and its ability to donate electrones. The anodic current corresponds to the concentration of eugenol. Calibration graph is linear in the range of 0.02÷1 mM eugenol and limit of detection - 0.01 mM. So far as the main source of eugenol is spices, its content has been determined. Preliminary extraction of eugenol from spices with ethanol has been developed. The maxima recovery has been archived by single extraction for 10 min. The spice/extragent ratio depends on spices nature. 3 mL of ethanol on 1 g of spice has been got for clove and nutmeg and 6 mL per 1 g – for cinnamon, bay leaf and basil. The highest content of eugenol has been obtained in clove (48±3 mg/g) and cinnamon (12.3±0.7 mg/g) that corresponds well with literature data. Eugenol concentration in other spices was 0.71±0.08, 0.40±0.05 and 1.23±0.07 mg/g for nutmeg, bay leaf and basil, respectively. The results obtained have shown that eugenol displays antioxidant properties comparable with well- known polyphenolic antioxidants. Eugenol content in spices has been evaluated using voltammetric method that could be used for some dietary recommendations for population as well as for design of new foodstuffs.

SOME PROPERTIES OF GREY ALDER HEMICELLULOSES BASED OIL-WATER EMULSIONS

J. Zoldners, A. Meija-Feldmane, L. Stiebra Latvian State Institute of Wood Chemistry, Riga, Latvija [email protected]

Hemicelluloses (HC) represent a considerable part of wood substance, in most cases, 16-30% from the mass of the material. In the resent years, there has been considerable interest in the application of HC in different spheres – food, cosmetic remedies and medicine as thickeners, stabilizers, emulsifying agents and biologically-active additives. Our task was to investigate the emulsifying properties of grey alder HC for their possible application in the food industry or preparation of hygienic remedies.

260 The HC were isolated by extraction of wood sawdust with 7% KOH during 3 h at 20oC. After the extract neutralization with acetic acid, the HC were isolated as water- insoluble (WIS) and water- soluble (WS) fractions, with the yield approximately 5-6 and 10-12%, calculated on the oven-dry wood. Suggar analysis demonstrated that the main component of HC was xylan (94-97%) with an admixture of rhamnose, arabinose, mannose and glucose. The influence of the WS and WIS fraction concentration in the water phase, deformation rate, presence of electrolytes (NaCl, CaCl2) and saccharose, solution pH, and temperature on the olive oil emulsions’ viscosity and stability in time was investigated. It has been demonstrated that, practically in all cases in logarithmic coordinates, emulsions’ viscosity versus deformation rate represent straight lines, which allows determining viscosity at the deformation rate equal to 0. For both HC fractions, the emulsions’ viscosity and stability sharply increase with HC concentration in the water phase till the critical concentration, exceeding which the obtaining of an emulsion is impossible. For the HC WIS fraction and the WS fraction, this concentration corresponds to about 8% and 9-10%, respectively, in the water phase. On the other hand, it is impossible to prepare emulsions, containing more than 80% by volume oil phase. The emulsions are comparatively stable at storing during 20-25 days. After that period, the beginning of some destruction of the emulsion by microorganisms was observed, which can be prevented by introducing about 10% of EtOH in the water phase. It has been demonstrated that emulsions are practically reversible at heating to the temperature 60-65oC. The emulsions are resistant to the electrolyte at the NaCl concentration in the water phase till 8%. The introduction of CaCl2 at comparatively low concentrations increases the emulsions’ viscosity, but it is impossible to obtain emulsions at the CaCl2 concentration above 2.5% in the water phasetaking in account some cross- linking effect induced by this additive. The emulsions were not stable at lowering pH of the water phase below 4.5, because the changing of the charge of acidic groups of HC. The introduction of saccharose till 15% in the water phase increased the emulsions’ viscosity, but did not influence its stability till the beginning of the attack of the fungus. Further experiments have demonstrated that alder HC can be used for obtaining comparatively stable emulsions upon using aromatic plant oils - lavender, fir, pine, orange, Australian tee-tree oil and menthol oil at different proportion of the components commonly used as components of cosmetic and hygienic remedies.

FEATURES OF THE COMPONENT COMPOSITION OF ESSENTIAL OIL OF FILIPENDULA ULMARIA (ROSACEAE) IN DIFFERENT PHENOLOGICAL PHASES OF PLANT DEVELOPMENT

I.D. Zykova, A.A. Efremov Siberian Federal University, Krasnoyarsk [email protected]

The study of medicinal and aromatic plants is the most important challenge facing the physiology of plants under conditions of innovative technologies. Herb Filipendula ulmaria (L.) Maxim has long been used in official and folk medicine to treat a wide range of diseases. Currently underway resource research, which focuses mainly on resource productivity F. ulmariae. In this case, important issues such as varying the content of certain biologically active substances in the raw material depending on the time of collection, source of raw materials, places of growth and weather conditions are at present not fully investigated. In connection with this work objective was to study the component composition of essential oil of aerial parts of F. ulmariae in different phases of plant development using the method of gas chromatography-mass spectrometry. Studies conducted in 2010 in natural populations of F. ulmaria in vicinity of Krasnoyarsk. Aboveground part of F. ulmariae collected during dry weather in the phase of forming rosettes of leaves, stem growth, budding, flowering and fruiting. Essential oil from the aboveground plant parts were obtained by exhaustive gidroparodistillyatsii from air-dry raw material. Component composition of oil was determined by using the method of gas chromatography-mass spectrometry (Agilent Technologies 7890 A). 261 Samples of oils are easily movable fluids which are heavier than water. They have intensive blue colour. Essential oil of aerial parts of plants blooming phase turn completely amorfous at a temperature about18-20 °C. Studying the dynamics of accumulation of essential oil in aboveground phytomass F. ulmaria showed that the highest oil content has a phase of budding plants, after which the oil yield decreases. Chromatography-mass spectrometric method for studying samples of essential oil of F. ulmaria revealed the presence of more than 100 components, most of which we have identified. Composition and quantitative content of essential oil components in different phases of plant development is rather variable, but in all the studied phenophase is detected salicylaldehyde and methyl salicylate. Almost in all samples were present bornyl acetate, α-bisabolol, mintsulfid and chamazulene. Contents chamazulene during the phases of vegetation, budding and flowering plants were relatively stable and amounts to 1.7-1.9 % in the fruiting phase of its content droped to 0.4 %. The main components of essential oil into the phase of formation of rosette leaves of the plant were bornyl acetate (28.1 %), α-bisabolol (10.8 %), caryophyllene (3.1 %) and chamazulene (1.8%). In the phase of stem growth was observed relatively high content of salicylaldehyde (57.2 %), the amount of methyl salicylate - 16.3 %. Salicylaldehyde and methyl salicylate containing 5.2 % and 1.9%, respectively, were part of the essential oil phase of budding, the main component of which can be considered bornyl acetate (19.5 %). The essential oil in the fruiting phase contained salicylic aldehyde (9.3 %), methyl salicylate (7.4 %), borneol (6.7%), caryophyllene (1.8 %) and bornyl acetate (2.0 %). Synthesis of methyl salicylate begins at the earliest stages of plant development and reaches a maximum in the flowering phase (up 18.7 %), with the greatest amount of it at this time is contained in the inflorescences (28 %). As a result of the work done was set the component composition of essential oil of overground parts of F. ulmaria, which grows in the vicinity of Krasnoyarsk, in different phenological stages of plant development.

262 PHYSICAL-CHEMICAL ANALYSIS OF ORGANIC COMPOUNDS OF PLANT ORIGIN

PROTEIN IDENTIFICATION WITH FOURIER-TRANSFORM INFRARED SPECTROSCOPY

A.P. Bayunov, S.N. Smarygin Russian State Agrarian University - MTAA K.A.Timiryazev [email protected]

Protein identification for raw material quality control is an abundant issue in the food industry. The application of Fourier-transform mid- and near infrared spectroscopy to protein classes identification possibility has been researched. Infrared spectra of all protein samples have been detected in the mid (attenuated total reflectance) and near infrared (diffuse reflectance). We used inter-material distances and distance ratios for method comparison which seem to be the most informative parameters [1]. The near infrared spectroscopy has shown significantly higher specified material distance ratio values for each sample referred to the sample chosen as the reference-point than the mid infrared (shown on a figure). In addition, near infrared spectra repeatability has been significantly higher than mid infrared spectra repeatability. It shows that diffuse reflectance near infrared spectroscopy is more informative than the mid infrared.

50 45 40

35 30 25

20 near infrared near 15

10 5 0 0.5 1 1.5 2 2.5 mid infrared

Optimal number of replicates has been defined. To generate and validate model for the individual protein samples identification, 20 replicates (10 for model generation and 10 for validation) for each of 23 samples have been made. Samples of the same type have overlapped. In the next phase the model for protein type identification has been generated. Samples belonging to the same types have been grouped into classes. Protein types are: functional animal protein, animal protein, soy flour protein, pig skin linking protein concentrate, animal linking protein isolate, soy protein isolate, soy meal protein. To validate the model 10 spectra for each individual sample have been used. Every sample has been identified and referred to its type. The following method gives possibility to identify protein type. Individual protein sample identification is also possible. Model stability and identification efficiency is affected by functional and structural difference [2], sample homogeneity and instrument performance stability. All IR- spectrometers are affected by different factors that result in the intensity and wavelength shifts. It is desired for IR-spectrometers to have an option that could to maintain wavelengths and spectrum intensity. This function should be supplied by measuring of a known sample spectrum and defined

263 by wavenumber calibration, instrument lineshape and ordinate accuracy. Application of such an option improves identification efficiency.

V. I. Dvorkin. Metrology and Quality Assurance of Quantitative Chemical Analysis, Moscow: Khimiya, 2001, 263 p. V. P. Krischenko. Near Infrared Spectroscopy, Moscow: Firm Agrotech, 1997, 638 p.

INFLUENCE OF CATALYSTS ON THE THERMOGRAVIMETRIC PARAMETERS OF THERMAL DEGRADATION OF PLANT MATERIAL

V.A. Beliy, E.V. Udoratina Institute of Chemistry, Komi Science Centre, Syktyvkar, Komi Republic, Russia [email protected]

A promising and widely used process of transformation of lignocellulosic biomass into different types of energy is its thermochemical conversion, the species which is pyrolysis of plant materials.To optimize this process recently used catalysts increase speed of chemical reactions, selection of which allows you to adjust the yield products of pyrolysis. It is important to understand the processes of thermochemical transformations of plant material during its pyrolysis. For this purpose widely used methods of differential scanning calorimetry (DSC) and thermogravimetry (TG). In this paper, the process of thermal (23-500oC, heating rate 10oC×min-1) samples of plant origin (spruce, birch sawdust and hydrolysis lignin) was model on the device simultaneous thermal analysis STA 409 PC Luxx фирмы NETZSCH (Germany). Studied the effect of catalysts and activators (KCl, CaCl2, ZnCl2, NiCl2, AlCl3, KHSO4, Mn2O3) on thermogravimetric process parameters (temperature of the beginning and end of thermal degradation, the mass loss of samples). It was establish that the use of acid type catalyst solution for pyrolysis of sawdust reduced the value of the mass loss of 4-5%, and does not affect the mass loss of lignin. Impregnation of wood raw material AlCl3 solution helps reduce the temperature range of pyrolysis to lower temperature values and temperature range of pyrolysis lignin slightly increases. Use to impregnate samples of plant material solution KHSO4 more pronounced effect on to thermal degradation of hydrolytic lignin, which leads to a shift in the temperature range of its intense decay towards higher values. Mineral acids, formed during the pyrolysis of lignin with the addition of acidic activators may lead to cross-linking of the polymer, which increases the temperature threshold for the beginning of its destruction. Used as a catalyst powder Mn2O3 especially did not affect in the process of thermal degradation of the samples.

COMPOSITE MATERIALS BASED ON CARBOXYMETHYLCELLULOSE WITH CLAY NANO-PARTICLES

A.M. Bochek1, N.M. Zabivalova1, V.E. Judin1, I.V. Gofman1, V.K. Lavrentev1, B.Z. Volchek1, E.N. Vlasova1, I.V. Abalov1, N.G. Brusilovskaya2, I.I. Osovskaya2 1 - Institute of Macromolecular Compounds of Russian Academy of Sciences 2 - Saint-Petersburg state technological university of vegetative polymers (SPb STUVG) [email protected]

For the purpose of producing of composite film materials with regulated stress-strain characteristics and new functional properties the rheological properties of aqueous solutions of carboxymethylcellulose (CMC) with additives of nano-particle of montmorillonite (MMT) and bentonitic clay have been studied. The film materials were obtained and their physico– mechanical properties and the structure have been investigated. The decrease of viscosity of systems has been shown to be observed in the range of small (1 – 2 wt %) additives. The observable effect is explained by disruption of spatial system of H- bonds

264 existing in polymer solutions and the possible change of network of macromolecules linkages in a solution, caused by adsorption of a certain part of macro-chains on surface nano-plates. In the obtained composite films nano-plates of MMT and bentonite exist in an exfoliation condition. Fourier IR spectrum of once disturbed total internal reflection have shown that the tendency of displacement of absorption band for Si-O groups from 1040 cm-1 to 990 cm-1 at an increase in MMT concentration in composite films was observed. Such mechanism can be caused as changing in inductive capacity of nano-plate surrounding environment as formation of H- bonds between Si- O groups and functional groups (OH– groups) of cellulose ether. Addition of MMT into NaCMC matrix in amount up to 7 wt % results in an increase of the module of elasticity Е and the forced rubber-like elasticity limit p of films obtained. At higher concentration MMT the decrease in the module of elasticity Е and p were found that gave evidence to the onset of nano-particle aggregation in a polymeric matrix. Approaching to "critical" concentration of nano-particles above which their aggregation can be arisen is fixed by means of IR– spectrum (by displacement of absorption band of Si-O groups in region of low frequencies). However, in the studied interval of compositions the number of aggregated nano-particles is not too large, as a result the change of the nano-plate structural organization (arising of lamellar structures) according to X-ray diffraction in range of small and large angles is not found.

EFFECT OF ANTHROPOGENIC FACTOR ON THE CONTENT OF BIOLOGICALLY ACTIVE COMPOUNDS IN BIDENS TRIPARTITA L. AND POTENTILLA ERECTA L

N.V. Ilyashenko, S.D. Khizhnyak, P.M. Pakhomov Tver State University [email protected]

Application of pharmacological preparations based on chemical components of medicinal plants is increasing. It is caused by a growth of diseases of various nature, when synthetic formulations are not sufficiently effective. It is known that plants accumulate various substances from the environment, and nowdays we observe an increase of a number and amount of different pollutants in atmosphere, water, soil. Thus, investigation of the effect of anthropogenic factor on the biological activity of the medicinal plants is urgently necessary. In this work the influence of environment on the content of phenolic compounds in Bidens tripartita L. and Potentilla erecta L. Raeusch is analyzed. These medicinal plants have found wide application in homeopathy and pharmacology as wound healing, bactericidal and homeostatic preparations. Pharmaceutical effectiveness of these medicinal plants is defined by a variation of biologically active compounds and among them are phenolic compounds, such as flavonoids, catechins, tannins, phenolic acids, etc. The samples for the study are collected in Tver and Tver’s region in places having different human impact. Liquid chromatography, FTIR and UV spectroscopy are used as the main techniques in this work. The IR spectra are recorded on “Equinox 55” spectrometer (“Bruker”), UV spectra of water-alcohol (70%) extracts are registered on “Specord M40” spectrophotometer (“Carl Zeiss”). Total content of water-soluble phenolic compounds in extracts of B. tripartita и P. erecta is evaluated by gallic acid with the Folin-Ciocalteu reactive by spectrophotometric method. Composition of the phenolic compounds in the samples is detected by liquid chromatography (LC) on Alliance 2695 with 2996 PDA (Waters 2998 Photodiode Array Detector; Waters e2695 Separations Module) with a Nova-Pak C18 4μm 3,9 x150 mm Column. By numerous experiments is established that essential differences in IR and UV spectra of the samples are determined by the place, where the herbs grew, the value of human impact. Major changes in IR spectra of the dried water-alcohol extracts of the samples are in the range of ~ 1740 – 1446 cm-1, in UV spectra of the extracts the main differences are observed in the region of 276 – 280 nm for P. erecta and 257 – 332 nm for B. tripartite. Content of some phenolic compounds (arbutin, gallic acid, hydroquinone, rutin) in the samples identified by retention time is determined by LC. Thus, it is established that composition and concentration of biologically active compounds

265 in the studied samples strongly depends on a place of their growth that is confirmed also by the results of optical spectroscopy.

The work is financially supported by the Foundation for the promotion of small enterprises in the scientific-technical sphere, the program «UMNIK», governmental contract № 8754р /14008.

PROPERTIES OF WATER IN NANOSTRUCTURES OF VEGETATIVE SYSTEMS AND DIAGNOSTICS OF A CONDITION OF PLANTS BY IK-SPECTROSCOPY METHODS

V.I. Ivanov-Omskii1, A.V. Gryazkin2, N.V. Kovalev2 1 - Fiziko-technical institute of A.F.Ioffe of the Russian Academy of Sciences 2 - The Saint-Petersburg State Forest Technical Academy of S.M.Kirova [email protected]

The estimation of a condition of plants, their frost resistance and drought resistance is carried out today mainly to qualitative signs (Sanitary rules…, 2007; Forest encyclopedia, 1985; Spurr, etc. 1984; Odum, 1986; F.Ramad, 1981). Meanwhile, the knowledge of such properties of plants allows to carry out purposeful selection of kinds for cultivation in various those or other conditions. It is important not only for agriculture, fruit growing, but also for the enterprises of a or landscape gardening economy but for the forestry as a whole. The estimation of a water mode of plants by means and methods of nanotechnologies allows to change essentially practice and methodology of studying of functional features of separate plants and plant systems. Different kinds of plants can carry out a metabolism (with water participation) in various temperature limits, from – 300 to + 500 C. Water in a liquid form is kept thanks to a dynamic grid of hydrogen bonds. These bonds are strong enough. The amount of energy necessary to breaking grid of a hydrogen bonds is of order of magnitude equal to 5 мэВ (i.e. 1000 C). However water in special conditions can change the properties. It is established that molecular structures of water changes in conditions of confinement into nanoscale cavities. Due to this water (structured water) in vegetative fabrics possesses features – during the winter period at negative temperature it DOES NOT FREEZE. So, according to T.Jamaguchi's Japanese group (P.Smirnov, T.Yamaguchi, S.Kittaka, S.Takahara, Y.Kuroda, J.Phys. Chem. B, 104, 5498-5504 (2000)) water in a capillaries of diameter less than 2 nanometers is stable to temperatures–133 0С that is unattainable for volume water. On the one hand such the behavior of the water at condition confinement and at negative temperatures, determines the mechanism of frost resistance of plants. And on the other hand it specifies in importance research nanosized structures of plant tissues. Also it allows for a find new approach to the studying of functional features of plants, their viability and stability to adverse factors. Processes of withering of plants and their death are connected first of all with change of their water mode. It is necessary to find out in what parity volume water and structured water should be in a healthy, viable plant and what their parity be weakened, impractical one. The infra-red spectroscopy of the wood fabrics containing free and bound (structured) water allows to differentiate not only wood breed on the sample of the minimum size of its structural units, but also to establish a plant condition, its viability at any stage of development. Use nanosize approach at definition of unique properties of water in condition of confinement will allow objectively to diagnose a condition of plants. At accumulation of enough of experimental data there is a possibility of drawing up of a scale of viability of wood plants by results of research of porosity of wood taking into account it Fractal structure.

266 PREPARATION, STRUCTURAL CHARACTERIZATION AND IN VITRO ANTIVIRAL ACTIVITY OF CARRAGEENAN OLIGOSACCHARIDES

A.A. Kalitnik, A.O. Barabanova, A.V. Reunov, V.P. Nagorskaya, I.M. Yermak Pacific Institute of Bioorganic Chemistry, Far-East Branch of Russian Academy of Sciences, Vladivostok [email protected]

Сarrageenans are a family of natural water-soluble sulfated galactans extracted from numerous species of red marine alga. They are composed of alternating 3-linked β-D-galactopyranose and 4- linked α-D- galactopyranose or 4-linked 3,6-anhydrogalactose and have a wide spectrum of biological and physiological activities, such as antiviral, anticoagulant, antitumor, immunomodulatory. Their biological properties depend on the chemical structure of polysaccharides and their molecular weight. Native polysaccharides do not always correspond to the properties required for application in various industrial fields; hence various modifications including depolymerisation have an important value to prepare the samples with necessary properties and to decrease a negative effect on organisms. So requirements to chemical purity and to regulation of their physicochemical properties, such as molecular weight and the position and number of sulfate groups are increased. Also it is important to determine the structural peculiarities, which are primary ones for biological activities of polysaccharides. A number of low molecular weight (LMW) fractions of carrageenans with different structural types were obtained by means of different chemical reagents and also by enzymatic hydrolysis with a specific enzyme. Two samples of carrageenans differing in the positions and number of sulfate groups were used for depolymerisation: kappa-carrageenan isolated from Chondrus armatus and kappa/beta- carrageenan isolated from Thichocarpus crinitus with molecular weights of 250 and 390 kDa, respectively (HMW-carrageenan). o Chemical degradation was performed using free radical depolymerisation with H2O2 at 37 C and mild-acid hydrolysis with HCl at 60oC. The products of the chemical hydrolysis were purified and separated by Gel-permeation chromatography with Bio-Gel P-6 and P-20. The LMW-derivations of carrageenans with molecular weight of 2.3 to 3.5 kDa were obtained as a result of hydrolysis with H2O2, and those (LMW-derivations) with molecular weight of 1.2 to 3.0 kDa were obtained after acidic hydrolysis with HCl. Using kappa- carrageenase from Аlteramonas carrageenovora the enzymatic depolymerisation of kappa/beta- carrageenan was carried out at 37oC and two fractions of polysaccharides with molecular weights of 4.3 and 190 kDa were obtained. By chemical methods and NMR- and IR-spectroscopy the chemical structure of LMW-fractions was determined to correlate with the structure of the initial high molecular weight (HMW) - polysaccharides The comparative analysis of antiviral activity of the obtained LMW-fractions and initial HMW- carrageenans on Tobacco mosaic virus infections in detached tobacco leaves was carried out. All the samples of carrageenans were shown to inhibit growth of local necrosis on tobacco leaves in compare with control leaves on 20-90 %. The antiviral activity depended on the type of carrageenan, so initial (HMW) kappa-carrageenan and their LMW-derivations possessed higher antiviral activity in compare with (HMW) kappa/beta- carrageenan and their derivations. It was shown that the antiviral activity of initial HMW- polysaccharides was higher of that for their LMW-derivations independently of depolymerisation method. The antiviral activity of both kappa- carrageenan and kappa/beta- carrageenan increases with molecular weight. The method of depolymerisation had not any influence on the antiviral activity.

