Terpenes As Starting Material in the Synthesis of Natural Products

ACADEMY OF SCIENCES OF MOLDOVA INSTITUTE OF CHEMISTRY STATE UNIVERSITY OF MOLDOVA INSTITUTE OF APPLIED PHYSICS INSTITUTE OF ELECTRONIC ENGINEERING AND NANOTECHNOLOGIES CHEMICAL SOCIETY OF MOLDOVA

The XVIII-th International Conference

"Physical Methods in Coordination and Supramolecular Chemistry"

(Dedicated to the memory of the professor Constantin Turta and professor Mihail Revenco)

BOOK OF ABSTRACTS

October 8-9, 2015

Chişinău, MOLDOVA

LIST OF SPONSORS

SUPREME COUNCIL FOR SCIENCE AND TECHNOLOGICAL DEVELOPMENT, ACADEMY OF SCIENCES OF MOLDOVA

INSTITUTE OF CHEMISTRY, ACADEMY OF SCIENCES OF MOLDOVA

STATE UNIVERSITY OF MOLDOVA

NITECH S.R.L.

STATE AGENCY ON INTELLECTUAL PROPERTY OF THE REPUBLIC OF MOLDOVA

REDOX LAB SUPPLIES S.R.L.

VALIEXCHIMP S.R.L.

INTERNATIONAL ADVISORY BOARD

Gheorghe Duca (Moldova) - Chairman Sebastien Floquet (France) Sergey Aldoshin (Russia) Christoph Janiak (Germany) Serghey Andronati (Ukraine) Janusz Lipkowski (Poland) Marius Andruh (Romania) Ionel Mangalagiu (Romania) Vladimir Arion (Austria) Marius Reglier (France) Juan Bartolome (Spain) Donald Poirier (Canada) Andrew Benniston (UK) Annie Powell (Germany) Isaak Bersuker (USA) Bogdan Simionescu (Romania) Rodolphe Clerac (France) Grigore Timco (UK) Boris Tsukerblat (Israel)

ORGANIZING COMMITTEE

Gheorghe Duca – Chairman Ion Geru Aurelian Gulea – Co-chairman Viorica Gladchi Vasile Lozan - Co-chairman Natalia Gorincioi Vadim Druta – Secretary Victor Kravtsov Aculina Aricu Tudor Lupashcu Polina Bourosh Mihai Macovei Ion Bulhac Igor Povar Ion Bulimestru Anatolie Sidorenko Diana Dragancea Constantin Turta

PROGRAM COMMITTEE

Vasile Lozan – Chairman Boris Pușcașu Victor Kravtsov - Co-chairman Piotr Petrenko Vadim Druta – Secretary Sergiu Shova Svetlana Baca Marina Fonari Maria Cocu Dumitru Sirbu Eduard Coropceanu Diana Șepeli Olesea Cuzan Tatiana Straistari Constantin Indricean Victor Tsapkov Ana Lazarescu Irina Voda Silvia Melnic

TRENDS OF COORDINATION CHEMISTRY DEVELOPMENT IN THE REPUBLIC OF MOLDOVA

Gheorghe Duca

Academy of Sciences of Moldova, 1 Stefan cel Mare Ave., MD 2001, Chisinau, Republic of Moldova