267 THE CONTENT OF BIOLOGICALLY ACTIVE SUBSTANCES IN SALIX SPP. (EASTERN EUROPE): THE PATTERNS OF ALTERATION

N.A. Kuzmichova, O.V. Sozinov Vitebsk State Medical University, pharmaceutical, Vitebsk, Belarus [email protected]

One of the goals of the economic botany is to reveal the populations with the maximal productivity and the highest containing of active substances. It’s clear that total phytochemical analysis of the plant samples of all populations is irrational. Consequently, it’s necessary to search for the patterns of the biologically active substances (BAS) accumulating in the raw medicinal material (RMM). That will enable the prediction of the BAS content, depending on the ecological, coenotic and other factors. We’ve studied the alteration of the phenol compounds in the bark and leaves of 4 species Salix genus: S. acutifolia, S. alba, S. triandra, S. viminalis on the territory of Eastern Europe at the latitude range. We’ve investigated morphological and chemical changes of some species: their individual changes, alteration within a population and between populations as well as the accumulation dynamics of some phenol compounds during the vegetative period. The analysis has resulted with the following data: the BAS accumulation in the most of the studied plants has some M-shaped dependence upon the edaphic and climatic factors. It can be caused by the concurrence of the ways of the primary and secondary metabolism that defines revealed dependence as a basis of physiological adaptation of the plants to the habitats conditions. A strongly marked ancipitate character of model species has a dependence of the content of glycosides luteolin and quertecine on: the sum of temperatures above 10˚ (with a maximum at 1900˚ (the Baltic Sea Coast) and 2500˚ (the Polessye)), the amount of precipitation in a vegetative period – a maximum of 400 and 700 mm for S. acutifolia, for S. alba: 300 and 450 mm. At the biotopical level this dependence is also traced: for S. triandra glycosides of flavonols accumulate in significant amounts in out flood-plain extreme sites, as well as in phytocenosis with Rubus caesius. This dependence has been marked at the level of seasonal changes of BAS as well. As for the content of flavonoids and phenilpropanoids in leaves and in bark of S. viminalis, two maximums of BAS are observed: the first maximum of flavonoids content in the bark occurs to vegetative phase of flowering; the second one to the leaf-fall beginning, with a maximal resource productivity in the middle of vegetative period. At all studied levels the maximal accumulation of BAS is observed in plants, growing in suboptimal or semioptimal conditions. The maximal resource productivity develops under synecological optimum. For instance, S. triandra has the most resource productive populations in a river-bed part of flood-plains (willow-shrubs with Phalaroides arundinacea), whereas high accumulation of BAS (willow-shrubs with Deschampsia caespitosa + Filipendula ulmaria) occurs on a plain with stagnant level of moisture. Since resource and phytochemical maxima do not coincide in model species, it’s practically impossible to reach simultaneously both maximal productivity and the greatest content of active substances in RMM. Thus, it explains the necessity of searching for the resource-phytochemical optimum of collecting raw material which is formed specifically in different ecologically-coenotic conditions within the areal. It is noted that maximal productivity of RMM in model species at the level of taxon areal is formed within the coenoareal (in conditions of synecological optimum), but relatively high content of flavonol glycosides is revealed in the south parts of the areal, while flavon glycosides occur in the north-western part of continuous spreading and aglycones are found along the periphery of the areal. On the basis of resource and phytochemical data analysis, resource- phytochemical optimum of collecting leaves of S. acutifolia was determined in the Baltic countries (maritime climate) on river-bed alluvial ridges and in plain conditions on loose sands; for S. triandra and S. alba it was determined in the steppe zone on high plots of floodplains. Thus, the dependence of accumulation of BAS in RMM has a universal M-shaped dependence at ecotopic, seasonal, different annual and climatic levels, and, presumably, at the level of age structure of populations. This allows making prognosis of populations with resource-phytochemical 268 importance on the basis of knowledge about the position of the population in the system of ecological coordinates of different scales.

MOLECULAR COMPLEXATION OF PARACETAMOL WITH TRITERPENE GLYCOSIDES

A.V. Lekar1, S.N. Borisenko2, L.A. Yakovishin3, V.I. Grishkovets4, N.I. Borisenko1, S.S. Mandzhieva5, S.N. Sushkova5, M.A. Kazmina2 1 - Ecological and Analytical Center, Southern Federal University, Rostov-on-Don, Russia 2 - Institute of Physical and Organic Chemistry, Southern Federal University, Rostov-on-Don, Russia 3 - Sevastopol National Technical University, Sevastopol, Ukraine 4 - Vernadsky Taurida National University, Simferopol, Ukraine 5 - Institute of biology of Southern Federal University, Rostov-on-Don, Russia [email protected]

Paracetamol (para-acetaminophenol) is currently one of the most common medicines. It exhibits analgesic and weak anti-inflammatory activity [1]. It is used independently and in drug combinations. It is insoluble in water. Nephrotoxic and hepatotoxic effects occur with prolonged use. One possible method for reducing therapeutic doses of drugs, increasing their solubility, and expanding the spectrum of biological activity is to form clathrates with plant glycosides [2]. We recently began a study of complexes of hederagenin 3-O-α-L-rhamnopyranosyl-(1→2)-O-α-L- arabinopyranoside (α-hederin, glycoside 1) and its 28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D- glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ether (hederasaponin C, glycoside 2). Triterpene glycosides 1 and 2 are characteristic of plants from various species of the genus Hedera L. Molecular complexes of triterpene glycosides with paracetamol have not been reported. Therefore, we investigated complexation of this drug with 1 and 2. The resulting complexes were characterized by ESI-MS. It was found that paracetamol forms 1:1 complexes with glycosides 1 and 2. The complex of 2 is more stable. The carboxylic acid of 1 is not involved in the complexation. Intermolecular interaction in the complexes occurs through H-bonds involving hydroxyls of the glycoside monosaccharides and O–H, N–H, and C=O bonds of paracetamol.

The work was performed with partial financial support of the CRDF (USA), the RF Ministry of Education under the Russian–American Program Basic Research for Higher Education, and the RF Rosobrazovaniya program Development of the Scientific Potential of Higher Schools (Projects RNP 2.2.2.2.3915(3.8.11), BP4M04, BG1104) and of the Russian Federation President Grant МК- 4425.2011.3.

References [1] M.D. Mashkovskii. Drugs. In 2 Vol., 13th Ed. Kharkov: Torsing. 1997, 2, 163-164. [2] T.G. Tolstikova, A.G. Tolstikov, G.A. Tolstikov. On the way to low-dose drugs. Vestn. Ross. Acad. Nauk. 2007, 77, N 10, 867-874.

COMPARATIVE ANTIRADICAL ACTIVITY OF ISOBORNYL- AND ISOBORNYLOXY- SUBSTITUTED PHENOLS IN DIFFERENT MODEL SYSTENS

L.I. Mazaletskaya1, N.I. Sheludchenko1, L.N. Shishkina1, I.Yu. Chukicheva2, I.V. Fedorova2, A.V. Kutchin2 1 - Emanuel Institute of Biochemical Physics of Russian Academy of Sciences, Moscow, Russia 2 - Institute of Chemistry, Komi SC, Ural Branch of Russian Academy of Sciences, Syktyvkar, Russia [email protected]

The actuality of the detail investigation of the isobornylphenol (IBP) properties in the different systems is due to both the accessibility of the raw materials for their synthesis and the existence of the biological activity for several compounds.

269 The aim of this work was the study of the antiradical activity of 2-isobornylphenol (I) and 2- isobornyloxyphenol (II) in three model systems: the initiated oxidation of ethylbenzene (333 K, Wi -8 -7 = 5×10 l/mol.s), the initiated oxidation of methyl oleate (333 K, Wi = 1×10 l/mol.s) and the interaсtion with the stable free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH). It is established that the rate constant of the reaction for IBP I and II with α-phenylethylperoxy radicals (k7) significantly differ: k7(I)/k7(II) = 6,5, while that difference for certain decreases to value k7(I)/k7(II) = 2 under interaсtion with peroxyl radicals of methyl oleate (RH). It is shown that the low antiradical activity of compound II results from the formation of the intramolecular hydrogen bond between the H-atom of OH-group and O-atom of ortho-oxyisobornyl substituent. This is confirmed by IR-spectroscopy data: the valence vibration frequency of the free OH-group in the IBP II molecule (ν = 3561,6 cm-1) is substantially lower than that for I (ν = 3618,8 cm-1). The diminish of the IBP antiradical activity in the methyl oleate oxidation reaction is associated with the formation of the intermolecular bond of OH-group of IBP with oxygen atom of methyl oleate, the most significant effect is revealed for IBP I. So, the substantial diminish of the intensity of the valance vibration band of the free OH-group and the appearance of the absorption broad band at ν = 3450 cm-1 which is characteristic for the intermolecular hydrogen bonds for OH-group and absent for components is observed in the IR-spectrum of the mixture of the compound I with RH (1:10) in hexane. Distinct from IBP I there is the small broadening of the valence vibration bond of OH-group in IR-spectra of the II and RH mixtures and its intensity is a slight decreased. However, the effectiveness of the compound II is the substantially higher than that for the compound I in reactions of the studied IBP with DPPH in ethanol. Obviously, molecules of the polar solvent (ethanol) destroy the intramolecular hydrogen bond in the compound II and owing to the reactivity of II which contains a more electron-donating substituent as compared with the compound I is becoming a more significant. Thus, the free radical nature and physicochemical properties of the reaction medium cause the substantial influence both on the absolute and relative antiradical activity of the phenolic antioxidants with isobornyl and isobornyloxy substituents. Obtained data allow us to suggest that the effectiveness of IBP molecules of which can form the intramolecular hydrogen bond and characterizing the low antiradical activity in the non-polar media will be increase in the biological systems.

THE ANALYSIS OF OLEANOLIC ACID BY CHROMATOGRAPHY-MASS SPECTROMETRY METHOD

N.V. Mironenko1, T.A. Brezhneva2, V.F. Selemenev1 1 - Voronezh State University, department of analitycal chemistry, Voronezh, Russia 2 - Voronezh State University, department of pharmaceutical chemistry, Voronezh, Russia [email protected]

Under the condition of the wide application of biologically active substances the problem of their standardization gets paramount value. In particular, for the majority of glycoside structures substances their aglicon is used as the standard at the quantitative analysis [1]. Triterpenic saponins, which are oleanolic acid derivatives, also aren't an exception. In view of the standard sample acid absence (as a finished drag), a keen problem occurs as to how one obtains and evaluates its quality using a complex of physic-chemical methods. The conducted experiments have allowed to develop the general algorithm of its obtainment, to analyse the purity of the sample by methods of UV-, IR- spectroscopy, TLC (thin-layer chromatography), to evaluate the physic-chemical indicators (Tmelting, specific rotation). Currently one of the highest sensitive and specific methods of the analysis is the mass spectrometry, especially in combination with a gas or liquid chromatography. Therefore the aim of the present work was the research of the obtained sample of an oleanolic acid by the above- stated method. At the work liquid chromatograph 1100 LCMSD (Agilent Technologies (USA)) with gradient pump Quaterynary Pump 1100 and automatic injector Autosampler 1100 was used. Chromatograph

270 is equipped with the mass spectrometer detector with chemical ionization under atmospheric pressure (APCI). The mass spectrometer detector scanning speed is 0.8 sec/cycle on a full ionic current. The mass spectrums were received in the mass range of 100-1500 Da. The chromatographic analysis was carried out under gradient elution conditions. The eluents were 0.1 % water solution of a formic acid and 0.1 % acetonitrile solution of a formic acid. The chromatographic data were processed by ChemStation A.09.03 program. Fig. 1 shows the obtained mass spectrum of the sample under the negative ionization conditions. *MSD1 SPC, time=2.252:2.312 of X:\GOZUN\RODINA\OMAN_666\CO_OMAN.D APCI, Neg, Scan, Frag: 30

Max: 20768 100 455.4

80 Figure 1. Mass spectrum of the sample

60 oleanolic acid

40 456.4

457.4 0 100 200 300 400 500 600 m/z According to Fig. 1 in a mass spectrum of negative ions the peak (m/z 456.4) identified as aglicon saponins – oleanolic acid [2] was found. Apart from the main substance, the low-level peak (m/z 632) was found (which isn't shown on a spectrum due to the small intensity). This peak corresponds to partially hydrolyzed saponin – 3-3 - [β-D-glucuronopyranosil] - oleanolic acids [3]. The basic substance content in the specimen made up 98 %. This allows to come to the conclusion of the principal possibility for the obtained oleanolic acid to be used as the standard sample. References: 1. The state pharmacopeia of the USSR: V. 2. The general methods of the analysis. Medicinal plant raw material / Ministry of Health of the USSR. – M: Medicine, 1989. – 400 p. 2. Mass spectrometry and a NMR-spectroscopy of curling ivy saponins extracts, obtained in the environment of subcritical water / Borisenko S.N., Tihomirova K.S., Rudnev M. I. and other//Materials of V conference on new technologies and applications of modern physic-chemical methods for environment studying. Rostov-on-Don, 2009, p.105. 3. New Triterpenic Saponins from the Aerial Parts of Medicago Arabica (L.) Huds / Aldo Tava, Mariella Mella, Pinarosa Avato at all. // J.Agric. Food Chem.- 2009.-№57.- p.2826-2835.

ANALYSIS OF BJORKMAN LIGNIN BY MALDI-MS METHOD

D.S. Ryabukhin, A.V. Vasilyev, M.Ya. Zarubin Saint-Petersburg State Forest Technical Academy, Saint-Petersburg, Russia [email protected]

Bjorkman lignin (Picea abies) was analyzed by Matrix-Assisted-Laser-Desorption-Ionization Mass Spectrometry (MALDI-MS). The data shows that lignin contains of oligomers with molecular weight 600 - 4400 Da. The main groups of oligomers have masses 1000-2000 and 2500-3500 Da (Fig.1).

271

Figure 1. MALDI-MS spectrum of Bjorkman lignin (Picea abies).

Additionally, the lignin was treated with superacid CF3SO3H (0C, 2h). The obtained products were analyzed by MALDI-MS. Under the action of superacid lignin is converted into lighter fragments with masses 600 - 1700 Da (Fig. 2).

Figure 2. MALDI-MS spectrum of products of Bjorkman lignin (Picea abies) destruction, obtained under the action of CF3SO3H (0°С, 2 h).

EFFECT OF SEMI-SYNTHETIC ANTIOXIDANTS - ISOBORNYLPHENOLS ON THE STRUCTURAL STATE OF THE MICE BLOOD ERYTHROCYTES

L.N. Shishkina1, O.G. Shevchenko2, S.N. Plyusnina2, A.V. Kutchin3, I.Yu. Chukicheva3 1 - Emanuel Institute of Biochemical Physics of Russian Academy of Sciences 2 - Institute of Biology, Komi SC, Ural Branch of Russian Academy of Sciences 3 - Institute of Chemistry, Komi SC, Ural Branch of Russian Academy of Sciences [email protected]

Substituted phenols synthesized on the natural raw material base and consisting isobornyl group as alkyl substituents are considered as the worthwhile biological active substances. However, the absence of the pronounced correlation between the membrane protective activity of isobornylphenols and their antioxidative properties causes the need a detail study of the mechanism of their effect on membranes in the different systems. The blood erythrocytes is one of the most applied model biological system by practice.

272 The aim of this work is the investigation of the effect for several isobornylphenols (IBP) both on the hydrogen peroxide induced hemolysis of the mice blood erythrocytes and their antioxidative activity and the membrane active properties (a spontaneous hemolysis and morphology of erythrocytes). The following IBP were investigated: 2-isobornyloxyphenol (I), 4-methyl-2- isobornylphenols (II), 2-isobornylphenol (III), 4-methyl-2,6,-diisobornylphenol (IV) and 6- methyl-2-isobornylphenol (V), and also the standard antioxidant ionol (BHT). The intensity of the oxidation processes is evaluated by the amount of products which are reacted with 2-thiobarbituric acid (TBA-RS). The accumulation of the oxidation products of hemoglobin (ratio of oxyHb/MetHb) is spectrophotometrically controlled. All studied IBP and BHT are obtained to inhibit the TBA-RS accumulation in the erythrocyte suspension. Besides, BHT and phenol I for certain inhibit of oxidation of oxyHb in MetHb. The ability of phenols I and IV and also BHT to inhibit the induced hemolysis of the blood erythrocytes at all investigated concentrations (0,001 – 0.1 mM) is revealed. Besides, IBP II, III and in less V showed the cytotoxic effect. By the diminution the cytotoxic effect (the Hb output to the extracellular medium under the erythrocyte incubation with compounds during 10 minutes) studied compounds at concentrations of 0,1 mM form following sequence: II > III > V > I > IV = BHT. The investigation of the surface architectonics of the blood erythrocytes is revealed by using of the scanning electron microscopy the raise of the cell morphological transformation extent with increasing duration of the incubation at the phenol presence to 4 h, that is testified to the ability of IBP and BHT to interact with the erythrocyte membrane. Pronounced hemolytic effect of compounds II, III and V at high concentrations obviously results from the ability of these IBP to penetrate into the inner layer of the erythrocyte membrane. IBP I, IV and BHT stimulating the echinocyte production no cytotoxic effect showed. Thus, the biological activity of IBP is due to both their inhibitory efficiency under the oxidation condition and also their ability to interact with the membrane structures of cell. The model of the hydrogen peroxide induced erythrocyte hemolysis could be used for the first select of the more worthwhile compounds obtained on the natural raw material base to investigate their biological activity.

References 1. Patent No 2 347 661 C2 (RF) 2. Shishkina L.N., Mazaletskaya L.I., Sheludchenko N.I., Kutchin A.V., Chukicheva I.Yu., Shevchenko O.G. Structure of isobornylphenols and their biological activity // Book of Abstacts of VI All-Russian Conference “Chemistry for Waste Management and Management of Chemical Waste. SPb, 2010. P. 345-346.

STRUCTURE AND MORPHOLOGY OF HYDROLYSIS LIGNIN

M.P. Sokolova, T.E. Sukhanova, A.I. Grigoryev, A.A. Kutin, M.V. Mokeev, Yu.N. Sazanov Institute of Macromolecular Compounds of the Russian Academy of Sciences, Saint-Petersburg, Russia [email protected]

Lignin (LG) is a branched heteropolymer of complex structure, whose empirical formula depends on the type of wood, method of its processing, and recovery prehistory. Hydrolysis lignin (HL) differs essentially from the native lignin and it is a waste from hydrolysis industry. Utilization problem of HL is very acute today, because the amount of HL accumulated annually at hydrolysis plants is sufficiently large [1]. In this study, to establish the ways of utilization, we investigated structure, morphology of HLs of different industries using Х-ray diffraction (XRD), scanning electron microscopy (SEM) and nuclear magnetic resonance spectroscopy (NMR). In addition, the influence of the extraction of alcohol-toluene mixture and modification on the structural and morphological transformations have been investigated.

273 It was shown that the morphology of HLs significantly depends on the processing technology and modification method. SEM micrographs of as-prepared HL (Fig. 1a,b) indicate the ground cell wall particles consists of cellulose fibrils with sizes varying from 10 to 200 μm. Morphology of modificated HL is quite different as compared with that of the initial one. It is clearly seen (Fig. 1c,d) that it consists of small oval aggregates with sizes of 5 μm, whereas a small number of larger inclusions about 50 μm in the length can be found in the samples. XRD study of HL reveals the presence of two diffuse reflections at 2θ = 16.5Å and 22.5Å relating respectively to the (110) and (200) reflections of cellulose I. The content of cellulose I in samples depends strongly on the processing technology, which agrees well with those obtained by other methods. In addition, a narrow intense reflection at 2θ = 26.5 Å relating to carbon (002) with a turbostratic structure was found in HL samples. Thus, both way of processing and modification method influence HLs structure and morphology.

Figure 1. SEM images of as-prepared HL (a, b), and modified HL (c, d).

1. Sazanov Yu. N., Gribanov A.V., Russian Journal of Applied Chemistry. V. 83, № 2, 175- 194.

STUDIES ON THE BARK OF THE POPULUS TREMULA

E.V. Stepanova National Research Tomsk Polytechnic University, Institute of High-Technology Physics, Tomsk, Russia [email protected]

It is known that phenolglycosides possess an extensive range of biological activity. Salireposide (1) exhibits an antiviral activity [1], antitumor activity [2], helminthicidic effect, could be useful in treatment of arthritis, and shows inhibitory activity against snake-venom phosphodiesterase [3]. Populosides A (3), B (4), C (5) possess antioxidant activity [4]. Salireposide was found in many plants [5]. Populosides A, B and C were first isolated from Populus davidiana in 2006 [4]. Populoside A was also isolated from P. ussuriensis [6]. Unfortunately there is no information about the presence of populosides A, B, C in other plants of the family Salicaceae. The fact that these substances are not commercially available as standards did not

274 allowed phythochemical researching on the presence of these glycosides in other plants previously. However it turns to be possible after synthesis of these glycosides. Recently we have developed synthetic pathway for some glucosides of 2-acyloxy derivatives of salicyl and gentisyl alcohols (1-5) [7]. Also, there are no published data on desoxysalireposide (2-O-benzoylsalicin) (2), although its structural isomers - tremuloidin (8), populin (6), chaenomeloidin (7) [8], which are 2'-O- benzoylsalicin, 6'-O-benzoylsalicin, 3'-O-benzoylsalicin respectively, were found in the family Salicaceae. H OR H OH H O H O HO O R4 HO R O O R 1 H HO OR H 2 OH H R O 3 H O

1 R=R1=R2=H, R3=COPh, R4=OH 3 R=OH, R1=H 2 R=R1=R2=H, R3=COPh, R4=H HO O 4 R=R1=H 6 R=COPh, R =R =R =R =H 1 2 3 4 5 R=H, R1=OCH3 7 R=R2=R3=R4=H, R1=COPh 8 R R=R1=R3=R4=H, R2=COPh 1 For detection of salireposide (1) and desoxysalireposide (2) GC-MS method was applied. Detection of populosides A(3), B(4), C(5) was carry out by HPLC and TLC methods. GC-MS method found to be unsuitable for analyzing of these glycosides (3-5) (neither acetyl- nor trimethylsilyl-derivatives) because they have low thermal stability. The EtOH-extract of bark of P. tremula and mixture of synthetic glycosides (3-5) were examined by HPLC (at 320 nm and 306 nm) and TLC. All three glycosides (synthetic and natural) were identified by comparing the retention times, Rf, the color reactions with sulfuric acid or diazotired 4-nitroaniline and blue fluorescence after treatment with NH4OH under 365 nm. The presence of glycoside (1) in P. tremula bark was determinate also by compare of GC-MS data of acetylated extract of P. tremula bark and peracetylated glycoside (1). At the same time peracetylated glycoside (2) was not found in the acetylated extract of P. tremula bark. Thus, populosides A, B, C were found in P. tremula bark at the first time. References 1. Van Hoof J., Torre J., Corthout L.A. J. Nat. Prod, 1989, 2, 875-878 2. Lee K. H., Yang M. C. Molecules, 2008, 13, 41-45 3. Ahmad V.U., Abbasi M.A., Zubair M., Fatima N., Farooq U., Choudhary M. I. Helv. chim. acta, 2004, 87, 67-72. 4. Zhang X.F., Thuong P. T., Min B.S. J. Nat. Prod, 2006, 69, 1370-1373 5. Boeckler G.A., et al., 2011, doi:10.1016/j.phytochem, 2011.01.038 6. Si C.L., Kim J.K., Bae Y.S., Li S.M. Planta Med, 2009, 75, 1165-1167 7. 13-th School-Conference for Young Scientists “Current Topics in Organic Chemistry”, Book of Abstracts, Novosibirsk, 2010, 156 8. Mizuno M., Kato M., Misu C., Iinuma M., Tanaka T. J. Nat. Prod, 1991, 54, 1447–1450

THE EFFECT OF STRUCTURAL FEATURES OF CARRAGEENAN AND CHITOSAN ON THE FORMATION OF SOLUBLE POLYELECTROLYTE COMPLEXES

A.V. Volodko, V.N. Davydova, V.P. Glazunov, A.O. Barabanova, V.I. Gorbach, I.M. Yermak Pacific Institute of Bioorganic Chemistry, Far East Division, Russian Academy of Sciences, Vladivostok, Russia [email protected]

Chitosan and carrageenan, marine polysaccharides, possess versatile biological activity and various physicochemical properties. They are widely employed in industry and medicine. Due to their polyionic structure, chitosan and carrageenan can be used for the production various polyelectrolyte complexes (PEC), which give the possibility of creating medical preparation with specific properties. Usually, chitosan-carrageenan PECs are obtained in the forms of films, microcapsules and gels. 275 The purpose of our work is to investigate the process of chitosan-carrageenan soluble polyelectrolyte complexes formation depending on environmental conditions and physicochemical features of primary components. Polycationic chitosan (Ch) with acetylation degree (AD) of 1% and molecular weights (MW) 143 and 11 kDa (Ch-HM, Ch-LM-1), respectively, and chitosan with AD of 11% and MW of 17 kDa (Ch-LM-2) were used for PECs formation. Carrageenans (Car) differing in the position and number of sulfate groups per a disaccharide unit - kappa/betta-, kappa-, iks-carrageenans extracted from red algae families Gigartinaceae and Thichocarpaceae - were used as polyanions. The effects of pH value, concentration and ratio of primary components as well as the structure of carrageenan, MW and AD of chitosan on the complexes formation were investigated. Using the turbidity method we have shown that the process of formation of soluble PECs depended on the concentration, ratios and structure of primary components. Kappa-carrageenan (0.5 mg/ml) formed soluble PECs with Ch-HM at the ratio of Ch:Car from 0.1:1 to 2.5:1 mol/mol, whereas with Ch-LM-1 - from 0.1:1 to 30:1 mol/ mol. The increase of chitosan AD to 11% (Ch-LM-2) was accompanied by the formation of soluble PECs with kappa-carrageenan both at the ratio of Ch:Car from 0.1:1 to 12.5:1 mol/mol and also at the ratio of Ch:Car from 100:1 to 210:1 mol/mol. A similar influence of MW and AD of Ch on the formation of PECs was observed in the case of Cars of the other structural types. The obtained PECs remained stable within 24 hours at pH range 5.0-7.0. The IR spectroscopy confirmed the formation of a soluble chitosan-carrageenan PEC with the appearance of a new absorption band at 1525 cm-1, corresponding to cross-linking –NH3+ groups. The high-speed sedimentation in a percoll gradient was another method to prove the complex formation. It was shown that kappa- and kappa/betta-carrageenans are completely bound with CH- LM-2 and formed two types of complexes with different MW. Their binding with Ch-HM was incomplete and some amount of free components were also registered in the gradient. It is interesting to note that iks-carrageenan with the highest content of SO4 groups was completely bound with all samples of Ch and formed two types of complexes. The binding constants and the number of binding sites of chitosan with carrageenans were determinated. Thus, iks-carrageenan was established to have the highest constant of binding with polycation (K=9.65*107 mol-1), and that was three times as large for kappa- and kappa/betta- carrageenans. The reason for that may be in the chemical structure of iks-carrageenan, i.e. in the high content of sulfate groups. Carrageenans in the PECs with Ch saved their ability to induce synthesis of such cytokines as a tumor necrosis factor alfa and interleukin-6 in human blood cells.

This work was partially supported by the grant of the Presidium of the Russian Academy of Science “Molecular and cell Biology” and grant FEB-UB RUS №09-II-УО-05-001 «Bioglycans: structure and properties».

276 NOVEL DRUGS BASED ON PLANT SUBSTANCES

THE EXPERIMENTAL STUDY OF 2-(1-HYDROXY-4-ISOPROPENYL-1- METHYLCYCLOHEXYL-2-THIO)-METHYLETHANOATE ULCEROGENIC ACTION

I.V. Akulina, L.E. Nikitina, R.S. Garayev, N.P. Artemova, L.Yu. Dorofeeva Kazan State Medical University,Kazan, Russia [email protected]

At the present time about 10 % of Russian Federation population have musculoskeletal joint pathology following by inflammation. The leading pharmacological group used to treat this syndrome is non-steroidal anti-inflammatory drugs. However, together with the positive effect of this group of drugs, there is essential undesirable ulcerogenic effect, limiting their clinical use. Earlier we have shown that 2-(1´-hydroxy-4´-isopropenyl-1´-methylcyclohexyl-2-thio)- methylethanoate synthesized in our laboratory has low toxicity and possesses by anti-inflammatory activity on the level of diclofenac. Purpose of this study was to examine ulcerogenic properties of 2-(1´-hydroxy-4´-isopropenyl-1´- methylcyclohexyl-2´-thio)-methylethanoate obtained. The assessment of the ulcerogenic action was carried out after single drug injection at a dose of 1/5 LD50. 2-(1´-hydroxy-4´-isopropenyl-1´- methylcyclohexyl-2´-thio)-methylethanoate was injected as an aqueous emulsion (as emulsifier was used Tween-80) intragastrically once into rats in volume not to exceed 0.5 ml. The experimental animals were previously deprived of food for 16 hours before beginning an experiment. The comparison group received the diclofenac at doses equated to thioterpenoid toxicity. The control group was injected the water in equivolume. Three hours later after a fluid injection the animals were slaughtered, the stomachs were dissected of the lesser curvature; severity of the effect was assessed using a 4 point scale. An anesthesia was ethaminal sodium at the dose of 50 mg/kg injected intraperitoneally. The evaluation using the Litchfield-Wilcoxon method determined the test substance dose inducing multiple gastric mucosa injuries, which correspond to two points (UD50). The dose was calculated on the basis of variation doses, from minimum dose to dose led to serious injuries covering the entire surface of the gastric mucosa after oral method of the substance injection. After a single injection of the comparison drag, which was the diclofenac, per os at the dose of 142 mg/kg (1/5 LD50) erosive and perforating injuries were expanded covering the entire surface of the gastric mucosa of a rats, that corresponded to 3.7±015 scores according to 4 point scale of the ulcerogenic effect. To the evaluation of this effect the diclofenac at the 48 mg/kg dose causes multiple gastric mucosa injuries, such as erosion, petechial hemorrhages, which match two points (UD50). Studied thioterpenoid at the dose 2000 mg/kg, that corresponds to 1/5 LD50, did not cause grave damages of gastric mucosa. Appearing of mild hyperemia at the gastric mucosa of rats was observed in the drugs application at the fatal dose (5 000 mg/kg); consequently the dose, causing multiple gastric mucosa injuries of rats (erosion, petechial hemorrhages) corresponding to two points, during 2-(1´-hydroxy-4´-isopropenyl-1´-methylcyclohexyl-2´-thio)-methylethanoate application could not be determined. Thus, thioterpenoid 2-(1´-hydroxy-4´-isopropenyl-1´-methylcyclohexyl-2´-thio)-methylethanoate was shown has no ulcerogenic action in contrast to standard non-steroidal anti-inflammatory drug, the diclofenac.

277 THE INFLUENCE OF PROPIONIC ACID (PHENOZAN) AND HYBRID ANTIOXIDANTS, BASED ON PHENOZAN, ON THE COMPONENTS OF ANIMAL CELLS

O.M. Alekseeva1, V.B. Voleva1, I.S. Belostotskaya1, N.L. Komissarova1, N.S. Domnina2, O.Yu. Sergeeva2, E.A. Yagolnik3, Yu.A. Kim4, E.B. Burlakova1, A.N. Goloshchapov1 1 - N.M.Emmanuel Institute of Biochemical Physics, RAS, Moscow, Russia 2 - Chemical faculty of Saint-Petersburg State University, Saint-Petersburg, Russia 3 - Tulsky State University, Russia 4 - Institute of Cell Biophysics, RAS, Pushchino, Russia [email protected]

Phenozan-acid is widely applicable antioxidant and adaptogen; this defines its choice as a base for the production of two sets of hybrid antioxidants - ICHFANs, characterized by “anchor-float” structure, containing onium fragment with lipophilic long-chain alkyl tail; and HMA – macromolecular conjugates with hydrophilic bio- and synthetic polymers. Also, the phenozan dehydrogenated analog - 4-hydroxy -3,5- di-tert-butil-cinnamic acid has been used recently. Such an approach gives rise to substances with certain targets and intensity of action on biosystems. The charged onium group (anchor) and lipophilic long-chain alkyl tail (float), contained in ICHFANs molecules, increase the efficiency of interaction with charged lipid bilayer of cell membranes maintained the required antioxidant state. The hydrophilic HMAs, witch contain phenols fragments covalently bounded with polymer chain, provide the certain distribution of redox-active phenol nuclei. In this investigation, comparison of actions of phenozan and its derivatives to the structural organization and function of animal cellular components was held. The structural effects were studied on two models. Multulammelar liposomes, formed from individual artificial phospholipid, were analyzed by the method of microcalorymetry; soluble protein - serum albumin (BSA), with aid of method of intrinsic fluorescence quenching. The functional changes were tested in erythrocytes by K+-releasing registration using potentiometric method. The results show that the phenozan has the softer action compared with ICHFANs both on membranes and on the whole cells. The destructive concentrations of phenozan are three orders more. The microdomains structure of liposomes membrane breaks down in the presence of testable substances already at active substances concentration 10-6 M. ICHFAN with 16 carbon fatty alkyl tail forms its own microdomains in membrane at such concentration. The soluble protein BSA looses and becomes greatly accessible to water penetration in the presence of large concentrations of testable substances. The protein structure becomes stronger in the presence of low concentrations; the lipophilic tails of ICHFANs adsorb on protein and protect it from water penetration. The degree of protection depends on proportion on tail length. The functional studies bring to light to the bimodal influence of ICHFAN on Са2+-depending activation of К+ releasing from erythrocytes and negligible influence of phenozan. Evidently, ICHFANs, when anchored in membrane, change the lipid phase, that influence to the proteins structure and function. It can be assumed that molecules of ICHFANs are concentrated when anchored in membrane or in protein by means of lipophilic tails. This allows decreasing in the concentration of active substances. The fragments of hydrophilic polymers in HMA molecules “dilute” the phenols concentrations, thus the HMA influences became weaker. The polymers exert the smaller effects itself. The structure of HMA hinders the accumulation of high local active phenol fragments in membrane and protein. Literature: 1 Nikiforov G.A., et al.// Biomed Chemistry. (2005) 51. 413-423; 2 Aref,ev D.V., Belostotskaya I.S., Vol,eva V.B., Domnina N.S., Komissarova N.L., Sergeeva O.Yu., Khrustalevа R.S.// Izvestiya of Academy of Science. Ser. Chem. (2007) 4. 751. “Hybrid macromolecular antioxidant on the basis of hydrophilic polymers and phenols”

278 CYCLIZATION OF ORTHO-FUNCTIONALIZED (BUTA-1,3-DIYNYL)ARENES AS A KEY STEP OF THE APPROACH TOWARD ENDIYNES FUSED TO HETEROCYCLES

I.A. Balova Saint-Petersburg State University, Department of Organic Chemistry, Saint-Petersburg, Russia [email protected]

Since discovery enediyne antitumor antibiotics in the 80-s1 a lot of researches have been devoted to study their chemical and biological properties as well as design and synthesis their analogs2. Synthesis of artificial enediynes was stimulated because of the lack of anthitumor selectivity and powerful DNA-cleaving activity of natural enediynes to understand and modify the biological activity of these toxins. Heterocycles possessing an enediyne system are promising objects for the investigation of general patterns of action and structure-activity relationships. However there is no general method to construct (Z)-3-ene-1,5-diyne system attached to a variety of heterocycles. Reported syntheses of such systems usually include transformation of functional groups to the ethynyl moieties or double cross-coupling of terminal acetylenes with dihalosubstituted heteroarenes, which are not widely accessible. Recently we demonstrated the cyclization of ortho-functionalized (buta-1,3-diynyl)arenes to be a short and efficient route towards heterocycles, having both ethynyl and halogen moieties at neighboring atoms2,3. This approach is promising for the direct synthesis of precursors of enediyne systems fused to various heterocycles. Moreover proposed synthetic methodology towards enediynes can get these connections to advance clearly defined position of substituents at both triple bonds which is important for further enediynes modification. Br R X LG X HBr I2 R z N -HLG -ILG N R I 2 O N=N = X = O, S, NMe, N(Et)Ph = LG = Me, Bn O R' R' o Pdo / Cu(I) R' Pd / Cu (I)

X R

The scope and limitation of the proposed methodology for obtaining of cinnolines, benzannulated S,N,O-five-membered heterocycles, isocumarines will be discussed as well as examples of enediyne systems synthesis. Research is supported by the research grant of Saint-Petersburg State University (12.38.14.2011). 1. K.C. Nicolaou, G. Zuccarello, C. Riemer, V.A. Estevez, W.M. Dai. J. Am. Chem. Soc., 1992, 114, 7360. 2. R.-G. Shao. Curr. Mol. Pharm., 2008, 1, 50. 3. O. V. Vinogradova, V. N. Sorokoumov, I. A. Balova. Tetrahedron Lett. 2009, 50, 6358. 4. N. A. Danilkina, S. Bräse, I. A. Balova. Synlett, 2011, No 4, 517.

279 COMPOSITE MATERIALS BASED ON WATER- SOLUBLE CELLULOSE ETHERS AND POLY-N-VINYLFORMAMIDE

A.M. Bochek, I.L. Shevchuk, I.I. Gavrilova, N.A. Nesterova, E.F. Panarin, V.E. Yudin, I.V. Gofman, M.F. Lebedeva, E.N. Popova, L.M. Kalyuzhnaya, V.K. Lavrent’ev Institute of Macromolecular Compounds of Russian Academy of Sciences [email protected]

In order to make composite film materials with regulated stress-strain characteristics and new functional properties, films have been obtained from aqueous solutions containing mixtures of carboxymethylcellulose (CMC) of different ionization degrees and hydroxyethylcellolose (HEC) with poly-N-vinylformamide (PVFA). Both thermodynamic compatibility of CMC or HEC with PVFA in solid state and composite structure have been investigated. X-ray diffraction patterns for composite films have been shown to be the same as those for the polymer prevailing in the mixture. At PVFA content lower than 50 wt % X-ray diffraction peaks are observed typical for CMC or HEC and at higher PVFA content its own characteristic peaks at angles equal to 2=15 and 2=25 are observed. The solvent vapor sorption method (water sorption), dynamic mechanical analysis (DMA) and thermo mechanics method have been used for investigating compatibility of CMC or HEC with PVFA in solid state. NaCMC has been shown to be compatible with PVFA in the whole range of mixture composition under study. For CMC of intermediate ionization degree (=0.5) polymers are compatible only at CMC content from 0 up to 30 wt %. For HCMC-PVFA mixtures thermodynamic compatibility has not been observed. This effect can be explained by increasing intermolecular interactions between HCMC molecules via non-ionized carboxyl-groups that results in the loss of cellulose ether water solubility. Thus, changing ionization degree of CMC one can vary the composition range for thermodynamically compatible CMC and PVFA. Addition of synthetic PVFA into CMC-matrix leads to decrease in tensile strength and deformation of composite films (they become more brittle). HEC has been found to be compatible with PVFA in the mixtures containing up to 50 wt % of PVFA. Addition of up to 10 wt % PVFA into HEC does not lead to significant change in mechanical characteristics of composite films. At higher PVFA content the Young’s modulus increases (up to 3.18 GPa for 90 wt % PVFA content compared with 2.57 GPa for pure HEC) and elongation at break decreases ( from 17% for pure HEC to 6% for 90 wt % PVFA content composite film). On the whole, HEC-PVFA composite films containing up to 50 wt % of PVFA possess quite satisfactory stress-strain characteristics.

FUNCTIONAL SUBSTITUTED VANILLIN AND VANILLAL DERIVATIVES

E.A. Dikusar The Institute of Physical Organic Chemistry of The National Academy of Sciences of Belarus, Minsk, Belarus [email protected]

Vanillin is contained in significant quantities in the fruits of Vanilla fragrant (Vanilla planifola, Andr. ), its content in fruits dried reaches 3%. At present the large part of the vanillin is obtained by synthetic method from the guaiacol or alkaline oxidation of the lignin – the by-product pulp and paper industry.

280 R2

H N CHO CHO C

OR OR OR

OH OCR1 OCR1 O O 1 R = Me, Et; R = Н, Ме, Et, Pr, Me2CH, Вu, Ме2СНСН2, С5Н11, С6Н13, С7Н15, С12Н25, СН2Cl, 4-МеС6Н4О(СН2)2, (CH2)8CH3, (CH2)16CH3, CH=CH2, C(CH3)=CH2, cis- (СH2)7CH=CH(CH2)7CH3, C6H5, 4-С6Н4СН3, СН2С6Н5, СН2СН(CH3)C6H5, trans-CH=CHC6H5, 1/2 -(CH2)2-, 2-C6H4Cl, 4-C6H4Cl, 2,4-C6H3Cl2, 2,4-СH2OC6H3Cl2, CH2Br, CHBrCHBrC6H5, 4-C6H4Br, 3-C6H4NO2, 4-C6H4NO2, (CH2)2C6H5, CHBrCCl=CCl2, 1 (CH2)2C(O)OMe, C(C≡N)=CHC6H5, C6H3(NO2)2-3,5, 1-Ad, 1/2[4,4 -C6H4-C6H4], CH2CCl=CCl2, 2 (Z)-CCl3CCl=CH, Cl2C=CClCHBr; R = C16H33, C18H37, c-C6H11, C6H5, 1-C10H7, 2-C10H7, 2-C6H4- C6H5, 4-C6H4-C6H5, et cetera.

Vanillin and vanillal, and also iso-vanillin and ortho-vanillin, because of the presence in their molecules of hydroxyl and aldehyde groups are accessible initial compounds for obtaining on their basis the series of the new chemical substances, which possess valuable and useful properties. Use 1 2 of an ester (–CO2R ) and Shiff bases (–HC=NR ) fragments as the linker for the covalent connection to aldehydes of a vanillin series of different functional and farmacoforic groups: aliphatic, cycloaliphatic, skeleton polycyclic, aromatic, 1,2-azolic, carboranic, condensed aromatic syntones and fragments of the structures of both the natural and the synthetic origin, it can serve as the bright example of molecular design.

Cl H C 1 C C C R = C Cl N N R S O C C C H Me Me O High chemical resistance of ester group to the hydrolysis and biological media action makes it possible to soundly consider it most perspective and convenient tool in the field of organic synthesis [1].

[1] The Substituted Benzaldehydes of a Vanillin Series in Organic Syntheses. Obtaining, Using, Biological Activity. / E.A. Dikusar [et al.]. Minsk: “Pravo & Ekonomika”, 2011. – 434 p.

BIOLOGICALLY ACTIVE EXTRACTS OF MULLEIN BLACK (VERBASCUM NIGRUM L.)

S.A. Kalinina, V.M. Petrichenko, B.Ya. Siropyatov Perm State Pharmaceutical Academy, Perm, Russia [email protected]

Mullein black (Verbascum nigrum L.) from the Scrophulariaceae family is widespread in the Urals region. The plant has a large above-ground and below-ground biomass, but as a raw material only corollas of flowers are used the result the majority of plant biomass is lost, so it is necessary to study all parts of the plant and to study their pharmacological activity.

281 The aim of our work was to obtain extractive preparations of various organs of plants and determine their anticoagulant, hypotensive and diuretic activities. To achieve this aim dried plant organs were cut to a particle size less than 2 mm, was extracted with 60% ethanol at a ratio of raw materials - 1:6 extractant, method reperсolation in a battery of three percolator with unequal loading of raw material (20:30:50). Time of infusion in each percolator was 8 hours. Anticoagulant, antihypertensive and diuretic activity in the extract was determined. Anticoagulant activity was tested in vitro using the coagulometer «Minilab - 701 at a concentration of 1 mg / ml, heparin in a concentration of 1 AU/ml was used as the standard. Hypotensive activity was studied in vivo, a solution of papaverine hydrochloride in doses of 3 mg/kg (0.1 LD50) was used as a standard. Diuretic activity was determined on white mongrel male rats weighing 250-300 g. The dry extracts were put into orally at a dose of 50 mg / kg, previously dissolved in 5 ml of water, drugs served as the aqueous extracts of Eqisetum arvense and leaves of Vaccinium vitis-idaea was used as a comparison standard. As a result of studies we have found that extracts from the overground parts (leaves, flowers, stems, grasses) of Mullein black show all kinds of activities, but the greatest pharmacological effect was observed in extracts of grass. The extract significantly slows down the process of blood coagulation in 17.0%, which is comparable with the effect of heparin anticoagulant activity of which is amounted to 22,4%. In the study of hypotensive activity, it was found that lowering blood pressure is already observed in the second minute after injection. Five minutes later, hypotensive activity was 8.4%, while the standard of comparison papaverine reduced the pressure on 9,9%. The duration of action of the extract was 20 minutes, papaverine was acted 7 minutes. Diuretic effect of the extract of the herb Mullein black observed within 6 hours. Increased urine output for first 3 hours was 158% with the putting into of the extract of Eqisetum arvense - 83%, with the putting into of Vaccinium vitis-idaea extract - 217%, and 6 hours after administration of the extract Mullein diuretic was 246% with the putting into of an extract of Eqisetum arvense - 100%, with the putting into Vaccinium vitis-idaea extract - 269%. Thus, in the course of our investigation it was found that extract of the herb Mullein black has three kinds of pharmacological activities: anticoagulant, antihypertensive and diuretic, which is prospectively for the treatment of patients with hypertension. As well as the development of new dosage forms of the herb Mullein black, tablets, capsules and films.