This report emphasizes the most relevant achievements obtained in the coordination chemistry in the Republic of Moldova. The main results of scientific investigations of the Moldovan research centres are presented, as well as the most important successes attained in various areas of inorganic, coordination, bioinorganic, and quantum chemistry. Historically, chemical science in Moldova started in the 1940s with investigations in the area of coordination compounds of transition metals, in particular, of dioximates of d-metals, the study of the structure and properties of this class of compounds using the newest, at that time, physical methods of research. Later, the range of scientific themes significantly expanded, comprising template processes, topochemical synthesis, obtaining of mono- and polynuclear coordination compounds, including those with macrocyclic and chelating ligands; the synthesis of biologically active complexes,development of the theory of electronic and vibronic structure of compounds with mixed valence, etc., optimization of quantum-chemical research techniques, as well as of methods of the molecular design of biologically active systems, with the focus on their action mechanism. In 2006 the Centre of “Physical Chemistry and Nanocomposites” was created at the Institute of Chemistry, hence the research with the view of obtaining nanoparticles has started. The aims of the Centre are to investigate the formation of nanoparticles and to elaborate the methods of their production required in nanoelecronics; to elaborate advanced technologies, to produce new substances necessary for the national economy for the development of alternative energy sources, of new medicinal preparations, applications in agriculture, solving the issues of environmental protection. During the past years, Moldovan scientists intensively investigated mono- and polynuclear coordination compounds of metals (transition and s-type) as photo-catalysts, MOFs for gas storage and as nanostructurated materials for water photolysis. Other current directions of investigations are: obtaining inhibitors of cancer cells proliferation; preparing materials with useful magnetic properties, good for various applications including agriculture (as plant growth stimulators). The report will reflect also the contribution of the famous Moldovan inorganic chemists - professors Constantin Turta and Mihail Revenco, into the developement of the coordination and supramolecular chemistry in the Republic of Moldova and the main scientific achievements of the both.

POLYMERS IN SUPRAMOLECULAR ASSEMBLIES FOR BIO-RELATED APPLICATIONS

Bogdan C. Simionescu

"Petru Poni" Institute of Macromolecular Chemistry of Romanian Academy & Department of Natural and Synthetic Polymers, "Gh. Asachi" Technical University of Iasi, Iasi, Romania

Last decades, a pronounced need for new materials for biomedical application, able to provide more efficient treatments and to insure minimization of the side effects, to increase patient compliance and satisfaction is evident. At the same time, advances in polymer science have led to the development of several novel systems designed for drug/gene delivery and tissue engineering, areas with pivotal role for both research/academic community and industry, generating new niche markets. In this respect, recent years have witnessed an increased interest in the rational design of complex polymeric structures. The main objectives are related to the development of tailored polymer materials, engineered to exert distinct biological functions, implying multifunctionality as well as appropriate form/architectural features, giving rise to specificity and high responsiveness. To gain further clinical importance the new materials must provide not only high physicochemical and biological performances but also processing ability. These demands – and especially the last one – often imply combination of natural and synthetic polymers (blends, block/graft copolymers, bioconjugates, interpenetrating networks, etc.), while improved performances may be mainly achieved by composite materials (inorganic/organic, biocomposites). The targeted application site or cargo may require specific material category (biodegradable, bioresorbable), dimension scale (micro/nano size) and topographic characteristics. Some of the existing essential obstacles and limitations may be surpassed by combining systems and approaches from apparently different application domains. Thus, controlled drug delivery and its application in tissue engineering for tissue growth support and stimulation attracted much attention over the last decade, while combination of gene therapy and tissue engineering within a single system resulting in a powerful synergism of treatment options for regenerative medicine (scaffold mediated gene therapy) seems to be the favored alternative for tissue healing. The presentation summarizes the history and challenges in the discussed domains, pointing on polymers as a possible solution to specific challenges, and outlines the current state of the art, focusing on the newest strategies to improve systems effectiveness and responsiveness (design keys, preparative approaches). Expected future directions are underlined. Acknowledgement. This work was financially supported by the Romanian National Authority for Scientific Research, CNCS - UEFISCDI, project PN-II-ID-PCCE-2011-2-0028.