BIOLOGICALLY SIGNIFICANT PRODUCTS OF PLANT RAW MATERIALS DEEP CHEMICAL MODIFICATION - DIHYDROQUERCETIN

G.Z. Kaziev, M.P. Koroteev, T.S. Kuhareva, A.M. Koroteev, E.E. Nifantyev Moscow State Pedagogical University [email protected]

Presently our department is conducting innovative scientific research which is of obvious interest for the national economy. Here we mean the development of new routes of synthesis, obtaining and investigation (medical and biological) of new compounds, namely, aromatic peracilic compounds of dihydroquercetin, with a higher degree of purity and enhanced bioactivity. We synthesized and investigated: (I) –pentaacetylsalicylate-, (II)-penta-n-nitrobenzonate-, and (III)-penta nictinate- of dihydroquercetin.

O N O C CH 5` O C O 3 5` 6` 4` 6` 4` O C NO O O 2 1 O H3C C O 8 3` N 5` 8 1 O C O 7 9 O 2 6` 4` O C 3` O2N C O 7 9 O 2 1` O C O 1` O C NO N 2` 1 O 2` 2 8 3` 5 4 3 C O 7 9 O 2 5 4 3 O 6 O 1` O C 6 10 2` 10 N 5 4 3 O 6 O O O C NO2 O O O C 10 O C CH 3 O C O O C O O O O C O O C O H C C O O C CH3 3 N O O NO2 I II III 282

The synthesized compounds have been tested in the Russian Military Medical Academy. The test results are presented in the application for an invention “A group of dihydroquercetin peraciliccompounds, methods of obtaining (preparation) and application” 29.04.2009, inc.022178, reg.2009116183. Much attention was paid to dihydroquercetin phosphorylation and obtaining dihydroquercetin - based sulphur- and selenium-derivants.

According to the data of the Cancer Detection Centre of the Russian Medical Sciences Academy the obtained preparations perform well in destroying tumors being non-toxic for human beings. One of these preparations characterized by a high antiproliferative activity on human tumor cells in vitro and by an evident antitumoral action on some transplantable tumors of mice was patented (№2349317). Having a number of unique biological properties has one drawback – its poor solubility in water at room temperature. We met the challenge and solved this important medical problem by finding a special way out. We managed to encapsulate dihydroquercetin into a polysaccharidic pouch and to prepare a new watersoluble inclusion complex compound dihydroquercetin according to the reaction: С15Н12О7 ·3Н2О + С42Н70О35 · 6Н2О → С57Н82О42 · 9Н2О dihydroquercetin β-cyclodextrin inclusion complex HO

OH HO O O O O OH HO HO O O OH OH O HO OH OH HO O O HO OH HO HO OH O O O OH OH 5' O 4' OH O OH 6' 1 HO O 8 3' HO O HO 7 9 O 2 OH OH HO 1' OH OH OH 2' O OH + O 6 10 3 OH OH OH 5 4 OH O OH OH O OH OH O O OH O OH OH OH O H OH O OH O O OH OH O H 3 C O OH 2 HO C H O C C 4 HO C 5 CH OH 1 O 2 H H 6 OH

It was noticed that watersolubility of this new supramolecular compound (dihydroquercetin-β- cyclodextrin) as compared with free dihydroquercetin (0.3g/l) and with free β-cyclodextrin (18.5g/l) has notably increased (53.2g/l). It was also found that individual dihydroquercetin gets combined with membranes and practically does not enter the cells. At the same time dihydroquercetin enters cells at doses within several hours, in other words, it is a slow-release drug. In 2.5 – 3 hours after the introduction of pure dihydroquercetin and its complex with dihydroquercetin - β-cyclodextrin as food additive was found in blood plasma of rats only in the experiment where the preparation was used. It follows that the introduction of the above-mentioned complex provides an effective conduction of dihydroquercetin into bloodstream. When pure free dihydroquercetin is introduced into rat’s stomach it is being accumulated in liver and at high concentration it can produce allergy an other complications. Thus, the use of dihydroquercetin holds the greatest promise in medicamentous terms as compared with the use of pure dihydroquercetin. The work has been patented in the Russian Federation.

283 DEVELOPMENT OF DRUG FILM BASED ON BIOLOGICALLY ACTIVE SUBSTANCES WITH POLYMERS

Ye. Kim, S. Rakhmadiyeva, Ye. Eskeldinova L.N. Gumilyov Eurasian National University, Department of Chemistry, Astana, Kazakhstan [email protected]

One of the most promising forms of drugs is a polymeric film. Transdermal system in the form of a film is convenient because it is glued directly on the skin. Diffusing out of the system of biologically active substances (BAS) penetrate through the skin, reaching the skin vessels and spread throughout the body [1]. Medicinal films of polymers are well kept, there are prolonged, ensure dosing accuracy and consistency of concentration of the drug for a long time, and also protects the drug substance from premature fracture [2]. Objective - development of drug-based films BAS with polymers. The study was derived model phytofilm based gelatin - a polymer of animal origin, the use of which is due to biocompatibility, biodegradability, low toxicity. To give the film the necessary elasticity of the films entered plasticizer - glycerol. Glycerol has a softening effect on the film, which increases the contact surface [3]. Active substrate in the film are biologically active substances from plants of Euphorbia soongarica Boiss. The films have a thickness of 0.5 mm and is a strong, elastic, homogeneous without gaps plate light - brown.

1. Vainshtein V.A. Naumchik G.N. Investigation of polymer composites for medical films and processes of their production / Chemical journal.-1983 .- № 3.-P.347-353. 2. Ananiev VN. Gelatin dosage film / Pharmacy - 2001 .- № 5 .- p.17. 3. Golbrayh L.S. Chitin and chitosan: structure, properties and application / / Soros of Educational journal.-2001.-V.7, № 7.- p.51-56.

THE NEUTRAL MATERIALS OF LEAVES GRASSY PLANT HIBISCUS TRIONUM OF MALVACEAE FAMILY

S.E. Kiyamova, N.I. Mukarramov, Kh.M. Shakhidoyatov, N.K. Khidyrova S.Yunusov Institute of the Chemistry of Plant Substances [email protected]

At the last 25 years are intensively developed the preparations on the base of polyprenols because of their wide spectrum of biological activity and small toxicity. In this connection plant polyprenols are very perspective for making the medicinal drags with different type of activities (antiulcer, immunotrope, antiviral and others) [1, 2]. So revealing the new sources of polyprenols and other isoprenoides from local plant materials and creation the domestic preparation on their base is the most actual problem. In continuation of the study polyprenols grassy plants of Uzbekistan, we investigated the chemical composition of the neutral part of extraction amounts of leaves endemic plant Hibiscus trionum, growing on the territory Samarkand area. As a result of studies the component neutral part leaves of plants Hibiscus trionum, is shown that main component are sterols, polyprenylic alcohols, tocopherols, high alcohols and their esters. Qualitative and quantitative analysis of polyprenylic alcohols of leaves plants Hibiscus trionum, was defined HPTLC. As a result was shown that the homological composition of polyprenols includes 9-13 isoprene units; dominant is an undecaprenol with contents 47,5%, the contents of nonaprenole does not exceed 20,2%, dodecaprenole is 28,5%, and tridecaprenole is 3,8%.

1. E. Swiezewska, W. Sasak, T. Mankowski, W. Jankowski, T. Vogtman, I Krajewska, J. Hertel, E. Skoczylas, T. Chojnacki. The search for plant polyprenols // Acta Biochim. Polon. – 1994. – V. 41 – P. 221-260.

284 2. N.K. Khidyrova, Kh.M. Shakhidoyatov. Poliprenole plants and their biological activity // Kim. prirod. soedin. [in Russian]. -2002. -№2. –P.89-103.

DRUG SAFETY STUDIES OF AGSULAR®

Ya.A. Kostyro1, K.V. Alekseev2, V.K. Stankevich1, B.A. Trofimov1 1 - A.E. Favorsky Irkutsk Institute of Chemistry SB RAS, Irkutsk, Russia 2 - V.V. Zakusov Institute of Pharmacology RAMS, Moscow, Russia [email protected]

Original pharmacologically active substance of AGSULAR® possessing hypolipidemic and anticoagulant activity has been developed at the A.E. Favorsky Irkutsk Institute of Chemistry SB RAS. According to the preclinical data, the efficacy of the AGSULAR® substance is equal to the one of VESSEL DUE F® (Sulodexside) (anticoagulant and antithrombotic) and ZOCOR® (Simvastatin) (hypolipidemic and antiatherogenic). High incidental rate of cardiovascular declinations is observed in Russia now, bringing on hypolipidemic drugs in high demand. So far, they have been presented by only expensive imported preparations of various chemical natures (e.g., statins, fibrates) having diverse side effects. Gastric stability of the AGSULAR® substance has been proved and oral solid drug form has been developed on its basis (the AGSULAR® preparation). This work is aimed to evaluate the drug treatment safety of AGSULAR® substance and its oral solid drug form according to safety specifications for the clinical implications. The experimental studies conducted at the Institute of Toxicology (St.-Petersburg, Russia) upon general (acute, subacute, chronic, local irritation) toxicity and specific one (allergenicity) of AGSULAR® have shown no toxic effects upon laboratory endothermal animals. Subacute (30 days) and chronic (90 days) daily intragastric administration of AGSULAR® to mice and rats of both sexes and oral medication to mongrel dogs of 30-40 times the maximum recommended human dose causes unessential effect on their general conditions and behaviors. No adverse effects on adaptation, metabolism or major homeostatic parameters have been registered. The subacute experiment for AGSULAR® administrated intragastrically and orally in the form of oral solid drug form allows to calculate safe health care course, it is 1525 days, therapeutic index (TI) is 16,9 which refers to Group III (TI > 5) of Low Toxicity Drugs Classification. Thus, AGSULAR® is recommended for clinical investigations to enter into the List of Vital and Essential Medicines of the Russian Healthcare and Social Development Ministry.

SYNTHESIS OF (2,3-DIHYDRO-1,2,4-OXADIAZOLE)PT COMPLEXES AS POTENTIAL ANTITUMOR AGENTS

A.S. Kritchenkov, N.A. Bokach, V.Yu. Kukushkin Department of Chemistry, Saint-Petersburg State University, Stary Petergof, Russian Federation [email protected]

In the past twenty years anticancer properties of trans-platinum complexes, as an example of non cisplatin based structure-activity relations, attracted significant attention in the area of the metal based drug discovery. Platinum(II) complexes with 2,3-dihydro-1,2,4-oxadiazoles are of biological importance exhibiting antitumor properties [1]. The higher cytotoxisity of trans- (dihydrooxadiazole)PtII compounds may relate to various features of interactions of the former on a cellular level and requires further investigation including synthesis of new complexes. II We found that Pt -coordinated NCNR’2 species are so highly activated toward 1,3-dipolar cycloaddition (DCA) that they react smoothly with the acyclic nitrones ArCH=N+(O–)R (Ar/R = C6H4Me-p/Me; C6H4OMe-p/CH2Ph)[2]. The reaction between trans-[PtCl2(NCNR’2)2] (R’2 = Me2, Et2, C5H10) and the nitrones proceeds as a consecutive two-step intermolecular cycloaddition to give mono- and bis-2,3-dihydro-1,2,4-oxadiazole complexes (Scheme).

285 O O NR' R NR'2 R 2 R'2N N C N C C H R H R C N Cl C N Cl C N C N N Cl Ar Ar H Ar O H Pt Ar O H Pt Pt Ar Cl N Cl N C N Cl C C N C R'2N R NR'2 O NR'2

We found a route for the decoordination of 5-NR’2-2,3-dihydro-1,2,4-oxadiazoles from the II corresponding (dihydrooxadiazole)2Pt complexes by treatment with excess NaCN. One should mention that the chemistry of 2,3-dihydro-1,2,4-oxadiazoles is very little developed and their properties, including biological activity, are unknown. [1] H.M. Coley, J. Sarju, G. Wagner, J. Med. Chem., 2008, 51, 135–141; [2] A.S. Kritchenkov, N.A. Bokach, M. Haukka, V.Yu. Kukushkin, Dalton Trans., 2011, 40, in press. The authors are very much obliged to the Russian Fund for Basic Research (grant 11-03-00262) and Federal Grant-in-Aid Program “Human Capital for Science and Education in Innovative Russia” (contract No P1294 from 09/06/2010).

IDENTIFICATION OF ARALOSIDES IN ARALIA MANDSHURICA EXTRACT OBTAINED IN SUBCRITICAL WATER ENVIRONMENTBY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY AND MASS SPECTROMETRY

A.V. Lekar1, S.N. Sushkova2, S.N. Borisenko3, S.S. Mandzhieva2, N.I. Borisenko1, E.V. Vetrova3 1 - Ecological and Analytical Center, Southern Federal University, Rostov-on-Don, Russia 2 - Scientific and research institute of biology of the Southern Federal University, Rostov-on-Don, Russia 3 - Sceintific and research institute of physical and organic chemistry of the Southern Federal Regional University, Rostov-on-Don, Russia [email protected]

Recent yearstriterpene glycosides are widely studied. Some of these compounds are aralosides [1] contained in the root of Aralia mandshurica.The main biologically active components of araliadrugs that cause pharmacological effect according to the published data [1], are aralosides A, B and C - triterpenesaponins of oleanolic acid. Extraction of Aralia rootsaralosideswas performed in subcritical water medium in the static mode [2].Aralosidespresence in extracts was determined by HPLCand resulted to 12,42 ± 0,27% of amount of aralosides.While comparing different extraction methods was found that subcritical water extraction in static conditions is comparable in efficiency to the traditional method and using ammonia additives - surpasses the traditional method in 1,9 times. The presence in the extract ofaralosides A, B and C, with typical molecular weights (926, 1058 and 1088) is proved by a LC- MS spectrometry [3]. Relative content of aralosides A, B and C is defined by normalization and were as follows: A: B: C = 57: 27: 16. In the same chromatogramslight peak ofaralosid with a molecular weight of 1118was found. Probably, this could be the fourth aralosid D. The identification of this compound requires further investigation. Thus, the results of this study prove the existence of major aralosides A, B and C in the extract of Aralia roots obtained in subcritical conditions and demonstrate the prospects of using subcritical water as extractantforaralosidesof Araliamandshurica.

Acknowledgments This work wasfunded by theCRDF (USA)and Ministry ofEducationand Scienceunder Russian- American program "Basic Research and Higher Education, the program"Development of Scientific Potential of Higher Education of the Ministry of Education and Science (RNP 2.2.2.2/12560 (3.8 .11), BP4M04, BG1104) and Russian PresidentGrant MK- 4425.2011.3.

286 List of references 1. Ed. Blinova K.F., Yakovlev, G.P. Phyto-pharmacologicaldictionary. 990,166.,M.D.Mashkovsky. Drugs. 1985, ed. 10. Volume 1. Medicine, Moscow, 1985, 141. 2. K.S. Tikhomirova, R.N. Borisenko, E.V. Vetrova, S.N. Borisenko, E.V. Maksimenko, N.I.Borise nko, V.I. Minkin. J. Supercritical Fluids: Theory and Practice, 2008, 3, 71-75 3. L. Rastrelli, F. De Simone, O. Scheltino, A. Dini. J. Agric. Food. Chem. 1996, 44,

EVALUATION OF THE MEMBRANE ACTIVE AND MEMBRANE PROTECTIVE PROPERTIES OF THE SERIES OF ISOBORNYLPHENOLS IN THE MODEL SYSTEMS

K.M. Marakulina, R.V. Kramor, I.G. Plaschina, L.N. Shishkina Emanuel Institute of Biochemical Physics of Russian Academy of Sciences [email protected]

As known, biological activity (BA) of antioxidants is specially due their ability to influence on the structural state of membranes. In recent years semisynthetic terpenophehols, synthesized on the base of green conifers are actively studied [1]. Since BA of compounds depends on their chemical structure, this makes it necessary of the initial selection in various model systems of the most promising and less toxic medicals for use in practice. The goal of the study was the investigation of the possibility evaluation of the membrane active and membrane protective properties of the isobornylphenols, which possess a different influence on the induced hemolysis of the red blood cells. The two representatives of the substituted phenols, containing one and two isobornil groups i.e. 2- izobornylphenol (I) and 4-methyl-2,6-diizobornylphenol (II) respectively, were studied. Compounds I and II were synthesized by collaborators of the Institute of Chemistry, Komi SC by the leadership of Corresponding member of the RAS A.V. Kutchin, and kindly provided to us for research [1]. The soy bean lecithin (L) and sphingomyelin from bovine brain (SM) were used in research. Purity and fractional composition of the phospholipids (PL) were controlled by thin layer chromatography (TLC). Phenomenon and the stoichiometry of the complexation between molecules of PL and IBP were studied by using the series solution in hexane both individual components of the PL, IBP and mixtures thereof by the UV-spectrophotometry method. Effect of IBP on the size and percentage of the PL micelles with different diameters in hexane was studied by the dynamic light scattering method at 25° C and a fixed scattering angle of 173 °. It is known that lecithin is a mixture of natural lipids. According to TLC, used L contained 65,6 ± 2,85% PL in the total lipid composition, from which was 92,2 ± 0,3% phosphatidyl choline. The same parameters for the SM were 75,4 ± 3, 6% and 97,2 ± 0,5% respectively. It was found that compound II did not significant affect the self-organisation of L and SM in hexane, whereas the addition of IBP I to solutions of SM and L leads to a size reduction of aggregates 2 and 20 times, respectively. This fact confirms the presence of the complexation between molecules of PL and IBP, which were found by UV-spectrophotometry. To determine the stoichiometric ratio of components in a complex, the method of the isomolar series of solutions in hexane both the individual PL, IBP and mixtures thereof was used. Analysis of results showed that the L interacts with the IBP I and II in a molar ratio of 6:4, and SM do with the IBP I and II in the molar ratio which is equal 9:1. The data obtained suggest that the ability of IBP to interact with the PL of the membrane bilayer is the reason of their biological activity. Besides, we can assume that the identification of membrane protective properties is result from the absence of the marked ability of IBP II affect the aggregation process of PL in the non-polar solvent [2], while IBP I, obviously, must have membrane-active properties.

References: 1. Chukicheva I.Yu., Kutchin A.V. Natural and synthesized terpenophenols. Russian Chemical journal. 2004, V. 48. №3. pp. 21-38. 287 2. Shishkina L.N., Mazaletskaya L.I., Sheludchenko N.I., Kutchin A.V., Chukicheva I. Yu., Shevchenko O.G. Structure of isobornylphenols and their biological activity. Book of abstracts of VI All-Russian conference “Chemistry for waste management and management of chemical waste”2010. P. 345-346.

BLACK SEA MARINE MACROALGAE AS A SOURCE OF BIOLOGICALLY ACTIVE SUBSTANCE

N.A. Milchakova, O.A. Shakhmatova Institute Biology of the Southern Seas, Sevastopol, Ukraine [email protected]

Most species of marine maсroalgae have a biological activity and belong to perspective source for medicine. The pharmacologically effect have 83 species of seaweeds growing in many region of the World Ocean (49 - Rhodophycophyta, 20 - Heterokontophycophyta and 14 –Chlorophycophyta), among them 69 species are known for the Black Sea. The drugs from marine algae could be divided into major groups by clinical applications: antifungal, anticoagulant and antihemorrhagic, antiviral, antihypertensive, antitumor, cardio- and cerebrovascular, supporting resistance to acquired immunodeficiency syndrome. Many claims have been made for the effectiveness of seaweeds in the treatment of tuberculosis, arthritis, colds and influenza. They are also prescribed to lower cholesterol activity, lipid effects and blood pressure. Combined with seawater hydrotherapy this treatment provides relief for rheumatism and osteoporosis. The antibacterial, antiviral, antifungal, antiprotozoal, antitumour activity have 38 species of the Black Sea macroalgae, among them 7 species belong to Chlorophycophyta (Bryopsis hypnoides, Bryopsis plumosa, Chaetomorpha linum, Cladophora albida, Cladophoropsis membranaceae, Ulva clathrata, Ulva flexuosa); 9 – Heterokontophycophyta (Cladostephus spongiosus, Cystoseira barbata, Cystoseira crinita, Dictyota dichotoma, Dictyota fasciola, Dictyota spiralis, Nereia filiformis, Scytosiphon lomentaria, Zanardinia typus) and 22 – Rhodophycophyta (Callithamnion granulatum, Ceramium arborescens, Ceramium сiliatum, Ceramium. deslongchampsii, Ceramium diaphanum, Ceramium virgatum, Chondria capillaris, Chondria dasyphylla, Corallina elongata, Corallina officinalis, Dasya baillouviana, Dasya hutchinsiae, Gelidium crinale, Gelidium spinosum, Haliptilon virgatum, Jania rubens, Laurencia coronopus, Laurencia obtusa, Lomentaria clavellosa, Polysiphonia elongata, Polysiphonia fucoides, Polysiphonia subulifera). 20 Black Sea species are a source of antitumour medicine, among them 2 species of green (Cladophora albida, Ulva prolifera), 5 - brown (Cystoseira barbata, Cystoseira crinita, Dictyota dichotoma, Ectocarpus siliculosus, Scytosiphon lomentaria) and 13 - red algae (Ceramium сiliatum, Ceramium deslongchampsii, Ceramium diaphanum, Ceramium virgatum, Corallina elongata, Corallina officinalis, Gelidium crinale, Gelidium spinosum, Haliptilon virgatum, Laurencia coronopus, Palisada perforata, Phyllophora crispa, Porphyra leucosticta). 17 species are a source of antioxidant biologically activity substance (BAS). This kind of activity have been shown 5 species of green (Cladophora laetevirens, Cladophora liniformis, Cladophora sericea, Ulva intestinalis, Ulva linza), 2 - brown (Padina pavonica, Scytosiphon lomentaria) and 10 – red algae (Ceramium arborescens, Corallina officinalis, Dasya hutchinsiae, Gelidium crinale, Gracilaria dura, Gracilaria gracilis, Grateloupia dichotoma, Haliptilon virgatum, Laurencia obtusa, Polysiphonia elongata). There are 4 species of the Black Sea macroalgae have antibacterial, antiviral, antifungal, antiprotozoal, antitumour and antioxidant activities (Corallina officinalis, Scytosiphon lomentaria, Gelidium crinale, Haliptilon virgatum), two from them belong to corragenous algae. Thus, common, generally distributed in the Black Sea macroalgae are resources for receiving BASs with volume economic and pharmacologic properties. Nowadays the seaweed resource in the Black Sea have been decreased in a few times, while the development of seaweed mariculture has high

288 economic and ecosystem effect and necessary for the protection of the biodiversity on a one hand and drug industry on other.

DEVELOPMENT OF HAEMOSTATIC PREPARATIONS ON THE BASIS OF PHYTO- RESOURCES

А.D. Mаtchanov1, D.N. Dalimov1, N.L. Vipova2, А.R. Erkabaev3, A.H. Islamov3 1 - National University of Uzbekistan named after Мirzo Ulugbek 2 - A.S.Sadykov Institute of Bioorganic Chemistry, Uzbek Academy of Sciences 3 - Sanitary Epidemiological Station of Медиcal Sanitary Association of the Ministry of Health, Republic of Uzbekistan [email protected]

Рlants of Lagochilus species are known for their valuable therapeutic properties for a long period of time. They comprise the number of the most known herbs of the East due to their effective haemostatic action. Broth and tincture on the basis of Lagochilus Inebrians as well as its dry extract, which recently restarted to be produced, find effective application for the treatment of bleedings of several etiologies. Acting component of plant Lagochilus Inebrians is diterpenoid tetraol – lagochilin; due to its presence this plant exhibits haemostatic action. However it has such a limitation as rather poor solubility in water, which causes its desired effect to develop considerably slowly. On the basis of lagochilin derivative – sodium salt of lagochirzinic acid a haemostatic preparation for intravenous introduction «Lagoden» has been developed; it finds a successful application in medical practice of Uzbekistan instead of widely applied intravenous preparation «Dicinon». However, on a basis of lagochilin water-soluble haemostatics with high bioaccessibility have not been developed. Taking into consideration the above-stated we have developed methods and conditions of synthesis of water-soluble supramolecular complexes of lagochilin with a number of glycyrrhizic acid derivatives and some bioaccessible medical polymers. We develop technologies of producing these supramolecular complexes of lagochilin with effective haemostatic action in forms of tablets, collagenic films, sponges, gauze tampons, gel and 0.15 % solution of a haemostatic preparation for intravenous administration.

Effect of Glilagin (3) on parenchymial bleedings of intact rats The conducted pharmaco-toxicological studies on specific compared with those of МАSGA (2), Lagoden (4) Gelevin (5) activity of the most known haemostatics in comparison with lagochilin-based preparations have shown the full 300 superiority of the latter ones over those of known. 250 A haemostatic Blood loss value of rats in 30 minutes after intraperitoneal introductions of Lagovin 200 preparation preparation (3, 4, 5, 6 are preparation dose of 0,5; 1; 2; 3 mg/kg respectively) compared with those of Dicinon (2-30 mg/kg) 150 having 367

time, second besides 100 400

essential 350 50 haemostatic 300

0 action, 250 12345

analgesic, 200 129 123 133

150 anti-inflammatory and tissue-regenerating effects as time, second 62 67 well has been named “Glilagin”. 100 The various drug forms of “Glilagin” and “Lagovin” 50 0 such as tablets, gel, film, haemostatic gauze, 123456 tampons, bandage and 0,15 % solution for intravenous administration were developed. The study of “Glilagin’ effect on parenchymial bleedings of intact rats at hypocoagulation conditions caused by heparin and compared to those of “Lagoden” and “Gelevin” (Russia), has shown, that the haemostatic action of “Glilagin” is not worse than that of its domestic analogue “Lagoden” and it was found to be even more efficient than «Dicinon» and «Gelevin». The study of the mechanism of “Lagovin” action has shown, that it is

289 related to the activation of thromboplastin and the acceleration of pro-thrombin transformation into thrombin (I and II phases of blood coagulation).

EFFECT OF FLAVONOIDS CONTAINING EXTRACT ON THE LABORATORY RATS WITH LIVER TUMORS ENTWINED PC-1

N.A. Navolokin1, N.V. Polukonova2, X.M. Kong1, A.B. Bucharskaya1, G.N. Maslyakova1 1 - Saratov State Medical University named after V.I. Razumovsky, kafedra pathology Saratov, Russia 2 - Saratov State Medical University named after V.I. Razumovsky,kafedra general biology, botany and pharmacognosy,Saratov, Russia [email protected]

Now actively search is conducted for new biologically active substances of plant origin with antitumor and antioxidant activity (AO) and low adverse effects. Flavonoid-containing substances are the most promising group in this regard. Purpose: to investigate the morphological changes in the internal organs and peripheral blood and antioxidant activity under the influence of flavonoid-containing extracts on the background of transplanted liver cancer in laboratory rats. Materials: flavonoid-containing extracts of medicinal hauran (Gratiola officinalis) and corn (Zea mays), 18 white male rats with transplanted liver tumors of PC-1. Methods: standard histological staining methods gematoxilin and eosin. Biochemical methods (Artyukhov, 2000) were used to analyze the AO. Determination of catalase activity was carried out in rat erythrocytes by spectrophotometric method. Design of experiment: animals with transplanted liver tumors of PC-1 has been divided into three groups on six rats in each groups. Rats received (1 ml once a day) extracts by oral gavage during three weeks: in the first group - extract of hauran, in the second – extract of corn. The third group was control and received peroral once a day 1 ml saline solution. Animals were removed from the experiment by decapitation at the end of the study, the blood, internal organs and tumor were climbed for further analysis. Results. Number of segmented neutrophils was significantly decreased by 22.3% (hauran) and 24,5% (corn), and lymphocyte count was increased by 55% (hauran) and 46% (maize) in the leucocyte formula of animals under the influence of hauran extract and corn extract compared with the control. In comparison with the control the changes in the brain, heart, lungs, intestine were not revealed by histological examination of animal received the hauran extract. In the spleen a moderate hyperemia and no large accumulation of gemosiderin granules were noted; in the kidney - a moderate hyperemia of the cortex and glomeruli and moderate degeneration convoluted tubule epithelium; and in the liver - a moderate hyperemia and mild degeneration of hepatocytes. The degeneration of hepatocytes was marked at two of six animals. At the histological study there were no changes extract in the brain, heart, lungs, kidneys, spleen, intestine of laboratory animals treated with the corn extract, the moderate zonal degeneration of hepatocytes was observed in the liver. In comparison with the control the increased quantity of malondialdehyde (by 171%), catalase (111%), superoxide dismutase (by 59%) were observed in the study of blood AO of rats in the experiment with hauran. Lipid peroxidation and the activity of AO enzymes did not differ from controls with the introduction of the extract of corn. Conclusion: The effect of flavonoid-containing hauran and corn extracts was found in lymphocytes of peripherical blood; the moderately expressed morphological changes were found in the internal organs of rats under the action of the hauran extract. Minor changes were found under the influence of the corn extract in the liver. High hauran extract AO and the absence of AO of the corn extract were revealed on the backdrop of transplanted liver cancer.

290 These findings suggest a low toxicity of flavonoid-containing extracts and the presence of positive effects on the animals with transplanted liver cancer, which made the further study of hauran and corn extract combination very perspective in different experimental models.

EXTRACTION AND STUDY OF BIOLOGICAL PROPERTIES OF POLYSACCHARIDES POTENTILLA ARGENTEA

A.A. Nazarova, S.D. Polishuk, T.V. Zheglova Ryazan State Agrotechnological University, Russia, Ryazan, Kostycheva str., 1 [email protected]

Carbohydrates play an important role in life processes. Their biological effects are very versatile, from being energy and construction materials to such functions as inhibition or activation of body enzymes preventing radiation injury, their ability to reduce inflammatory processes and to intensify the generation of nerve and muscle tissues. These properties of polysaccharides led to the emergence of numerous domestic medicines based on carbohydrates. However, all known methods of isolation of polysaccharides have some significant drawbacks. For example, the well-known extraction method [1] is technologically complex, but it gives only a slight increase in the content of polysaccharides. We have considerably improved this method of extraction of water-soluble polysaccharides from various medicinal herbs such as Polygonum aviculare and Potentilla Anserina. This patented by us method [2] allows avoiding factors leading to damage, oxidation, and enzymatic destruction of polysaccharides. Moreover, this method leads to increase in yields of polysaccharides (Table 1).

Table 1. Yield of polysaccharides (as a percentage out of the absolutely dry raw material).

№№ Time of harvest 2008-2010 years (control) 2008-2010 years (experiment) Extraction Extraction I II Sum I II Sum 1 15.06 3.2 3.0 6.2 4.9 2.6 7.5 3 2.07 6.2 6.2 12.4 9.7 4.4 14.1 5 18.07 7.6 6.2 13.8 7.2 8.3 15.5 6 25.07 6.3 4.2 10.5 5.5 4.2 9.7 9 17.08 3.9 2.7 6.6 4.4 4.5 8.9

The second step in our research was to study the biological activity of water-soluble polysaccharides isolated from medicinal herbs. The extracts were daily injected to laboratory rats at a dose of 0.5g/kg of the body weight for 30 days. The results showed that the animals that have been administered the preparation of water-soluble polysaccharides to, increased body weight faster than control. The gaining of body weight was at maximum on 28th day counting from the moment of taking the preparation (+17.5% compare to control). The use of water-soluble polysaccharides of Potentillas did not lead to a significant difference in morphological composition of blood, but resulted in the increase in the number of red blood cells, level of hemoglobin, and the leukocytes number. Probably, the water-soluble polysaccharides have stimulating effects on the blood-forming organs by means of activating them.

References: 1. Yakovlev A.I., Churilov G.I., Ginak A.I. Polysaccharide composition of Polygonum aviculare.// Chemistry of Natural Compounds . Moscow, № 5. 1985. p. 619-622. 2. Polishuk S.D., Churilov G.I., Kovalenko L.V., Folmanis G.E., Nazarova A.A. Method of obtaining water-soluble polysaccharides from plants. Patent number 2.378.288. Published 10.01.2010. Bull. № 1.

291 THE USING OF THE WORLD PHARMACOLOGICAL AND MEDICAL COMPOUNDS AND COMPOSITIONS FROM WOOD AND PLANTS IN THE MEDICAL TREATMENT. THE POTENTIAL OF RENEWABLE RESOURCES

E.R. Platonova1, S.A. Rubaev2, P.V. Coy3 1 - Nonstate firm - Nevskaya school on innovation technologies, Saint-Petersburg, Russia 2 - Ltd. Co. First assistance, Saint-Petersburg, Russia 3 - Ltd. Co Spine Clinic, Saint-Petersburg, Russia [email protected]

Sustainable Nature resources using includes the using of the plant and wood raw material for the pharmacological and medical drugs production also. Medical methods of the treatment using such drugs from all the world may be used for the treatment of a human being locomotor system. Here the pharmacology and medical drugs are discussed as attendant and principal means during the treatment side by side with traditional methods. The traditional methods include exercise therapy complex including the massage also, the physiotherapy treatment, the sanitating water procedures, an observance of orthopedic regime, etc. During the2010 – 2011 years an approbation of the plant drugs, produced in Germany, was approbated in the form of the ointments, tablets, injections. The chondroprotector as drug, produced in Rumania, was approbated during the injections course too. Russian drugs on the base of plant and forest raw materials were used for the decreasing of knee joints inflammation, the improvement of the local blood flow. In the complex therapy the drug on the base of Ginco-Biloba plant was used for the general blood supply improvement. It is produced in France. This treatment course was a hard and danger investigation for the patient. The results of this treatment are the improvement of the patient functional state of the locomotor system, the obtaining of the spine elasticity, the reducing of the tissues swelling around the knee joints, the legs swelling taking away, the tonus stimulation action the patient nervous system. The cybernetic method was used during the treatment course. The keeping information back bond permitted to influence the treatment course. These questions will be illustrated in the report in details during the conference. This method was realized thanks to cooperation between the physician, the pharmacological drugs adviser and the patient. The significant drugs using the plants and forest raw materials will be given in our report, so as the plant and forest resources names in the composition of drugs. The reproduction problems of plant and forest raw materials will be discussed also. The significance of the black sea fauna preservation will be discussed too.

INTERFERON INDUCING ACTIVITY OF AZODERIVATIVES OF GOSSYPOL IMINES

K.Zh. Rezhepov, Kh.L. Ziyaev Institute of Bioorganic Chemistry of AS RUz, Laboratory of Polyphenols, Tashkent, Uzbekistan [email protected]

Gossypol is a specific pigment of cotton plant, which was found to be the first interferon inductor of plant origin. In medical practice the organic compounds of different classes are used, however, almost nothing is known about the medical application of azo-dyes being the most important group of organic dyes represented by enormous number of compounds. At the same the use of biologically active compounds as diazo-components, diazotized amines, that themselves exhibit a wide range of physiological activity, the poly-functionality of formed compounds, their capability to tautomerize, form complexes and interact with protein molecules allow suggesting that among azo-dyes there can be found interesting objects to work with on developing medicines. Since phenols and naphthols are much frequently used as reactants for producing azo-dyes it was interesting to apply this reaction to gossypol. Poly-functionality of gossypol molecule allows to

292 obtain imines by condensation of its aldehyde groups with primary amines as well as to obtain its azo-derivatives by reaction with diazonium salts on C-4 position. Gossypol imines, azo-derivatives and azo-imines have been synthesized by using the same arylamines to introduce to both positions. Comparative studies of interferon inducing activity of these compounds demonstrated that gossypol imines and azo-derivatives induced the formation of relatively low levels of interferon of 80-160 IE, units/mL. The level of interferon formation induced by gossypol azo-imines has been found to be much higher, 320-1280 IE, units/mL, which suggests that the activity of the substances can be related to the number of introduced substituents. The comparison of interferon inducing activity values for compounds having an introduced substituent with different position (o-, m-, p-) of functional groups in it demonstrates that the highest value can be achieved by using o-aminophenol and o-aminobenzoic acid. Their m-isomers were found to be least interesting in terms of interferon inducing activity. Obtained results suggest that titer of produced interferon also depends on dose and time for a substance to contact a cell (see Fig. 1.).

IE, units/mL IE, units/mL 1300 1300 1200 a) 1200 b) 1100 1100 1000 1000 900 900 800 800 700 700 600 600 500 500 400 400 300 300 200 200 100 100 0 0 1 8 15 2 9 16 3 10 17 4 11 18 5 12 19 6 13 20 7 14 21 1 8 15 2 9 16 3 10 17 4 11 18 5 12 19 6 13 20 7 14 21 compounds compounds gossypol imines gossypol azoderivatives gossypol azoimines gossypol imines gossypol azoderivatives gossypol azoimines Fig. 1. Interferon inducing activity of gossypol derivatives. a)- dose of 100 mg/kg, after 24h; b)- dose of 100 mg/kg, after 48h.

The studies of biological activity of gossypol and its derivatives are in progress.

NEW GOSSYPOL-BASED MEDICINES: INTERFERON INDUCTORS OF PLANT ORIGIN

K.Zh. Rezhepov, Kh.L. Ziyaev, A.I. Ismailov, A.M. Ermatov Institute of Bioorganic Chemistry of AS RUz, Laboratory of Polyphenols, Tashkent, Uzbekistan [email protected]

The results of recent investigations suggest that a major barrier to be overcome by a viral infection is the system of interferon and its inductors. The capability of interferon to suppress the reproduction of viruses and to have immunomodulation effect allows using interferon itself and its inductors to cure a broad range of infectional diseases. Diverse biological functions of interferon (antiviral, anti-proliferative, immunomodulation effects, effect on cellular regeneration and others) allows considering this factor of non-specific protection of an organism as multi-potent system of homeostatic regulation. Effects of interferon are caused by the cascade of mechanisms and the effect of medicines inducing the formation of endogenous interferon can be a result of several intracellular processes induced by them. Responding on the introduction of different interferon inductors the certain populations of immunocytes synthesize different types of interferon (-, -, ). The amount and type of formed interferon depend on the way of introduction, type of immunocyte, dose and time for inductor to contact a cell. The all above-listed on the process of interferon induction by an inductor can be clearly seen by studying interferon inducing activity of gossypol derivatives. The introduction of heterocyclic amines to gossypol molecule leads to the formation of its derivatives producing high titers of (-, -) interferon in the organism. Detailed study of gossypol derivatives allowed developing an interferon inducing medicine-Ragosin. Mechanism of Ragosin’s action is based on its capability to induce the formation of endogenous interferon in the organism.

293 Ragosin is licensed to be produced in a 0.05g tablet form for a wide medical application as hepatoprotector for prophylactics and curing acute and chronic hepatitis B, C and D. When organism is infected with hepatitis B, C or D Ragosin demonstrates its antiviral effect by inducing the synthesis of endogenous interferon in different organs and tissues. This medicine dramatically increases the level of - and -interferon in blood, causes earlier disappearance of dyspepsia symptoms, symptoms of asthenia, icterus, speeds up the normalization of level of liver enzymes and bilirubin, causes the removal of hepatitis viruses out of organism. A Registration Certificate (Guvohnoma #07/481/2 from 30.10.2007) was obtained and it registers A.S. Sadykov Institute of Bioorganic Chemistry of AS RUz as a producer of Ragosin substance. The license on the production of 0.05g Ragosin tablets was given to OAS “Uzkhimfarm”. On base of ragosin’s complex with N-polyvinylpyrrolidone a medicine with anti-chlamydial effect (0.1g Gosalidon tablets) has been developed. It is used for prophylactics and curing the patients with chlamydia infection. 0.1g Gosalidon tablets can be used to cure diseases caused by chlamydia, such as primary and secondary sterility, inflammatory processes of pelvis organs (cervicitis, epididymitis), prostatitis, reactive arthritis of urogenital etiology, Reiter’s disease. A Registration Certificate (Guvohnoma #08/90/1 from 29.02.2002) was obtained and it registers A.S. Sadykov Institute of Bioorganic Chemistry of AS RUz as a producer of Gosalidon substance. The license on the production of 0.1g Gosalidon tablets was given to OAS “Uzkhimfarm”. (Guvohnoma #03/46/9 from 29.02.2008).

DIURETIC ACTIVITY OF DRY EXTRACTS OF YELLOW TOADFLAX (LINARIA VULGARIS)

O.V. Scherbakova, V.M. Petrichenko, B.Ya. Syropyatov Perm State Pharmaceutical Academy, Perm, Russia [email protected]

Yellow toadflax - Linaria vulgaris Mill. (Scrophulariaceae family) is a perennial herbaceous plant widespread on the territory of Russia. The above-ground part of yellow toadflax is used in folk medicine as an anti-inflammatory and diuretic agent and a remedy for haemorrhoids. According to pharmacological research aqueous and alcoholic extracts, derived from the plant possess cardiotonic effect and antibacterial properties whereas the influence of biologically active substances on diuresis has not been researched. This problem is actual because diuretic drugs are used for treatment of numerous kidney diseases and stabilization of hypertension patients’ condition. The aim of the research is to determine diuretic activity of dry extracts, derived from herb and separate parts of yellow toadflax. Material and methods Dry alcoholic extracts from yellow toadflax were derived the following way: 50 g of vegetable material were put into a round-bottom flask, covered with 300 ml of 60% ethyl alcohol and were being heated on boiling water bath for 2 hours; the extraction product was cooled and run through paper filter; sequence of actions described above was repeated with the derived toadflax cake; the extracts were poured together and ethyl alcohol was distilled off. Dry extracts had been being kept in drying oven at the temperature of 70oC until the eluting agent completely evaporated. The diuretic activity of yellow toadflax extracts was assessed in compliance with “Methodological guidelines…” (1989). The experiments were conducted on male albino rats of Wistar line that weighed from 190 to 200 g. Dry extracts of yellow toadflax, dissolved in 5 ml of distilled water were once introduced enterally (dose: 50 mg/kg) without any surplus water. Animals from the control set were given equivalent volume of water distilled in a similar way. Bottle brush (Equisetum arvense) prepared according to state pharmacopoeia with posterior distillation of the eluting agent (distilled water) until its evaporation was used as a comparator agent. The derived extract (dose 50 mg/kg) was introduced in conformity with the previously described procedure. Collection of urine was performed in exchange cages in 3 and 6 hours after the introduction of the extract. Then the volume of urine was measured. 294 Results and Discussion It follows from the acquired data that extracts from yellow toadflax possess diuretic activity. It should be noted that the extracts show ultimate activity within the first three hours after the introduction of the agent. The volume of urine under the effect of yellow toadflax extracts derived on 60% ethyl alcohol increased by 86% and by 137% in comparison with the control set, which exceeds the activity of bottle-brush by 22% and 39% respectively. The activity of extracts derived from the stem, fruit and flowers of yellow toadflax is consistent with the activity of extracts derived from the herb itself. The volume of urine, effused under the effect of these extracts is twice the amount of the volume in the control set within the first 3 hours and within 6 hours 2.5 times more than the volume in the control set.

ESSENTIAL OIL OF THYMUS JENISSEENSIS: BACTERICIDAL AND ANTIOXIDANT ACTIVITY

L.S. Sokolova, A.A. Efremov Siberian federal university, Krasnoyarsk, Russia [email protected]

Species of thyme (Thymus L.) belong to a number of valuable medicinal plants. In medical practice, drugs from the aboveground part of Thymus serpyllum L. and Thymus marschallianus Willd. widely used. In Siberia, Thymus serpyllum is the most common of many species. It is highly polymorphic species, as represented by numerous similar forms: Thymus jenisseensis, Thymus sibiricus, Thymus elegans Serg., and others, that is difficult distinguishable from each other. The object of our study is Thymus jenisseensis I. Previously by gas chromatography / mass spectrometry, we have installed the component composition of essential oil of Thymus jenisseensis, growing in Khakasiya. Also bactericidal activity of essential oil of Thymus jenisseensis was studied. Minimum inhibitory concentration (MIC, in mkg / ml) of essential oil of Thymus jenisseensis was established in relation to: Escherichia coli - 42,5; Proteus vulgaris - 2,55; Klebsiella pneumonia - 2,55; Acinetobacter calcoaceticus - 2,55; Pseudomonas aeruginosa - 21,25; Staphylococus aureus - 2,55. Bactericidal activity of essential oil varies in relation to different types of conditionally pathogenic microorganisms. The values obtained of MIC showed high bactericidal activity of essential oil of Thymus jenisseensis. In this study, using the reaction of inhibition of auto oxidation of trans-2-hexenal, antioxidant activity (AOA) that was received fractions of essential oil of Thymus jenisseensis in different concentrations, was identified. Fig. shows the histogram of the content of trans-2-hexenal in a model system in the presence of supplements of individual fractions of essential oil of thyme.

295 120

100 trans-2-hexenal

80 1 fr

60 3 fr 40 4 fr 20 Whole oil content trans-2-hexenal , % 0 10 days 30 days 50 days

Fig. The content trans-2-hexenal in model systems in the presence of different fractions of essential oil of Thymus jenisseensis at a concentration of 200 mkg / ml.