POLYFUNCTIONAL NITROSYL IRON COMPLEXES AS A NEW CLASS OF NO DONORS FOR MEDICINE, WHICH HAVE UNUSUAL “ENTANGLED” MAGNETIC AND ELECTRONIC PROPERTIES

S.M. Aldoshin1, N.A. Sanina1, A.V. Palii2

1Institute of Problems of Chemical Physics, 1, Institutskii Av., 142432 Chernogolovka, Moscow Region, Russia 2Institute of Applied Physics, Academy of Sciences of Moldova

The method of synthesis has been developed and dinitrosyl iron complexes of a new class (DNIC) have been obtained, which contain functional sulfur-containing ligands and are mimetics of the active sites of nitrosyl non-heme proteins. The structure of cationic, neutral and anionic forms of paramagnetic mononuclear, diamagnetic binuclear of µ-S type and paramagnetic of µ- S-CN type nitrosyl complexes has been studied. Based on precision X-ray data and quantum- - chemical calculations, specific features of the electronic structure of the basic (NO)2Fe unit of these complexes have been studied, as well as the influence of the ligand surrounding on NO donating properties and mechanism of decomposition of the complexes in various solvents at different pH values of the solutions. The obtained results open possibilities for the development of promising medicines on their base, i.e., NO donors for the therapy of socially relevant diseases [1]. In some paramagnetic mononuclear cationic DNIC absolutely unusual magnetic properties have been detected, which cannot be explained in the frame of usual spin model The performed calculation shows a considerable contribution of unquenched orbital moment of the NO group in the magnetic properties of these complexes, which is also responsible for the residual magnetism of diamagnetic anionic DNIC of µ-S type. Specific features of the crystalline and molecular structure of DNIC, which are responsible for orbital paramagnetism have been studied. Bi-nuclei paramagnetic DNIC of μ-S-C-N type having a Heisenberg dimer structure and characterized by antiferromagnetic intramolecular exchange appeared to be promising compounds, which at low temperature possess quantum-information correlations in the form of quantum entanglement of the two-qubit model. The possibility has been shown for these complexes to determine the magnitude of these quantum-information correlations from the magnitude of magnetic susceptibility. The obtained results open prospects for molecular electronics [2] and magnet-controlled target delivery of medicines.

Literature: 1. Sanina, N.; Aldoshin, S., Structure and properties of iron nitrosyl complexes with functionalized sulfur-containing ligands. Russ.Chem. Bull, 2011, 60 (7), 1223-1251; (b) Sanina, N.; Kozub, G.; Zhukova, O., et.al., Synthesis, structure, NO donating activity of iron-sulphur nitrosyl complex with 2-aminophenol-2-yl and its antiproliferative activity against human cancer cells, J. Coord. Chem., 2013, 60 (20), 3602-3618; (c) Sanina, N.; Aldoshin, S.;. Shmatko, Yu., et.al., Mesomeric tautomerism of ligand (L) is the pathway for synthesis of cationic DNICs. Х-ray structure and properties of [Fe(L)2(NO)2]ClH2O with L- thiocarbamide, Inorg. Chem. Comm. 2014, 49, 44–47. 2. Aldoshin, S.; Fel’dman, E.; Yurishchev, M., Quantum entanglement and quantum discord in magnetoactive materials. Low Temp. Phys., 2014, 40, 1, 3-16.

In memory of Prof. Mihail REVENCO Corresponding member of ASM

ACTIVATIN OF CHEMICAL AGENTS BY COORDINATION AND SYNTHESIS OF NEW MATERIALS AS BIOLOGICAL ACTIVE SUBSTANCES, CATALYSTS, ANALYTICAL REACTIVES AND MOLECULAR MAGNETS

Aurelian GULEA

Laboratory of Advanced Materials in biopharmaceuticals and Techniques, Center of Applied and Ecological Chemistry, State University of Moldova

Investigations of Professor Revenco Mihail were dedicated on study of changes in thiosemicarbazidic fragment H2N(1)-N(2)H- C(3)(=S)-N(4)H2 under the coordination to the complex generator. At the starting point of such investigations three types of transformations in thiosemicarbazidic fragment were been known:  Condensation via H2N(1) group with carbonylic derivatives and formation of thiosemicarbazones  Cyclisation with α-dicetones and formation of heterocyclic compounds  Thioalkylation with alkyl halogenures The impact of coordination under the each atom of thiosemicarbazidic fragment was investigated and for the first time those results were implemented for obtaining of new materials with anti bacterial properties, catalysts, analytical agents, molecular magnets etc.:  For the nitrogen atom N(1): . Monoelectronic redox reaction with formation of anionic radicals and its stabilization as ligands in coordination compounds . Selective oxidation of radicals and formation of bielectronic oxidation products  For the nitrogen atom N(2): . Amplification of the acid properties of N(2)H group during coordination and by variation of the substitution in N(4) position . Intermolecular coordination of N(2) with formation of polymers . Amino-iminic tautomerism for thioalkilderivatives  For the sulphur atom: . Change of coordination mode after thio-alkilation . Oxidative dimerisation with disulfuric bonds formation  For the carbon atom C(3): . Reaction of total desulphurization . Reaction of reetherification and formation of O-alkyl derivatives  For the nitrogen atom N(4): . Appearance of acid properties on N(4)H2 group and its deprotonation after coordination . Reaction of amido-nitrosation . Reaction of nucleofilic addition and formation of symmetric ad asymmetric amminals . Amplification of photolytic properties under the coordination effects . Reaction of esterification . Reaction of condensation . Reaction of oxidative amidation

Ion Madan “ The Knight of Knowledge and Devotion-Professor Mihail Revenco at his 60th Anniversary” BIOBIBLIOGRAPHY, Chisinau 2007, CEP USM

MOFS FOR CYCLING HEAT TRANSFORMATION PROCESSES

Christoph Janiak

Institut für Anorganische Chemie und Strukturchemie , Heinrich-Heine-Universität Düsseldorf, 40204 Düsseldorf, Germany. E-mail: [email protected]

Microporous MOFs with high water uptake capacity are gaining attention for low temperature heat transformation applications in thermally driven adsorption chillers (TDCs) or adsorption heat pumps (AHPs) (Fig. 1). TDCs or AHPs are an alternative to traditional air conditioners or heat pumps operating on electricity or fossil fuels. By using solar or waste heat as the operating energy TDCs or AHPs can significantly help to minimize primary energy consumption and greenhouse gas emissions generated by industrial or domestic heating and cooling processes. TDCs and AHPs are based on the evaporation and consecutive adsorption of coolant liquids, preferably water, under specific conditions. The process is driven and controlled by the microporosity and hydrophilicity of the employed sorption material. Here we summarize the current investigations, developments and possibilities of MOFs for the use low temperature heat transformation applications as alternative materials for silica gel, aluminophosphates or zeolites.[1]

Fig. 1 Principle of adsorption chilling or adsorption heat pump.

Top: The infrared photograph in the right part visualizes the different temperature levels after opening the manual valve with cooling to –5 °C of the water container and heating to 45 °C of the sorbent material thereby depicting the working cycle. Bottom: 1. Working cycle: A working fluid (typically H2O) is evaporated at low pressure by application of evaporation heat Qevap, and adsorbed at a microporous material, releasing adsorption heat Qads. 2. Regeneration cycle: When the adsorbent is saturated, driving heat Qdes is applied for desorption of the working fluid. The vapour then condenses in a cooler, and condensation heat Qdes is released. Low temperature heat is depicted in blue, medium T heat in green and high T heat in red.

1 F. Jeremias, D. Fröhlich, C. Janiak, S. K. Henninger, RSC Advances 2014, 10, 1006-1016. F. Jeremias, D. Fröhlich, C. Janiak, S. Henninger, New J. Chem. 2014, 38, 1846-1852. F. Jeremias, V. Lozan, S. K. Henninger, C. Janiak, Dalton Trans. 2013, 42, 15967-15973. A. Khutia, H. U. Rammelberg, T. Schmidt, S. Henninger, C. Janiak, Chem. Mater. 2013, 25, 790-798. F. Jeremias, S. K. Henninger, C. Janiak, Chem. Commun. 2012, 48, 9708-9710. F. Jeremias, A. Khutia, S. K. Henninger, C. Janiak, J. Mater. Chem. 2012, 22, 10148-10151. Review: S. K. Henninger, F. Jeremias, H. Kummer, C. Janiak, Eur. J. Inorg. Chem. 2012, 2625– 2634. J. Ehrenmann, S. K. Henninger, C. Janiak, Eur. J. Inorg. Chem. 2011, 471-474. S. K. Henninger, H. A. Habib, C. Janiak, J. Am. Chem. Soc. 2009, 131, 2776-2777. 5