Experimentally we established that virtually all concentrations of added fractions of essential oil of Thymus jenisseensis AOA of last fraction is considerably higher than the first fraction of AOA, and it exceeds corresponding value for the whole oil. This is due apparently by differences in the component composition of oil fractions, which suggests a larger value of AOA sesquiterpene hydrocarbons compared to monoterpene hydrocarbons.

COMPOSITE MATERIALS BASED ON METHYLCELLULOSE WITH SYNTHETIC BIOLOGICALLY ACTIVE POLYMERS

N.M. Zabivalova, A.M. Bochek, I.I. Gavrilova, N.A. Nesterova, E.F. Panarin, V.E. Judin, I.V. Gofman, V.K. Lavrentev, E.N. Vlasova, B.Z. Volchek Institute of Macromolecular Compounds of Russian Academy of Sciences [email protected]

For the purpose of obtaining of composite film materials with new functional properties and with regulated for the biomedical purposes stress-strain characteristics the rheological properties of aqueous solutions of mixtures methylcellulose (МC) with poly – N - vinylformamid (PVFА) and poly-N-methylvinylacetamid (PМVАA) have been investigated and also thermodynamic compatibility (МC) with synthetic polymers in a solid state and the structural organization of composites have been determined. In diluted (0.2 wt %) and moderately concentrated (3 wt %) solutions the negative deviations of viscosity from additive values were observed. It is shown that with growth concentration PVFА and PМVАA in mixtures an increase in temperature of gelatinization onset Тgel in the solutions occurs, that is caused by the diluting effect of gel-forming polymer MC. Films from solutions have been obtained by dry forming method and their physical and mechanical properties, the structural organization as well as thermodynamic compatibility of polymers in solid state have been studied. X-ray scattering experiments on composite films against their composition have shown that superposition of reflexes of one polymer on those of another has been observed. Temperatures of relaxation transitions in systems and also the ranges of composite contents in which MC was compatible with PVFА and PМVАA were defined by the methods of the dynamic mechanical analysis and thermo-mechanics. For two systems under study the partial compatibility of polymers has been observed. In the films formed from aqueous solutions of mixtures of cellulose ether with PVFА compatibility was observed in the range of small additives (to 10 wt %) PVFА to MC. Addition of PVFА into matrix MC leads to change of the polyamide structure. The conformational transition caused by intermolecular interaction of macromolecules MC and PVFА on phase boundary and in region of

296 composition in which polymers are compatible is found. Addition of up to 20 wt % PVFА into MC matrix does not lead to essential deterioration of composite properties. It has been shown that МC was compatible with PМVАA in mixtures at the composition of the last up to 50 wt %. Addition of up to 10 wt % PМVАA does not lead to essential change of mechanical characteristics of composite films. At higher PМVАA content the decrease in the module of elasticity Е, breaking strengths p and lengthening at rupture p were observed, (Е 3.79 GPa, p 140 MPa, p 38 % for pure MC and Е 3.31 GPa, p 92 MPa,, p 34 % for a film with 30 wt % of PМVАA accordingly), that reflects a tendency of increasing of films brittleness. As a whole, composite films with the content up to 30 wt % PМVА possess satisfactory stress-strain characteristics.

COMPARISON OF POLYPRENOLS FROM THE LEAVES OF TWO SORT’S GRAPE

U.T. Zokirova1, N.M. Mamatkulova1, N.K. Khidyrova1, T.P. Kukina2, Kh.M. Shakhidoyatov1 1 - S.Yunusov Institute of the Chemistry of Plant Substances 2 - Novosibirsk institute of the Organic Chemistry [email protected]

The wide spectrum of the biological activity of polyisoprenoides spur to study polyprenole composition of grape leaves - a departure of vine production. Earlier, polyprenols of grape leaves wine sort were compared, the growing in different region of Uzbekistan. As a result it was revealed that of grape leaves collected in Tashkent area contains the most amounts of polyprenols. We have matched polyprenoles of grape leaves "Buvaki" and "Lady sticks". The extraction of 96% by ethanol of grape leaves got the extractive material. Leaving the amount extractive material form 10,3% and 12,2 %, neutral material - 3,6% and 2,4%, and polyprenols - 1,5 and 0,98% accordingly from air dry mass of the plant material. The comparisons of the contents of grape leaves from high sorts have shown determined similarity qualitative and differences quantitative composition. The analysis is organized with using HPTLC. The homological composition to fraction of polyprenols from sort "Buvaki" is determined by HPTLC and HPLC. The contents of dominant undeca- and dodecaprenoles are 36,2, 46,8%, deca-, trideca- 6,9 and 9,3% accordingly, phenols with 9 and 14 isoprene unit are noted in a few amounts.

297 RUSSIAN-AUSTRIAN SEMINAR ON CELLULOSE CHEMISTRY

CONSERVATION SCIENCE OF HISTORIC CELLULOSIC OBJECTS

K. Ahn, T. Rosenau, A. Potthast, U. Henniges University of Natural Resources and Life Sciences Vienna (BOKU) [email protected]

Cellulose is one of the most durable organic materials on earth and has been used – for instance in textiles and paper manufacture – for many centuries. Thanks to the permanence of cellulose important information from past cultures, habits, and traditions, some of them vanished long time ago, and also from simple life has been preserved and traded down to our days. In order to preserve historic objects many methods are placed at the conservators´ disposal. Not all of these procedures are safe and sustainable, and they fail to prolong the lifetime of the respective work of art, as lessons from the past have taught. Understanding the aging of cellulose on the molecular level will help to further safeguard historic objects and keep them intact for upcoming generations. The presentation will focus on ways to determine the state of deterioration of cellulosic materials. Special focus is placed on rag papers of different origin, as well as Asiatic materials and South American textiles from the Inca period. We have investigated different protocols for cellulose treatments of paper and textiles (bleaching, phytate treatment, washing, etc.) applying fluorescence labelling of oxidized groups in combination with size exclusion chromatography (CCOA and FDAM protocols) in combination with artificial aging. The methods applied help to judge the impact of conservational treatments on the state of deterioration of cellulose.

BIOETHANOL FROM LIGNOCELLULOSICS

A.V. Kind, E.A. Ploshko, V.A. Yolkin, V.V. Vyglazov Saint-Petersburg State Forest Academy [email protected]

Beginnings and development of wood hydrolysis ethanol production in USSR since 1935 was connected with demand for technical ethanol as essential part of a rubber. In nowadays the hydrolytic industry used the valuable softwood for bioethanol. Raw materials sources for this type of wood for many companies today are inaccessibly. The ethanol production utilized about 40-50% of the biomass of coniferous wood. But other part of the biomass is not used. Therefore, it is necessary hardwood refine into ethanol. At the departments of biotechnology, wood chemistry, physical and colloid chemistry Forest academy makes the investigations on hydrolytic technology of low quality hardwood into valuable products. The new complex processing technology of low quality birch wood will allow more efficient use of biomass and get out of it liquid bioethanol; sugar substitute for diabetics - xylitol, biologically active substances and other products. In particular from 1t dry raw material can be obtained: ethanol fuel - 14-15 dal; xylitol 100-120kg and other valuable products. Ethanol is used as the pollution-free additive to fuel for internal combustion engines. Ethanol is not only the high quality substitute of fossil gasoline, it also can save natural resources as it produced from renewable material. Importance of problem is caused by raise of high-grade gasoline cost, its deficiency in connection with growth of the car fleet and exhaustibility of oil resources; end the difficult ecological circumstances which have developed in large cities. The solution of this problem lays in use of oxygenic high-octane components, fist of all alcohol or additives on its basis. Ethanol in the capacity of capacity of engine fuel was started widely to be used in the world in the late seventies. Today about 2/3 of world ethanol production is used as the additive to engine fuel.

298 Use of ethanol as part of engine fuels o 5-7% allow to improve quality of fuel (octane value raises, lover toxicity of an exhaust) that opens perspectives in connection with usage of euro-3 and euro-4 petrol. Therefore for expansion of product markets and use of a wood and vegetative agricultural waste, transforming of the hydrolysis plants to production of fuel ethanol (additive to engine fuel) is expedient. Fuel ethanol does not require the high grade purification. So, in standard specification of the USA of denaturated fuel ethanol as additive in gasoline (to 10 about %) the following indexes are required water content ≤ 1,25%; nonvolatile impurities ≤ 5 mg/100ml; chloride of ions ≤ 32 mg/l; copper ≤ 0,03 mg/l; acidity (in conversion on an acetic acid) ≤ 56 mg/l. In this connection ethanol production in two-column distiller that allows reduces a specific consumption of energy (steam) to its production considerably.

FORMATION OF BIOACTIVE COMPOUNDS UPON AMMONOXIDATION OF LIGNOCELLULOSIC MATERIALS

K.-M. Klinger, A. Potthast, T. Rosenau, F. Liebner University of Natural Resources and Life Sciences Vienna (BOKU) [email protected]

Ammonoxidation is a technical process that has been known for a long time and has been successfully applied in converting various ligneous feedstocks such as coal, peat, and technical lignin into soil improving materials. Currently, lignin-rich fractions from modern biorefineries are increasingly moving into the limelight of such utilization concepts, as the operating efficiency of biomass processing units largely depends on the profitability of all product lines. Concepts aiming at the synthesis of artificial humic substances acting simultaneously as slowly nitrogen releasing sources are promising concepts in this respect. However, ligneous fractions obtained from biomass processing units usually contain residual amounts of mono-, oligo-, and polysaccharides. If such fractions are considered as starting materials for the production of soil improvers, the reaction of the “sugar” part has to be studied thoroughly, as only little is known about their fate upon the ammonoxidation and the formation of bioactive and possibly phytotoxic compounds. The present poster will report on main ammonoxidation products obtained from cellulose, xylan, glucose and xylose at different temperatures (70°C, 100°C, 140°C) and pressures (0.2 MPa, 1 MPa). The products were identified and partly quantified using GC/MS, Curiepoint pyrolysis, and NMR spectroscopy. Furthermore, first results of phytoactivity tests conducted for selected compounds will be communicated.

CELLULOSE AGING AND YELLOWING – A VIEW AT THE MOLECULAR LEVEL

P. Korntner, T. Hosoya, U. Henniges, A. Potthast, T. Rosenau University of Natural Resources and Life Sciences Vienna (BOKU) [email protected]

The CRI procedure has been developed as the first generally applicable method for isolation and identification of residual chromophores in/on cellulosic materials, which are responsible for brightness losses (“yellowing”) and other aging effects. Difficulties in isolation and exact structural characterization are mainly due to the extremely low concentrations of these colored compounds in the ppm-ppb range. The technique has been successfully applied to different (highly bleached) cellulosic pulps, cellulosic fibers (Lyocell, viscose) and cellulose derivatives (triacetate, 2.5 acetate), providing well-defined chromophoric structures in all cases. Chromophores in bleached pulps are either primary or secondary chromophores. The structures of the former are largely comparable as they are made up of carbohydrates and their degradation/oxidation products under different conditions. Such main sources of color are hydroxy-

299 [1,4]benzoquinones, hydroxynaphthoquinones, and hydroxyacetophenones. These compounds are much more resistant towards conventional bleaching than other chromophores due to their exceptionally strong resonance stabilization, so that they are consistently found as the residual chromophores “surviving” bleaching. Secondary chromophores involve process chemicals, for instance, N-heterocycles in Lyocell material. Based on the exact structure of the residual / remaining chromophores it was possible to optimize bleaching sequences and target even higher brightness and brightness stability. In the first part of the paper, the CRI approach will be briefly recalled, presenting the chromophores isolated from different cellulosic materials and structurally determined. In the second part, in-depth mechanistic studies on chromophore formation and formation pathways are contained, e.g. with regard to the roles of polysaccharidic carbonyls and carboxyls in chromophore formation. Already a single “oxidized spot” – one carbonyl in an anhydroglucose unit (AGU) – is sufficient to generate exactly the chromophores (hydroxy-[1,4]benzoquinones) found in the pulps. The whole formation pathway from this oxidized AGU to the final chromophore is supported by complete analytical data including X-ray structures. Isotopic labeling studies (13C) confirmed that such oxidized moieties are degraded into reactive C2- and C3-units, which upon re-condensation form the chromophores.

SUPERCRITICAL CARBON DIOXIDE: A POWERFUL TOOL FOR MANUFACTURING VALUE-ADDED PRODUCTS FROM NATIVE CARBOHYDRATES

C. Schimper, E. Haimer, A. Potthast, T. Rosenau, F. Liebner University of Natural Resources and Life Sciences Vienna (BOKU) [email protected]

The operating efficiency of new biomass processing units and thus the sustainability of current activities (or the current “hype”) in the biorefinery sector are largely dependent on the profitability of all product lines and the value of individual products. Thus, many attempts have been made in the last year aiming at the development of innovative, biopolymer based materials. Carbon dioxide as an easily available, cheap and “green” solvent increasingly attracts interest in material science and chemistry. The low supercritical point of only 31.2°C and 7.38 MPa is obviously the most outstanding feature of CO2 as it allows for very gentle processing of thermally and mechanically sensitive materials. The present paper will report on selected applications of supercritical carbon dioxide (scCO2) for the preparation of shaped ultra-lightweight cellulosic aerogels from both, plant and bacterial cellulose, preparation of cell scaffolding materials from cellulose phosphates, reinforcement of bacterial cellulose aerogels, loading of bacterial cellulose with bioactive compounds, and controlled antisolvent precipitation and purification of hemicellulose micro particles. Furthermore, selected properties of the all types of novel materials will be communicated.

BIOMASS PROCESSING IN IONIC LIQUIDS: INSIGHTS INTO THE DISSOLUTION BEHAVIOR OF RENEWABLE MATERIALS

M. Schrems, T. Rosenau, A. Potthast University of Natural Resources and Life Sciences Vienna (BOKU) [email protected]

Cellulose is the most abundant natural organic polymer on earth. Due to fading petrochemical, i.e. non-renewable resources, the interest on biodegradable and renewable organic starting materials is steadily increasing. So far, cellulose and other plant cell wall constituents, such as hemicellulose and lignin, have limited applications in large-scale biorefinery scenarios. When looking at the molecular scale, one reason for this are the strong intra- and inter-molecular bonds and interactions in these materials. Strongly interacting solvents are needed to achieve complete dissolution even for pure cellulose. Only a very limited number of solvent systems, such as N,N-

300 dimethylacetamide/lithium chloride (DMAc/LiCl), are currently available, which are capable to form a transparent cellulose solution that can be used in analytical systems. Specific and sometimes tedious preparations are usually needed before complete dissolution can be achieved. Ionic liquids have a high potential as powerful cellulose solvents. Ionic liquids have the ability to dissolve biorefinery products without any derivatization in their pure form and in a considerable high concentration. This applies even to unmodified wood. The possibility to dissolve not only cellulose, but also the whole surrounding matrix, gives a unique opportunity to analyze all major cell wall components under pristine conditions. By applying appropriate anti-solvents, lignin and carbohydrates can be separated in a rather unaltered form. The present study provides insight into the dissolution behavior of renewable materials in ionic liquids. Beech, spruce and rye straw were dissolved in EmimOAc as the ionic liquid of choice, which is currently one of the most frequently used cation-anion combinations among ionic liquids for biomaterial processing. The dissolution was followed by selective precipitation of cellulose, hemicelluloses, and lignin. The obtained lignin was analyzed with Curie-point pyrolysis gas chromatography/mass spectrometry (Cu-Py-GC/MS) and found to keep its chemical composition as the native ratios of H/G/S units remain unaltered. The separated cellulose/hemicellulose fractions were analyzed with gel permeation chromatography (GPC) investigating the time-dependence of the dissolution process of rye straw, eucalyptus kraft pulp and beech sulfite pulp in the ionic liquid. Unexpectedly, the molecular weight distributions are not constant in the course of time-dependent dissolution experiments. The results show a changing dissolution profile over time which is due to progressing degradation of the cellulose in the ionic liquid. This effect is more pronounced in pure IL and at higher temperatures. This observation has consequences in terms of alternative green strategies for biomass processing by means of ionic liquids and underlines the importance of adequate analytical methodology in the development of new biorefinery processes.

ADVANCED CELLULOSE ANALYTICS BY MULTIDETECTOR GPC

M. Siller, K. Ahn, T. Rosenau, A. Potthast University of Natural Resources and Life sciences, Department Chemistry, Vienna, Austria [email protected]

Cellulose is perhaps the most important biopolymer which, however, is rarely obtained as a neat polysaccharide. For most applications it has to be liberated from the matrix of accompanying lignin and hemicellulose constituents. Thus, during industrial cooking, pulping, bleaching and processing, various additional functional groups, such as aldehyde, keto, and carboxyl functions, are introduced into the cellulose chain in minor quantities. Even though such “impurities are present only in the µmol/g range, they exert distinctly negative effects on material and fiber properties, such as losses in tensile strength or brightness. Previously, these groups have been determined as sum parameters only, which is of limited value in evaluating material properties and in monitoring oxidative processes. Using pre-column derivatization with group-selective fluorescence labels, it became possible for the first time to record chemical group profiles by gel permeation chromatography (GPC) with N,N- dimethylacetamide / lithium chloride as the solvent. The fluorescence labeling is performed for both carbonyl groups (CCOA method) and carboxyl functionalities (FDAM method). Thus, the CCOA and FDAM methods record not only the total amount of carbonyl/carboxyl groups in pulps, but yields the respective concentrations in relation to the molecular weight distribution, i.e. a functional group profile similar to a detailed “degree of substitution”. DMAc/LiCl-insoluble pulps, which were inaccessible according to the original protocol, can be analyzed by a novel approach involving hydrolysis followed by HPLC quantification of the released label. In addition, a method to differentiate between keto and aldehyde groups will be discussed. In summary, novel analytical methods to analyze, quantify and profile oxidized functionalities (carbonyl, carboxyl) in cellulosics have been developed. The approaches have meanwhile been 301 applied to monitor and quantify various oxidative and degradation effects on cellulosics upon different treatments and processing steps, such as bleaching, chemical oxidation, alkalization, electron beaming, as well as thermal and light-induced aging processes. Illustrative examples of these applications will be presented and discussed along with a general introduction into the novel analytical methodology. The measurement of more than 600 different cellulose samples in more than 4000 single runs in our lab have proved the method to be quite robust and suitable for routine analysis.

SONOCHEMICAL DEGRADATION OF POLYSACCHARIDES

B. Stefanovic, T. Rosenau, A. Potthast University of Natural Resources and Life Sciences Vienna (BOKU) [email protected]

Producing fuels and chemicals from cellulose requires cellulose degradation into cellooligosaccharides and glucose monomers without much byproduct formation. Sugar monomers are then available, for instance, for further fermentative processing into fuels or bulk chemicals. Among different ways of cellulose degradation, sonochemical treatment is a very efficient and mild method, in which is in full accordance with "Green Chemistry" principles. Still, it is a non-classical approach that – in comparison to enzymatic or acidic hydrolysis – is not very widely used. Sonochemical degradation can offer a straightforward means to convert high-molecular weight polysaccharides to useful lower weight molecules. Sonochemical degradation of cellulose by 24 kHz ultrasound and the oxidative changes upon this treatment were studied. The treatment was done both in cellulose suspensions as well as in cellulose solution, with a significant reduction in degree of polymerization and significant changes in the molecular weight distribution in both cases. The rate and the yield of the degradation process depends on the degree of polymerization of the starting material, the cellulose concentration in suspension and solution, the pH value of suspension, and the temperature of suspension and solution. Cellulose degradation by ultrasound is synergistic process comprising both hydrolytic and oxidative paths of degradation.

NEW APPROACH TO CELLULOSE PHYSICAL STRUCTURE DESCRIPTION

D.A. Sukhov Sankt-Petersburg state technological university of plants polymers [email protected]

The results of our long term systematic complex investigations of cellulose molecular and supramolecular structure by Fourier Transform Infra-Red (FTIR) and Raman spectroscopy methods allowed storing unique data base and developing new approach to its physical structure description. Our model consists of four carbohydrate constituents taking into account phase and modification heterogeneity of macromolecular chains of real samples. The structural component compositions are evaluated from FTIR spectra and their concentrations predetermine fiber properties. The chain phase uniformity depends on cellulose crystallinity. The modification heterogeneity depends on co- existence of two cellulose polymorphs CI and CII in all samples. The experimental data confirm that cellulose CI and CII macromolecules have different H-bonding organizations in ordered and disordered regions [1,2]. The new idea is helpful in understanding cellulose fiber structure- properties quantitative relationships and providing plant polymer research from nano to macro. 1. Sukhov D. A. Analysis of interralation of structure and property of cellulose fibers after their vibrational spectra: dis. ... doct. of chem. sc. / STUPP. SPb., 2002. 34 с. 2. Sukhov D. A., Zilkin N.A., Valov P.M., Terentiev O.A. Cellulose structure in relation to paper properties. Tappi 74(3) 201-204 (1991).

302 APPLICATION OF THE NEW CELLULOSE STRUCTURE APPROACH FOR REFINING EFFECTS STUDY

D.A. Sukhov, O.Yu. Derkacheva, A.V. Fedorov Sankt-Petersburg state technological university of plants polymers [email protected]

The fiber structure variations of bleached kraft pulps originating from softwood (SW) and hardwood (HW) were investigated by Fourier-Transform Infrared (FTIR) spectroscopy method. The presentation will demonstrate how the new model of cellulose supramolecular structure helps understand some principal refining effects in detail [1-3]. During refining due to mechanical destruction of H-bonding system the cellulose phase and modification composition changed. In general there were observed partial decreasing relative content of native cellulose (CI) and increasing relative content of amorphous cellulose regions having CII chain conformation. This structural transformation stimulates developing bonding between fibres and increasing amount of inter fibre contacts, at the same time losing of CI ordered meant single fibre strength decreasing. So during refining paper making properties development occurs while single fibre strength decreases. The important feature of the structural transformations was nearly linear dependencies between three main cellulose parameters with equal slopes for HW and SW pulps treated in conical and plate fillings of laboratory refiner at different loads. It allows to speaking about the general similarity of refining process for the laboratory (Voith) refiner. It is worth noting that the correlations of spectral structural parameters with conventional physicochemical and mechanical test data were found out. The FSP parameter value describing internal fibrillation of fibre showed nearly linear correlations with cellulose structural parameters at all stages of refining. One can say phenomenon of internal fibrillation is connected with the transformation of cellulose supramolecular structure. The feature of SR parameter variation was its more intense increasing on second stage of refining. The found at different refining stages the pulp structure – properties relationships prove the validity of our cellulose structure model.