THE BEAUTY OF COORDINATION POLYMERS Marius Andruh

University of Bucharest, Faculty of Chemistry

Crystal engineering of coordination polymers represents one of the most fascinating fields in modern chemistry. It encompasses both inorganic and organic synthesis. The metal ions, through their stereochemical and electronic predilections, play a key role in controlling the assembly of the molecular components into well-defined architectures.1 The ultimate goal of crystal engineering is to design solids with technologically useful functionalities (molecular magnetic materials, conducting solids, zeolite-like materials, catalysts, luminescent materials, etc.). Originating from Robson’s seminal papers published in 1990,2 the node-and-spacer approach became a largely employed strategy for the construction of a rich variety of coordination polymers. It relies upon the strong directionality of the coordination bonds established between the metal ions (nodes, connectors) and the exo-dentate ligands (spacers, linkers). We enlarged the classical node-and-spacer approach employing homo-and heterometallic complexes as nodes.1,3 Several families of such compounds synthesized recently in our Laboratory will be presented in this lecture.4

1. M. Andruh, Chem. Commun., 2007, 2565; (b) M. Andruh, Chem. Commun., 2011, 47, 3025; (c) M. Andruh, Chimia, 2013, 67, 383; M. Andruh, Pure Appl. Chem., 2005, 77, 1685. 2. (a) R. W. Gable, B. F. Hoskins, R. Robson, J. Chem. Soc., Chem. Commun., 1990, 1677. 3. (a) M. Andruh, D. G. Branzea, R. Gheorghe, A. M. Madalan, CrystEngComm., 2009, 11, 2571; 4. (a) M.-G. Alexandru, D. Visinescu, M. Andruh, N. Marino, D. Armentano, J. Cano, F. Lloret, M. Julve, Chem.-Eur. J., 2015, 21, 5429; (b) A. E. Ion, S. Nica, A. M. Madalan, C. Maxim, M. Julve, F. Lloret, M. Andruh, CrystEngComm., 2014, 16, 318; (c) C. Paraschiv, A. Cucos, S. Shova, A. M. Madalan, C. Maxim, D. Visinescu, B. Cojocaru, V. I. Parvulescu, M. Andruh, Cryst. Growth & Des., 2015, 15, 799; (d) T. Mocanu, C. I. Raţ, C. Maxim, S. Shova, V. Tudor, C. Silvestru, M. Andruh, CrystEngCoom, 2015, 17, 5474 ; (e) G. Marinescu, C. Maxim, R. Clérac, M. Andruh, Inorg. Chem., 2015, 54, 5621.

BIOINORGANIC CHEMISTRY APPROACH IN THE DEVELOPMENT OF TYROSINASE INHIBITORS

Marius Réglier

Aix Marseille Université, CNRS, ISM2 UMR 7313, Marseille. Tyrosinases are ubiquitous Cu-containing enzymes belonging to the type-3 or “coupled binuclear” family (Fig. 1). Ty’s catalyze the two-step oxidation of phenolic compounds into the corresponding catechols (monophenolase activity) and ortho-quinones (catecholase activity). In mammals, their biological function is to convert L-tyrosine into dopaquinone, which is the key product for melanin pigment biosynthesis. Melanin-related disorders are known to cause serious skin lesions, Parkinson’s disease and melanoma. In addition, Ty’s are responsible for the browning of plant foods, which creates an important economic problem in the field of nutrition. Ty inhibition is a well-established approach for controlling in vivo melanin production and food browning, so the development of Ty inhibitors has a huge economical and industrial impact. To control the Ty activity, the best strategy is to target the Ty binuclear copper active site by transition state analogues, which have structural analogies to catechol but are not oxidizable. Recently, we reported on HOPNO as TS analogues featuring competitive inhibition constants below to 1 .1 In this communication, we will describe our strategy to develop efficient Ty inhibitors derived from HPNO and aurones. Our approach includes synthetic chemistry and enzymology as well as structure-function studies using structural and functional models (Fig. 3) of the Ty active site.2-9

R O 4' 1 3' 1 B R2 N OH HO 6 O 2' HO O 1' A R3 2 O O

1a (R = R = R = H) 1 2 3 O 1b (R1 = OH; R2 = R3 = H) OH 1c (R1 = H; R2 = OH; R3 = H) N 1d (R1 = R2 = H; R3 = OH) HOPNO 1e (R1 = R2 = OH; R3 = H) Figure 3. Ty structural Figure 1. Structure of the active site of the met2 Ty. Figure 2. HOPNO and aurones (1-2). model in interaction with HOPNO.

References. 1 E. Peyroux, W. Ghattas, R. Hardré, M. Giorgi, B. Faure, A. J. Simaan, C. Belle, M. Réglier Inorg. Chem. 2009, 48, 10874. 2 M. Orio, C. Bochot, C. Dubois, G. Gellon, R. Hardré, H. Jamet, D. Luneau, C. Philouze, M. Réglier, G. Serratrice, C. Belle Chem. Eur. J. 2011, 17, 13482. 3 C. Dubois, R. Haudecoeur, M. Orio, C. Belle, C. Bochot, A. Boumendjel, R. Hardré, H. Jamet, M. Réglier ChemBioChem 2012, 13, 559. 4 C. Bochot, E. Favre, C. Dubois, B. Baptiste, L. Bubacco, P.-A. Carrupt, G. Gellon, R. Hardré, D. Luneau, Y. Moreau, A. Nurisso, M. Réglier, G. Serratrice, C. Belle, H. Jamet Chem. Eur. J. 2013, 19, 3655. 5 C. Bochot, A. Gouron, L. Bubacco, A. Milet, C. Philouze, M. Réglier, G. Serratrice, H. Jamet and C. Belle. Chem. Commun. 2014, 50, 308. 6 R. Haudecoeur, A. Gouron, C. Dubois, H. Jamet, M. Lightbody, R. Hardré, Anne Milet, E. Bergantino, L. Bubacco, C. Belle, M. Réglier and A. Boumendjel. ChemBioChem 2014, 15(9), 1325. 7 E. Buitrago, A. Vuillamy, A. Boumendjel, W. Yi, G. Gellon, R. Hardre, Renaud, G. Serratrice, M. Réglier, C. Belle. Inorg. Chem. 2014, 12848. 8 C. Justino Nunes, B. Essenfelder Borges, L. Sumie Nakao, E. Peyroux, R. Hardré, B. Faure, M. Réglier, M. Giorgi, M. Pietro Bach, C. Columbano de Oliveira and A. M. Da Costa Ferreira. J. Inorg. Biochem. 2015, 149, 49.

9 E. Buitrago, R. Hardré, R. Haudecoeur, H. Jamet, C. Belle, A. Boumendjel, L. Bubacco and M. Réglier. Current Topics in Medicinal Chemistry. 2015, under press.