1. Sukhov D. A. Analysis of interralation of structure and property of cellulose fibers after their vibrational spectra: dis. ... doct. of chem. sc. / STUPP. SPb., 2002. 34 с. 2. Sukhov D. A., Zilkin N.A., Valov P.M., Terentiev O.A. Cellulose structure in relation to paper properties. Tappi 74(3) 201-204 (1991). 3. Sukhov D.A., Privalov V.I., Derkacheva O.Yu. Cellulose structure- properties relationships. / Cellulosics: Materials for Selective Separations and Other Technologies. Ellis Horwood Series in POLYMER SCIENCE AND TECHNOLOGY, Eds.: J.F.Kennedy, G.O.Phillips, P.A.Williams - Ellis Horwood, London, 1993.

303 MOLECULAR DESIGN OF BIVALENT OR DUAL ACTION DRUGS ON THE BASIS OF NATURAL COMPOUNDS

N. S. Zefirov, V. A.Palyulin, O. N. Zefirova Department of Chemistry, M. V. Lomonosov Moscow State University Institute of Physiologically Active Compounds RAS E-mail: [email protected]

Design of new drugs is a sophisticated process involving the application of molecular modeling and QSAR techniques, virtual screening and molecular docking. The joint application of these approaches provides deeper understanding of both structure-activity relationships and ligand- receptor interactions as well as facilitates lead finding and optimization. These techniques can be successfully used for the design of twin drugs, which mean drugs containing two pharmacopoeia groups combined covalently in a single molecule or dual action drugs – i.e. the compounds which combine two desired different pharmacological actions at a similarly efficacious dose. Dual action of a drug can be sub-classified into (1) its action on two different biotargets and (2) action on two different sites of the same biotarget. The first case will be exemplified by our design of new neuroprotective compounds. The second case will be clarified using (a) the bivalent positive modulator of AMPA receptor and (b) dual action conjugate of a chemical component of a plant Colchicum autumnale –colchicine – with a “simplified” taxol analogue interacting with tubulin:

Ph O O (CH2)n NH

BocNH O O O OCH3 O OH CH3O OCH3 CH3O

Colchicine part of the molecule

In general, this approach was successfully used in the design of new neuroprotectors with cognition enhancing properties (extraordinary high potency of some designed compounds starting from picomolar concentration had been revealed – absolute record among all currently known positive AMPA receptor modulators) as well as for synthesis of dual action compounds active against human lung carcinoma А549 cell line.

1. N.S.Zefirov, V.A. Palyulin. Molecular Modelling of Central Nervous System Receptors. Mendeleev Commun. 2010, 20, 243-248. 2. O.N. Zefirova, E.V. Nurieva, H. Lemcke, A.A. Ivanov, D.V. Shishov, D.G. Weiss, S.A. Kuznetsov, N.S. Zefirov. Design, synthesis and bioactivity of putative tubulin ligands with adamantane core. Bioorg. Med. Chem. Lett. 2008, 18, 5091–5094.

304 FORMATION OF OXALIC ACID IN ALKALINE PEROXIDE TREATMENT OF DIFFERENT WOOD SUBSTANCES

M. Häärä, L. Vähäsalo, A. Sundberg, St. Willför Åbo Akademi University, Process Chemistry Centre, c/o Laboratory of Wood and Paper Chemistry, Porthansgatan 3, FI-20500, Turku/Åbo, Finland

Calcium oxalate is one of the most problematic scale salts occurring in pulping and papermaking, and particularly in the oxidative bleaching stages. Calcium oxalate scale is formed when dissolved calcium reacts with oxalate ions to form a salt with very low solubility in water. The scaling often leads to production disturbances and losses and it is also a limiting factor for water system closure. Calcium oxalate scaling is a well-known problem also in other industrial processes like sugar plants, breweries and biorefineries, where extensive oxidation of organic material takes place. In humans, calcium oxalate precipitates occur in the form of kidney stones. It has been shown that in alkaline peroxide bleaching of mechanical pulps, oxalic acid is mainly formed as oxidation products of lignin and hemicelluloses. Some studies have presented results that support the hypothesis that it is the functional groups in lignin that are the main precursors, whereas others have concluded that hemicelluloses, especially xylans, are the main contributors to the formed oxalate. The aim of this work was to study the formation of oxalic acid from spruce wood components under alkaline peroxide bleaching conditions. Different wood substances were treated with alkaline peroxide bleaching chemicals in 2% consistency in test tubes, and the amount of oxalate/oxalic acid released was analysed by IC. The substances included in the experiments were spruce mill wood lignin, lignin isolated from spruce TMP, spruce wood galactoglucomannan isolated by accelerated solvent extraction (ASE), powders of spruce inner and outer bark, commercial birch xylan and acetic acid. Unbleached spruce groundwood pulp was included in the experiments as a reference. The treatments were carried out in a water bath at 73°C for 90 minutes. The chemicals used were 3% sodium hydroxide, 2% sodium silicate and 6% hydrogen peroxide. After the treatment, the samples were acidified with 2 M HCl to pH 1 for total oxalate analysis in order to keep the oxalate in dissolved form and to dissolve possible precipitates. Before IC analysis, the samples were filtrated with a 0.45 µm membrane filter. The amount of soluble oxalate was also analysed in the peroxide treated bark and pulp samples, as these materials contain oxalate already before the treatment. This was done by filtrating the sample directly after peroxide treatment using a 0.45 µm membrane. In this study, xylan and lignin were found to be the main precursors for oxalic acid formation under alkaline peroxide bleaching conditions, whereas galactoglucomannan was a smaller contributor. Most oxalic acid was formed from xylan, but taking into account the relatively low content of xylan in spruce wood, lignin is at least an equally important source. Due to the fact that birch xylan with some degree of acetylation was used in this study, also acetic acid was included in these experiments. This was done to clarify whether the acetic acid formation during deacetylation of natively acetylated hemicelluloses has any relevance for oxalate formation. However, only a minor amount of oxalic acid was formed in alkaline peroxide treatment of acetic acid. The spruce bark samples, especially the outer bark, were the biggest sources of oxalate from the treated substances. This means that good debarking is critical for calcium oxalate scale control in mechanical pulping.

305

PARTICIPATION OF CATALYSTS FE-ARD(NI-ARD) IN BIOSYNTHESIS OF ETHYLENE AND POLYAMINE.

L.I. Matienko, V.I. Binukov, L.A. Mosolova, E.M. Mil, G.E. Zaikov N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences [email protected]

Two aci-reducton dioxygenases ARD and ARD´ are remarkable that they posses the same polypeptide sequence, but bind different metal ions (Ni2 + and Fe2 + respectively). So they transform aci-reducton into various products. Methionine is a product of oxygenation by molecular O2 of aci-reducton, which is carried out with ARD´. Carbon monoxide, CO, and carbonyl products are formed at aci-reducton conversion under the action of dioxygen and catalyzed by Ni(II)- containing dioxygenase ARD. CO is a representative of the new class of neural messengers, and like NO seems to be a signal transducer. It is possible to assume an important directing role of H- bonds, in regulation of synthesis of methionine (and also ethylene and polyamine, formed in a methionine cycle) at the expense of braking of action ARD. Conversion of monomeric to multimeric forms could be a general way of regulating ARD activity in plants [1]. The Ni(II)-ARD in plants may be an unwanted enzyme and catalyst association in macrostructures at expense of the intermolecular H-bonds may be a mechanism to reduce Ni(II)-ARD activity in mechanism of Ni(II)(Fe(II))-ARD functionalization . Earlier we have established that heteroligand complexes Ni2(AcO)3(acac)MP·2H2O (MP=N- methylpirrolidone-2) (Q), are real selective catalysts in alkylarenes oxidations (ethylbenzene, cumene, toluene) with molecular oxygen into corresponding ROOH. We have proved that particles Q are formed in the course of reactions of oxidation in the presence of system {Ni(acac)2+MP} as a result of oxygenation by molecular oxygen of one of (acac) – ligands in complex Ni(acac)2·MP on the mechanism similar to action of Ni(II)-containing ARD. In the present work by means of АFМ method (Atomic Force Microscopy) we observed the growth of the nanostructures on the basis of complexes Ni2(AcO)3(acac)MP·2H2O, at the expense of intermolecular hydrogen bonds, on special prepared silicon surface. The received results confirm the our assumption of an important role of H-bonds in the mechanism of catalysis with nickel complexes Ni2(AcO)3(acac)MP·2H2O. These data can be useful to an explanation of the mechanism of a catalysis with Ni(II)(Fe(II))-ARD also. Key words: Ni(II)(Fe(II))-ARD, methionine cycle, ethylene, polyamine, CO, nanostructures, Ni2(OAc)3(acac)MP•2H2O (MP=N-methylpirrolidon-2), H-bonds.

[1] M. Sauter, R. Lorbiecke, Bo OuYang, T.C. Pochapsky, G. Rzewuski, The Plant Journal (2005), 44, 718-729.

306 OXIDATION OF FERULIC ACID BY HYDROGEN PEROXIDE USING POLYOXOMETALATES AS A CATALYSTS

A.L. Beloglazova, Popova N.R., Bogolitsyn K.G. Northern (Arctic) federal university [email protected]

In the delignification and bleaching processes homogeneous catalysis by early-transition-metal- oxygen-anion clusters, henceforth referred to as polyoxometalates, is an interesting area, in part as a consequence of the effectiveness of these catalysts and their compatibility with environmentally friendly conditions (e.g. molecular oxygen and hydrogen peroxide). As a result of oxidation we can derive new high-value chemicals as products of catalytic oxidation of lignin compounds. Moreover polyoxometalates intensify the oxidation of lignin and don’t attack the cellulose. All of this is very important for the complex conversion of plant raw materials. The purpose of the given work is establishment of the main rules in process of catalytic oxidation of lignin compounds by hydrogen peroxide in acidic medium using polyoxometalates as a catalysts. In this connection, influence of the рН of solution, the concentration of oxidant, oxidized compound and catalyst on the kinetics of catalytic oxidation process of model lignin compound, ferullic acid, were investigated. Being preliminary treated by hydrogen peroxide in acidic medium without using any catalyst, ferullic acid revealed no oxidization. The optimal рН of solution in catalytic reaction is pH3 when processes of oxidized compound activation realize more intensive and active form to reoxidation of the catalyst is generated. Results of investigation of hydrogen peroxide concentration influence showed that highest value of initial rate of reaction is observed when relation of concentrations of catalyst and oxidant is 1:20. Probably, this is associated with generating of the most active form of the catalyst. Accoding with the literature [1] peroxointermediates (compounds including in the structure before 24 peroxogroups) are generated in reaction of interaction between hydrogen heroxide and polyoxometalate. When the relation of concentrations of catalyst and oxidant is more than 1:20 peroxointermediates decay and as a consequence value of initial rate of reaction decreases. The products were investigated using GC/MS analyses.

[1] Kuznetsova, L.I.; Maksimovskaya, R.I. other//Izvestiya Akademii nauk, seriya himicheskaya, 1983, 4, 733-737.

307 INDEX

Barabanova A.O...... 211, 267, 275 A Baryshnikov S.V...... 190 Bayunov A.P...... 263 Abalov I.V...... 264 Bazarnova N.G...... 129 Abdel-Salam H.S...... 127 Begum S...... 79 Abilov Zh.A...... 58 Bei M.P...... 20, 21 Abraeva Z.Ch...... 5 Beksaev S.G...... 140 Absalon C...... 136 Belash D.Yu...... 248 Adekenov S.M...... 5, 122 Belgacem M.N...... 25, 26 Afanasieva A.S...... 19 Belgacem N...... 22 Agabekov V.E...... 218 Beliaev S.A...... 251, 252 Agabekov V.Е...... 198 Beliy V.A...... 264 Ageev A.Ya...... 7 Belmokhtar N...... 23 Ageev M.A...... 7 Beloglazova A.L ...... 307 Ageeva A.A...... 73, 74, 143, 144, 249, 250 Belostotskaya I.S...... 278 Agudelo A.J...... 132, 133 Belska N.V...... 189 Ahabalajeu A.A...... 80 Belskii Yu.P...... 82 Ahabalayeva A.D...... 8 Belsky Y.P...... 189 Ahmedov A.N...... 9 Belyaeva N.V...... 23, 66 Ahn K...... 298, 301 Belyasova N.A...... 48 Aimakov O.A...... 10 Belykh O.A...... 24 Akhmedjanova V.I...... 5, 11 Ben Mabrouk A...... 25, 26 Akhmetshina D.Z...... 60 Berdnikova P.V...... 26 Akim E.L...... 28 Beregovtsova N.G...... 190 Akmalova G.U...... 11 Berezina E.V...... 27 Akulina I.V...... 277 Bezborodova T.G...... 28 Al’metkina L.A...... 152 Bildukevich T.D...... 35, 36 Alekhina M...... 12 Bilyk A.V...... 166 Alekseev K.V...... 285 Bizhanov Z.A...... 19 Alekseeva L.I...... 13 Blinova I.A...... 7 Alekseeva O.M...... 278 Bludenko A.V...... 85 Alen R...... 220 Bobakulov Kh.M...... 55 Alinkina E.S...... 245 Bochek A.M...... 264, 280, 296 Alinovskaya V.A...... 252, 253 Bochek А.М...... 28 Almetkina L.A...... 13, 150, 151 Bogdan V.I...... 86 Andreev A.Yu...... 191 Bogdanchikova T.V...... 122 Andrukhova M.V...... 14 Bogdanova T.V...... 29 Angenot L...... 11 Bogdanovich L.N...... 211 Anisimova N.A...... 15 Antipin V.K...... 16 Bogolitsyn K.G...... 307 Antsupova T.P...... 19 Bokach N.A...... 285 Ardashov O.V...... 242 Boldyrev V.V...... 118 Arias A.J...... 17, 180 Boltovskii V.S...... 30, 148 Arias G...... 213 Bondarenko I.I...... 122 Arias G.P...... 17, 180 Borisenko N.I...... 31, 32, 269, 286 Artem’eva E.Yu...... 98 Borisenko S.N...... 31, 32, 269, 286 Artemenko E.A...... 188 Borisova N.S...... 33 Artemkina N.A...... 17 Borovitsky N.Y...... 149 Artemova N.P...... 277 Borovyk O.O...... 96 Asemova M.K...... 115 Boufi S...... 25, 26 Autlov S.A...... 129 Boyko M.I...... 47 Auyezov A.B...... 19 Brenner-Weiss G...... 126 Avdeeva E.Y...... 106 Brezhneva T.A...... 270 Aymonier C...... 136 Brilkina A.A...... 27 Azeez A...... 135 Brosse N...... 41 Brovkina J...... 196 B Brusilovskaya N.G...... 264 Bucharskaya A.B...... 290 Babkin V.A...... 158 Budinski Simendic J...... 246 Babykina A.M...... 19 Budnikov H.C...... 260 Balova I.A...... 279 Budykina N.P...... 34

308 Buhtiyarov V.I...... 42 Domnina N.S...... 278 Buinov М.V...... 35 Dorofeeva L.Yu...... 277 Bukhtiyarova G.A...... 43 Dreval K.G...... 47 Binukov V.I...... 306 Driker B.N...... 246 Burkova V.N...... 128 Dubkova V.I...... 48 Burlakova E.B...... 245, 278 Dundich V.O...... 248 Butrim N.S...... 35, 36 Duran D.C...... 49, 184, 212, 213 Butrim S.M...... 35, 36 Durnova N.A...... 50 Bychkovsky P.M...... 252, 253 Dushkin A.V...... 137 Bykov K.I...... 225 Dzhan T.V...... 97 Bykova M.V...... 37, 248 Dzhumanova Z.K...... 50 Bystrova V.V...... 236 Bystrushkin A.G...... 13 E Bystrushkina Е.V...... 13 Eckerman C...... 67 Efanov M.V...... 51 C Efremenko E...... 214, 215 Caballero D...... 213 Efremov A.A...... 52, 145, 175, 261, 295 Cabulis U...... 86 Efremov E.A...... 52 Cakic S...... 246 Egamberdiyev E.A...... 232 Cala M.P...... 213 Egorov V.A...... 60 Caragia V...... 123, 147, 200 Eklund P.C...... 207, 208 Carrier M...... 136 El Hage R...... 41 Celzard A...... 219 Eliseev O.L...... 108 Cerempei V...... 170 Elokhovsky V.Ju...... 212 Ceskova I...... 207 Erasov V.S...... 85 Chabbert B...... 23, 179 Eremenko O.N...... 182 Chepulsky S.A...... 77 Erkabaev А.R...... 289 Cherkasov R.A...... 13, 150, 152 Erkhitueva E.B...... 53 Chernishova O.A...... 38 Ermatov A.M...... 293 Chernobrovkina D.I...... 168 Erohin V.N...... 245 Chernyak M.Yu...... 210 Erzhanov K.B...... 115 Chernyavskaya S...... 231 Esaulko N.A...... 54 Chirau I...... 170 Eshbakova K.A...... 55 Chistovalov S.M...... 39 Eskeldinova Ye...... 284 Chukicheva I.Yu...... 57, 117, 125, 269, 272 Estrada M...... 44 Chulkov V.N...... 85 Evstafyev S.N...... 56 Coy P.V...... 292 Evstigneyev E.I...... 56 Evtuguin D.V...... 181 D F Dalimov D.N...... 289 Dalimova G.N...... 50 Faizullina L.Kh...... 183 Danchenko M.A...... 39 Faminskaya L.A...... 65 Darwish A.G...... 127 Fatkullina L.D...... 245 Davis R.J...... 203 Fedorishcheva G.A...... 160 Davis S...... 203 Fedorov A.V...... 303 Davlyashin K.S...... 40 Fedorova A.I...... 76 Davydova V.N...... 275 Fedorova I.V...... 57, 269 Deglise X...... 41 Fedoseeva G.M...... 35, 107 Deleanu M...... 147 Fedulina T.G...... 87 Delidovich I.V...... 42 Fetisova A.A...... 23, 66 Deliy I.V...... 43 Filpponen I...... 67, 176 Demidova Yu.S...... 44, 201, 202 Fleisher V.L...... 14 Denisova M.N...... 45 Fomina E.S...... 56 Derkacheva O.Yu...... 303 Franzreb M...... 126 Derkacheva О.Yu...... 46, 220 Freire C.S.R...... 46 Dikusar E.A...... 280 French A...... 181 Dmitruk A.F...... 121, 165 Fridrihsone A...... 86, 216 Do Trung S...... 214 Frolova L.L...... 117 Dogadina A.V...... 53 Dolgikh M.P...... 137 G Domingues M.R.M...... 239 Gabdullin G.T...... 13 Domingues R.M.A...... 46 309 Gabdullina G.T...... 150, 151, 152 Holmbom B.R...... 67, 170, 247 Gadetskaya A.V...... 58 Holmbom T.R...... 67 Gaidukevich O.A...... 8 Hosoya T...... 299 Gaidukevich О.А...... 20 Hripunov A.K...... 209 Galayko N.V...... 59 Hurshkainen T.V...... 68 Galbraikh L.S...... 99 Husenov A.Sh...... 69 Galynkin V.A...... 166, 174 Hvizdos P...... 204 Gandini A...... 60 Gapanovich V.N...... 251 I Garabadjiu A.V.... 73, 74, 143, 144, 166, 174, 249, 250 Iakovlev M...... 70 Garayev R.S...... 277 Garyntseva N.V...... 219 Ibragimov B.T...... 227 Gataullin R.R...... 206 Ibrahim V...... 243 Gavrilova I.I...... 280, 296 Ignatev A.N...... 70 Gavrilova K.Y...... 122 Igosheva E.V...... 71 Il’ina I.V...... 242 Gein V.L...... 191 Gimalova F.A...... 60 Ilushka I.V...... 140 Giniyatova E.R...... 260 Ilyashenko N.V...... 265 Ionin B.I...... 53 Glazunov V.P...... 275 Gofman I.V...... 264, 280, 296 Ionova D.A...... 153 Gogin L.L...... 257 Isaeva E.V...... 72 Ischenko O.V...... 73, 74, 143, 144, 249, 250 Goloshchapov A.N...... 278 Golovanchikov A.B...... 62 Ishmuratova M.Yu...... 115, 221 Golovco Ju...... 147, 200 Islamov A.H...... 289 Ismailov A.I...... 293 Golub N.V...... 252, 253 Golyazimova O.V...... 61, 62 Ivaniutsina A.V...... 75, 251 Golynskii P.S...... 199 Ivanova A.N...... 82, 189 Ivanova I.K...... 76 Gorbach V.I...... 275 Gorbacheva T.T...... 17 Ivanov-Omskii V.I...... 266 Gorbatovskyi A.A...... 79 Ivaska A...... 218 Izmestev E.S...... 76 Gorbunova N.V...... 121 Gorina Y.V...... 106 Goryachikh A.D...... 232 J Goto M...... 221 Jaeger C...... 181 Gracheva N.V...... 62 Jorobekova Sh.J...... 121 Granholm K...... 218 Judin V.E...... 264, 296 Gribkov I.V...... 63, 222 Grigoriev Yu.A...... 64 K Grigoryev A.I...... 273 Grishechko L.I...... 190 Kadirov O.Sh...... 69 Grishko V.V...... 59, 71 Kadirova Z. Ch...... 77 Grishkovets V.I...... 248, 269 Kadyrova T.V...... 106 Gromov N.V...... 42 Kaldstrom M...... 78 Gruzdeva A.E...... 65 Kalinina S.A...... 281 Gryazkin A.V...... 23, 66, 266 Kalitnik A.A...... 267 Grytsenko N.A...... 96 Kalmykova E.N...... 79 Gudkov D...... 215 Kalyuzhnaya L.M...... 280 Kaminskaya O.V...... 122 H Kaminskiy I.P...... 106 Karankevitch H.G...... 80 Habasescu I...... 170 Karapun M. Yu...... 80 Habrant A...... 23 Karelina E.V...... 73, 74, 143, 144, 249, 250 Haimer E...... 300 Karimi K...... 127 Hanin V.P...... 161 Karimova E.V...... 193 Harju L...... 218 Karpitsky V.I...... 112 Hatti-Kaul R...... 243 Kartel M.T...... 149 Hemming J...... 67 Kayan E.S...... 82 Henniges U...... 298, 299 Kaygorodov K.L...... 224 Herzig R...... 91 Kazantsev A.V...... 10 Hill C.A.S...... 66 Kaziahmetova D.T...... 10 Hoeger I.C...... 67 Kaziev G.Z...... 225, 282 Hohrina E.A...... 167 Kazmina M.A...... 31, 32, 269 Holmbom B...... 218, 223 Kelley S...... 67