PHOTO- AND ELECTRO-ACTIVE MOLECULAR SYSTEMS FOR FUEL PRODUCTION

Andrew C. Benniston

Molecular Photonics Laboratory, School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU

The production of fuels from sunlight remains as one of the main challenges for the scientific community. In recent years, various steps towards efficient systems have been taken although no example having the desired properties of stability and price has been discovered. The main components of a full device for light-driven water splitting can be divided as catalysts for oxidation and reduction reactions, light-harvesting compounds, semiconducting electrodes for electron and hole transport and a membrane for conducting protons and separate the generated gases. Many examples of molecular catalysts have appeared in the literature for water oxidation and proton reduction, some of them exhibiting incredible performances. However, there are not many examples of sensitisers for water oxidation, limited mainly by the high oxidation potential needed to drive the reaction and their stability in aqueous media. Molecular sensitizers for water splitting are restricted to ruthenium(II) tris(bipyridine) and porphyrin derivatives. In both cases, the molecules are directly attached to a semiconductor and fast recombination reactions from the injected electrons are observed. On the other hand, the use of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (Bodipy) as a chromophore has become very popular owing to its exceptional optical properties, photostability, and ease of preparation and purification. Very complicated structures have been prepared based on dendritic scaffolds, cassette light harvester or multi-dyad showing the versatility of such dyes. They can be easily functionalised to tune redox and optical properties to meet the demands for the water oxidation reaction. Recently, Bodipy dyes have been published as sensitizers for light-driven hydrogen production although no examples in photochemical oxidation reactions have appeared so far. In view of such considerations, we envisioned the possibility to designing Bodipy-ruthenium dyads with directional control of electron and hole transport within the sensitizer to minimise recombination reactions and improve the performance of the system. Both subunits are bridged by a triazole linker to avoid coupling between the Bodipy and the ruthenium. Moreover, the dyad BDR2 has an ethylene-bipyridyl ligand that is easier to reduce than bipyridine and should direct the electron towards this end of the molecule. The two targeted molecules are shown in Scheme 1 and this talk will discuss the progress made so far in the field of artificial photosynthesis.

CHEMICAL SYNTHESIS, NMR CHARACTERIZATION AND BIOLOGICAL ASSESSMENT OF TWO STEROIDAL ANTICANCER AGENTS.

Donald Poirier

Laboratory of Medicinal Chemistry, CHU de Québec – Research Center and University Laval, Québec, Qc, Canada

PBRM and RM-133 are two steroid derivatives recently developed in our research group as anticancer agents. PBRM, or 3-{[(16β,17β)-3-(2-bromoethyl)-17-hydroxyestra-1(10,2,4-trien- 16-yl]methyl} benzamide, was synthesized in solution from estrone (E1) using a sequence of eight steps in an overall yield of 11%. The structure was confirmed by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. 2D-NMR experiments, such as HSQC (heteronuclear single-quantum correlation), HMBC (heteronuclear multiple-bond correlation), COSY (correlation spectroscopy) and NOESY (nuclear Overhauser effect spectroscopy), were also needed to identify all protons and carbons. PBRM inactivated the transformation of E1 into estradiol (E2), the most potent estrogen, by the action of steroidogenic enzyme 17β- hydroxysteroid dehydrogenase (17β-HSD) type 1, which is thought to play a pivotal role in the progression of estrogen-sensitive breast cancer. In fact, PBRM inhibited the 17β-HSD1 in T-47D -1 cells (IC50 = 83 nM), the pure enzyme (Ki = 381 nM, kinact = 0.084 min ) and did not inhibit other key enzymes such as 17β-HSD2, 17β-HSD7, 17β-HSD12, CYP3A4 and CYP-2D6, suggesting a good selective action. When tested in vivo on the T-47D xenograft tumor model in female ovariectomized nude mice, PBRM (250 µg/mouse/day) fully blocked (100%) the tumor growth induced with exogenous E1 (0.1 µg/mouse/day).