310 Khalikova G.M...... 60 Korotkikh E.A...... 102 Khalitova R.R...... 82 Korotkov A.N...... 99 Khassin A.A...... 194, 205 Korulkin D.Y...... 103, 238 Khidyrova N.K...... 284, 297 Koryakina V.V...... 76 Khizhnyak S.D...... 265 Korzh E.N...... 248 Khlebnicova T.S...... 165 Kosterova R.I...... 252, 253 Khlebnikova T.B...... 26, 83 Kostyro Ya.A...... 285 Khodachek A.S...... 23 Kovalev N.V...... 23, 66, 266 Khodachek А.S...... 66 Kovalyov V.N...... 104 Khodov N...... 84 Kovjgina A.L...... 158 Kholodkova E.M...... 85 Kowalski P.W...... 230 Khramchihin A.V...... 53 Kozhamkulova Zh.A...... 58 Khromova S.A...... 37 Kozhevnikov I.V...... 105 Khudaibergenova B.M...... 121 Kozlov G.V...... 73, 74, 143, 144, 166, 249, 250 Khudaibergenova E.M...... 121 Kozlov V.A...... 153 Khudoshin A.G...... 86 Krakovsky I...... 246 Khusainova M.F...... 27 Kramor R.V...... 287 Khvostov M.V...... 137 Krasavtsev B.E...... 106 Kim Ye...... 284 Krasnikova T.A...... 104 Kim Yu.A...... 278 Krasnov E.A...... 106 Kind A.V...... 298 Kritchenkov A.S...... 285 Kirichenko E.B...... 112 Krivosheev I.M...... 107 Kirpluks M...... 86 Kruchkov M.V...... 108 Kiryushina M.F...... 87 Krutko N.P...... 48 Kitaeva M.V...... 88 Krutov S.M...... 63, 212, 222 Kiyamova S.E...... 284 Kryuchkov V.A...... 131 Kladiev A.A...... 252 Kryuchkova T.N...... 104 Klimchuk A.T...... 115 Kryukova A.V...... 166 Klimenko S.V...... 97 Krywuc J...... 230 Klinger K.-M...... 299 Kuchin A.V...... 76 Knyazev A.V...... 89, 90 Kudryashov V.K...... 109 Knyazeva O.A...... 89, 90 Kuhareva T.S...... 282 Kobrakov K.I...... 93 Kuimov A...... 84 Kochetkov K.A...... 39 Kukharenko J.A...... 158 Kokurina N.Yu...... 65 Kukina T.P...... 297 Kolbas A.P...... 91 Kukushkin R.G...... 110, 185 Kolbas N...... 92 Kukushkin V.Yu...... 285 Kolnogorov K.P...... 240 Kulikova E.M...... 212 Kolpachova O.A...... 93 Kumar N...... 78 Koltasheva A.V...... 246 Kurapova M.Y...... 256 Koltunov K.Yu...... 93 Kurbanbaeva A.E...... 111 Komissarov G.G...... 124 Kurganov A.K...... 112 Komissarova N.L...... 278 Kurilov D.V...... 112, 114 Konev V.N...... 83 Kurmankulov N.B...... 115 Kong X.M...... 290 Kurov V.S...... 137 Konkina I.G...... 89, 90, 94 Kushnereva E.V...... 64 Konnova G.N...... 95 Kutakova N.A...... 100, 116 Konon A.D...... 96 Kutchin A.V...... 57, 117, 269, 272 Konovalova E.Yu...... 97 Kutin A.A...... 273 Konovalova G.N...... 98 Kuvaeva Z.I...... 80 Konshin V.V...... 98 Kuzhaeva A.A...... 15 Konshina D.N...... 98 Kuzmichova N.A...... 268 Konstantinova S.A...... 99 Kuznetsov B.N...... 117, 190, 219, 237 Koptelova E.N...... 100 Kuznetsova S.A...... 118, 119, 120, 237 Kopytov Yu.P...... 248 Kydralieva K.A...... 121 Korbut V.I...... 218 Korenev A.N...... 39 L Kormilkina D.Y...... 101 Laine J...... 67, 176 Kornienko T.S...... 155 Korntner P...... 299 Laka M...... 231 Korostelev A.V...... 155 Lakhvich F.A...... 165 Lamotkin S.A...... 8, 240, 241 Koroteev A.M...... 282 Koroteev M.P...... 225, 282 Lapidus A.L...... 108

311 Larina G.V...... 197 Meier D...... 135 Lavrent’ev V.K...... 280 Meija-Feldmane A...... 260 Lavrentev V.K...... 264, 296 Mench M...... 91, 136 Lazdina B...... 216 Mereiter K...... 181 Lebedev M.Yu...... 37 Mertin E.V...... 246 Lebedeva M.F...... 280 Meshchaninov M.A...... 64 Lehnen R...... 173 Meteleva E.S...... 137 Lekar A.V...... 31, 32, 269, 286 Metreveli A.K...... 85 Leonovich A.A...... 176 Metreveli P.K...... 85 Leontiev V.N...... 148 Michura P...... 182 Lesishina Yu.O...... 121, 165 Midukov N.P...... 137 Lezhneva M.Y...... 122 Miheev K.V...... 128 Liebner F...... 169, 299, 300 Mikhailenko M.A...... 118 Linda L...... 123 Mikhailova E.A...... 138 Lipatova N.S...... 224 Mikheyeva T.A...... 122 Lisitskaya T.B...... 174 Mil E.M...... 306 Litovka Yu.A...... 72 Milchakova N.A...... 288 Litvinets S.G...... 133 Milutina A.V...... 158 Llinas M...... 49 Minakova A.R...... 139 Lobanov A.V...... 124 Minina E.V...... 116 Loginova I.V...... 125 Minyukova T.P...... 194, 205 Lopes-Ferreira N...... 23 Mironenko N.V...... 270 Loppinet-Serani A...... 136 Mirovich V.M...... 107 Loureiro N...... 239 Misane M...... 216, 250 Lozovskaya T.S...... 126 Misharina T.A...... 245 Lunin V.V...... 70, 86, 129 Misin V.M...... 112 Lupascu T...... 170 Mochna V.N...... 73, 74, 143, 144, 249, 250 Lуpez Y...... 127 Mokeev M.V...... 78, 273 Molotcov I...... 170 M Monakhova T.V...... 162 Monogioudi E...... 208 Machmudah S...... 221 Monteiro De Araujo silva M...... 92 Macneil D...... 223 Mora A...... 212 Maevskaya O.I...... 48 Morgulis I.I...... 119 Magnin A...... 25, 26 Moroz B.L...... 42 Mahmoud H.I...... 127 Moskalenko Yu.E...... 78 Makangara J.J...... 79 Mosolova L.A...... 306 Makhotina L.G...... 28 Mukarramov N.I...... 284 Maltseva E.V...... 128 Mukuseva O.V...... 139 Malyar Yu.N...... 118, 120 Mulyashov S.A...... 140 Malyshev R.M...... 109 Murinov Yu.I...... 89, 94 Mamatkulova N.M...... 297 Murodov M.M...... 141, 142, 178, 232 Mamleeva N.A...... 129 Murzin D.Yu...... 44, 78, 203 Mammadov R...... 130 Murzina E.V...... 203 Mammadova Z...... 130 Musatov A.V...... 74, 143, 144, 249, 250 Mandzhieva S.S...... 269, 286 Mustafin A.G...... 33 Mandzhiyeva S.S...... 31, 32 Myasnikov A.G...... 39 Marakulina K.M...... 287 Mаtchanov А.D...... 289 Marchand L...... 91 Marias F...... 136 N Marina N.V...... 131 Martianov Ye.M...... 13, 150, 151, 152 Nagorskaya V.P...... 267 Martin C...... 127, 131 Nakatsubo F...... 181 Martinez J.R...... 17, 49, 132, 133, 180, 184, 212, 213 Narchuganov A.N...... 145 Martinson E.A...... 133 Nasakin O.E...... 191 Maslakova T.I...... 246 Navolokin N.A...... 290 Maslova O...... 215 Nazarova A.A...... 291 Maslyakova G.N...... 290 Nedopekina D.A...... 189 Matienko L.I...... 306 Nehnevajova E...... 91 Mattsat Yu.V...... 26 Nemceva A.V...... 146 Matvienko L.G...... 42 Nesterova N.A...... 280, 296 Mazaletskaya L.I...... 269 Nguyen Dinh T...... 214 Medvedeva T.M...... 134 Nguyen Ngoc T...... 214

312 Nguyen Thi D...... 214 Piskunov M.A...... 163 Nguyen V.T...... 165 Piven Yu.A...... 165 Nicolaeva D...... 123, 147, 200 Pizzi A...... 41 Nifant’ev E.E...... 225 Plaschina I.G...... 287 Nifantiev E.E...... 148 Platonov A.K...... 146 Nifantyev E.E...... 282 Platonova E.R...... 292 Nikiforov A.O...... 137 Pliekhova E.L...... 165 Nikitina L.E...... 277 Ploshko E.A...... 298 Nikitsenko A.I...... 148 Plyusnina S.N...... 272 Nikolaevich V.A...... 165 Podogova M...... 123, 147 Nikolaichuk A.A...... 149 Polishuk S.D...... 291 Nikonov V.Y...... 122 Politov A.A...... 61, 62 Nizamov I.S...... 13, 150, 151, 152 Polukonova N.V...... 50, 290 Novikov K.V...... 153 Polyakova N.V...... 160 Novikova E.N...... 154 Pomeshalkin E.I...... 166 Novikova I.V...... 102, 155 Ponomarev A.V...... 85 Novoselova G.N...... 131 Ponomarev D.A...... 101 Nurakyshev A...... 19 Ponomarev E.A...... 40 Nusser M...... 126 Ponomareva M.A...... 15 Popov S.A...... 167 O Popova A.A...... 51 Popova E.A...... 232 Obluchinskaya E.D...... 156 Popova E.N...... 212, 280 Odermatt J...... 135 Popova N.R ...... 307 Odinokov V.N...... 82 Popova O.P...... 80 Odyakov V.F...... 257 Popova O.V...... 168 Okatova O.V...... 28 Potthast A...... 169, 181, 298, 299, 300, 301, 302 Oliveira E...... 46 Pourjavadi A...... 169 Onuchina N.A...... 158 Povar I...... 170 Oskonbaeva J.A...... 185 Pranovich A...... 218 Osovskaya I.I...... 158, 264 Pranovich A.V...... 170, 247 Ostapchenko L.I...... 259 Prilepina I.I...... 161 Ostapko I.N...... 255 Prosvirin I.P...... 202 Osterberg M...... 67, 176 Prusov A.N...... 171, 172 Ostroukhova L.A...... 158 Prusova S.M...... 171, 172 Ostrovskii V.A...... 232 Pryakhin A.N...... 70 Puls J...... 131, 173 P Pushkarev M.A...... 174 Pai Z.P...... 26, 83, 159 Pushkareva E.S...... 175 Pakhomov P.M...... 265 Pylina Y.I...... 187 Pakkanen H...... 220 Pyrog T.P...... 96 Panarin E.F...... 280, 296 Panasenko A.E...... 160 Q Panov E.I...... 161 Quintana E...... 176 Pantyukhov P.V...... 162 Parmon V.N...... 42, 159, 248 R Parpiev N.A...... 77 Parshikova V.N...... 163 Rabysh A.A...... 176 Pascoal Neto C...... 46 Radbil A...... 84 Pavlova A.V...... 242 Rahmadieva S.B...... 221 Palyulin V. A...... 304 Rahman M.M...... 177 Pazuhina G.A...... 40, 139 Rahmonova D.S...... 77 Peregudov A.S...... 39 Rakhimova N.K...... 5 Pereslavceva A.V...... 59 Rakhmadiyeva S...... 284 Perez Y...... 49 Rakhmanberdiev G.R...... 11, 69 Pervova I.G...... 246 Rakhmonberdiev G.R...... 178 Petrenko E.V...... 163 Rakhmonberdiyev G.R...... 142 Petrichenko V.M...... 281, 294 Rakotoarivonina H...... 179 Petrov A.V...... 219 Ramashka V.A...... 75 Piligaev A.V...... 110 Ramirez C.B...... 49 Ping L...... 41 Ramirez E.A...... 17, 180 Pintilie B...... 170 Ravizkiy M.M...... 63, 222 Pirjaev P.A...... 42 Redikultsev Yu.V...... 109 313 Rei Vilar M...... 26 Shakurova E.R...... 189 Remezov A.I...... 99 Shapovalov V...... 195 Remond C...... 179 Sharipov Kh.T...... 77 Reshetnikov S.I...... 44 Sharypov V.I...... 190 Reshetnikov V.N...... 8 Shchegolikhin A.N...... 124 Reunov A.V...... 267 Sheludchenko N.I...... 269 Rezhepov K.Zh...... 292, 293 Sheng Goh C...... 41 Ristic I...... 204, 246 Shevchenko O.G...... 272 Rojas O...... 176 Shevchuk I.L...... 280 Rojas O.J...... 67 Shevchuk N.Y...... 251 Romanteeva Yu.V...... 50 Shevchuk O.M...... 255 Rosenau T...... 169, 181, 298, 299, 300, 301, 302 Sheveleva N.N...... 154 Roshchin V.I...... 38, 82, 112, 237 Sheverdov V.P...... 191 Ross S.A...... 58 Shibaeva T.G...... 34 Rubaev S.A...... 292 Shiretorova V.G...... 192 Rubtsova S.A...... 76 Shishkina L.N...... 269, 272, 287 Rudnitskaya A...... 181 Shitz E.Yu...... 76 Ruiz C.A...... 17, 180, 213 Shkidchenko A.N...... 109 Ruschih D...... 170 Shkolnikov E.V...... 192 Ryabukhin D.S...... 146, 271 Shneyder Yu.A...... 193 Ryazanova T.V...... 72, 182 Shpatov A.V...... 167 Shpironok O.G...... 174 S Shtertser N.V...... 194 Shtrants I.V...... 122 Saake B...... 131, 173 Shubakov A.A...... 138 Sadykov V.M...... 112, 114 Shulga G...... 195, 196 Safarov A.K...... 5 Shurova M.V...... 197 Sagitdinova Kh.F...... 60 Sidorenko Y.S...... 122 Salakhutdinov N.F...... 242 Sidorenko А.Yu...... 198 Samet A.V...... 183 Silchenko L.A...... 199 Samsonova Z.P...... 15 Siller M...... 301 Sanabria B.E...... 184, 212 Silva C.M...... 46 Sanayeva A.Y...... 197 Silvestre A.J.D...... 46, 239 Sandric M...... 200 Simac V...... 147, 200 Santos S.A.O...... 239 Simakov A.V...... 44 Sartova K.A...... 185 Simakova I.L...... 44, 201, 202, 205 Sasaki M...... 221 Simakova O.A...... 203 Sazanov Ju.N...... 222 Simendic V...... 204, 246 Sazanov Yu.N...... 273 Simkin V.B...... 106 Sazhina N.N...... 112 Simoes M.M.Q...... 239 Sazon N.I...... 218 Simonov M.N...... 201, 202, 205 Scheglova T.A...... 112, 114 Siropyatov B.Ya...... 281 Scherbakova O.V...... 294 Sirovski F.S...... 140 Schimper C...... 300 Sixta H...... 12, 226 Schreiber A...... 131, 173 Skakovskii E.D...... 8 Schrems M...... 169, 300 Skakovskii Е.D...... 20 Selemenev V.F...... 270 Skakovskij E.D...... 241 Selishcheva S.A...... 110, 185 Skladchikov D.A...... 206 Semenov V.V...... 183 Skripova N.N...... 68 Senko O...... 215 Skudra S...... 195, 196 Senkov G.M...... 198 Skute M...... 231 Serbinovsky M.Y...... 168 Skvortsova G.N...... 118 Serdobintseva I.R...... 98 Smarygin S.N...... 263 Sergeeva O.Yu...... 278 Smeds A.I...... 207, 208 Sevastyanova I...... 250 Smirnov A.A...... 248 Shabiev R.O...... 186 Smirnova E.G...... 209 Shadrin D.M...... 187 Smirnova I.P...... 193 Shafeeva M.V...... 188 Smirnova M.A...... 210 Shakels V...... 195 Smirnova M.Yu...... 48 Shaker E.S...... 127 Smolin A.S...... 186 Shakhidoyatov Kh.M...... 284, 297 Smolin N.A...... 233 Shakhmatova O.A...... 288 Sobolev V.I...... 93 Shakhtshneider T.P...... 118 Sofilkanych A.P...... 96

314 Sofronov A.V...... 13 Terenzhev D.S...... 152 Sokolova A.M...... 236 Testova L...... 226 Sokolova E.V...... 211 Tilyabaev K.Z...... 227 Sokolova L.S...... 295 Timbaliuc N...... 170 Sokolova M.P...... 273 Timofeev N.P...... 228, 229, 230 Soleyman R...... 169 Tojiev P.J...... 142, 178 Solntsev A.P...... 218 Tokarev P.N...... 16 Solovskiy M.V...... 48 Toktasynov S.K...... 19 Song T...... 170 Tolmacheva I.А...... 59, 71 Sorokina K.N...... 110 Tolstikova T.G...... 137, 242 Sosnov D.A...... 153 Torlopov M.A...... 117 Sousa G.D.A...... 46 Tran Dinh T...... 214 Sozinov O.V...... 268 Treimanis A...... 231 Spinu O...... 170 Tretyakov S.I...... 100 Spirina T.N...... 212 Trifonov R.E...... 232 Spitsyn A.A...... 101 Trishin Yu.G...... 188 Spivak A.Yu...... 82, 189 Trofimov B.A...... 285 Stankevich V.K...... 285 Tsaturyan A.S...... 106 Starkova E.V...... 133 Tselikova G.A...... 93 Stashenko E...... 180, 212 Tsoy E.A...... 160 Stashenko E.E...... 17, 49, 132, 133, 180, 184, 213 Tsygankova L.E...... 233 Stavarache C...... 147 Turobjonov S.M...... 232 Stefanovic B...... 302 Tuyen N.D...... 198 Stepanov N...... 214, 215 Tychinskaya L.Yu...... 8, 20 Stepanova E.V...... 274 Tyulkova Yu.A...... 182 Stepen R.A...... 163 Stiebra L...... 260 U Stirna U...... 86, 216, 250 Stoyko O.V...... 77 Udoratina E.V...... 264 Strand A...... 217, 223 Ugraitskiy A.A...... 109 Um B.H...... 167 Strashnova S.B...... 64 Strelyaeva A.V...... 112, 114 Urazaeva A.I...... 90 Strizhakov D.A...... 218 Urozov M.Q...... 142, 178 Su P...... 218 Uryadnikov A.A...... 233 Sudakova I.G...... 219 Uryash V.F...... 65 Uryupin A.B...... 39 Sudarikov D.V...... 76 Sukhanova T.E...... 273 Us A.S...... 122 Sukhov D.A...... 302, 303 Ushakov V.M...... 239 Ushanova V.M...... 234 Sukhov D.А...... 46, 220 Suleimen Ye.M...... 221 Sumersky I.V...... 63, 212, 222 V Sundberg A...... 217 Vahasalo L...... 217, 223 Sundberg A.C...... 223 Valeev F.A...... 183 Sushkova S.N...... 31, 32, 269, 286 Valenkov A...... 195 Suvanova F.U...... 9 Valieva O.I...... 33 Syropyatov B.Ya...... 294 Van Heiningen A...... 70, 235 Varfolomeev S...... 214, 215 T Vasilyev A.V...... 146, 271 Vasilyev V.V...... 236 Taherzadeh M.J...... 127 Tamm L.A...... 98, 188 Vedernikov D.N...... 237 Tanygina E.D...... 224, 233 Vejdovszky P...... 169 Veprikova E.V...... 237 Tarabanko V.E...... 210, 224 Taran O.P...... 42 Vereschagin N.A...... 103, 238 Taraskevich M.R...... 109 Veselova O.F...... 118, 120 Tashmatov Z.O...... 55 Vetrova E.V...... 31, 32, 286 Tchemerkin I.V...... 224 Vigranenko Yu.T...... 239 Vikele L...... 231 Teissedre P.-L...... 92 Teleshev A.T...... 225 Villaverde J.J...... 239 Teng Tan H...... 41 Vilsone D...... 216, 250 Vipova N.L...... 289 Tenho M...... 78 Teong Lee K...... 41 Vladykina D.S...... 240, 241 Terenina M.B...... 245 Vlasova E.N...... 43, 264, 296 Volchek B.Z...... 264, 296 315 Volcho K.P...... 242 Yuvchenko А.P...... 20 Voleva V.B...... 278 Yuzikhin O.S...... 254 Volkova N...... 243 Volkova N.M...... 122 Z Volodchenko I.I...... 121 Volodin V.V...... 187 Zabivalova N.M...... 28, 264, 296 Volodina S.O...... 187 Zaikov G.E...... 306 Zakharova N.G...... 121 Volodko A.V...... 275 Vologdina O.S...... 244 Zakusilo D.N...... 254 Vorobyova A.K...... 245 Zaletok S.P...... 259 Zarubin M.J...... 63 Voskoboinokov I.V...... 99 Vostrikov S.V...... 29, 54, 102, 155 Zarubin M.Ja...... 222 Votintseva G.V...... 188 Zarubin M.Ya...... 87, 146, 271 Vuai S.A...... 79 Zefirov N.S...... 255, 304 Vukic N...... 204, 246 Zefirova O.N...... 304 Vurasko A.V...... 246 Zemlianikina A.S...... 222 Vyglazov V.V...... 298 Zemnukhova L.A...... 160 Zgonnik P.V...... 15 W Zhakina A.H...... 256 Zhavoronkova T.Y...... 255 Wadso L...... 243 Zheglova T.V...... 291 Willfor S...... 67 Zhivotova T.S...... 256 Willfor S.M...... 170, 203, 207, 208, 247 Zhizhina E.G...... 257 Zhumabaeva S.E...... 258 Y Zhuravleva N.M...... 209 Yagolnik E.A...... 278 Zhuravlyov N.S...... 104 Yakovishin L.A...... 248, 269 Zhusupova G.E...... 58 Yakovlev V.A...... 37, 110, 185, 248 Zhylenko V.V...... 259 Yakshilov D.S...... 74, 143, 144, 249, 250 Zimin Y.S...... 33 Yakushin V...... 250 Zinoviev M.A...... 109 Yarovoy I.R...... 248 Ziyaev Kh.L...... 292, 293 Yazvenko M.A...... 188 Ziyatdinova G.K...... 260 Yermak I.M...... 211, 267, 275 Zlobin A.A...... 133 Yolkin V.A...... 298 Zokirova U.T...... 297 Yudin V.E...... 280 Zoldners J...... 260 Yudina N.V...... 128 Zonova E.E...... 68 Yuldashev A.M...... 227 Zozulkina A.S...... 122 Yurkshtovich N.K...... 75, 251, 253 Zubareva N.D...... 112, 114 Yurkshtovich T.L...... 35, 36, 252, 253 Zuev S.S...... 112 Yushchenko D.Yu...... 83 Zykova I.D...... 261 Yuvchenko A.P...... 21

316