RM-133, or {4-[(2β,3α,5α,17α)-3,17-dihydroxypregn-20-yn-2-yl]piperazin-1-yl}[(2S)-1- (quinolin-2-ylcarbonyl)pyrrolidin-2-yl]methanone, was synthesized in small quantity in 97% purity by solid-phase synthesis using the new diethylsilylacetylenic linker we have previously developed. It was next synthesized in solution and in larger quantity for in vivo assays starting from androsterone and using a sequence of six steps in an overall yield of 14%. NMR spectroscopy, especially 2D-experiments (HSQC, HMBC, COSY and NOESY), confirmed the right structure and to identify all protons and carbons. The presence of two conformers in proportions that range according to the NMR solvent was also clearly observed. RM-133 has been reported to be a promising pro-apoptotic agent showing antiproliferative activity (IC50 ranging from 0.1 to 4.5 µM) on various human cancer cell lines (HL-60, PANC-1, LNCaP, LAPC-4, MCF-7, T-47D and OVCAR-3). When tested in vivo on the OVCAR-3 xenograft tumor model in female ovariectomized nude mice, RM-133 (6 mg/mouse/day) fully blocked (100%) the tumor growth.

In summary, both PBRM and RM-133 steroid derivatives were synthesized, characterized and generated promising in vivo results against breast cancer and ovary cancer tumor models, respectively.

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THE CONCEPT OF ORGANIC ZEOLITE AND ITS PRACTICAL USES

Janusz Lipkowski

Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01 224 Warszawa, Poland; [email protected]

The term organic zeolites has been originally introduced to chemical literature in early 1970ths by R.M. Barrer, to describe molecular crystals having open structures, able to reversibly absorb and desorb organic species with relatively weak, if any, sorption of water or other hydrophilic molecules. The compound studied by the Authors cited above was Co(NCS)2(4- methylpyridine)4, one of the formerly studied series of, reportedly, clathrate forming coordination complexes. The reversible sorption property of the compounds have been the basis for their use as stationary phases in clathrate chromatography and, in particular, as the sorbent useful for separation of isotopomers. Basic physicochemical information of these compounds has been summarized in review chapters [1]. A characteristic feature of the organic zeolite structures, when compared to classical ‘inorganic’ zeolites based on aluminosilicates, is their relatively weak intermolecular bonding, both guest-host and host-host. The latter is the reason for significant flexibility of the host crystal structure which changes its parameters upon guest absorption, desorption or exchange. The importance of the concept of organic zeolites is presently seen in the relatively new field, namely in Metal Organic Framework structures. Porous compounds of fantastic sorption capacities have been reported in the literature and the field is developing remarkably. Typically the papers are limited to basic characteristic of the product: synthesis and structure, with particular emphasis on its porosity. It is well known that the porosity depends on the presence of the guest species and, in particular, it vanishes upon guest desorption. On the other hand, the properties of the materials derived from MOFs are an interesting function of collective guest- host phenomena, including lattice dynamics [3]. In principle, an organic zeolite structure is formed as the result of supramolecular aggregation of any substrate having a hydrophobic or amphiphilic character. A special, curious example is an organic zeolite formed by water molecules which encapsulate organic guest species in such a way that all hydrophilic functions of water ,molecules are directed outwards the intermolecular space left for the guest component. In general, organic zeolite behavior may be observed on a large variety of supramolecular materials, including solvates of macrocyclic compounds. In the paper solvation of cyclodextrins and synthetic macrocycles will be used as the convenient example, based on brand new, mostly yet unpublished large structures of heavily solvated cyclodextrin complexes in the solid state.

References: 1) J. Lipkowski - "Werner Clathrates" - in J.L. Atwood, J.E.D. Davies, D.D. MacNicol, F. Vögtle, J.-M. Lehn (Eds.) "Comprehensive Supramolecular Chemistry", D.D. MacNicol, F. Toda and R. Bishop (volume eds.) Vol. 6 "Solid-State Supramolecular Chemistry: Crystal Engineering", Pergamon (1996), 691-71; "Structure of Clathrates" - in G.A. Webb (Ed.) "Annual Reports on the Progress of Chemistry", (1996), Vol. 92, Section C, 307-338 2) Lewiński J., Kaczorowski T., Prochowicz D., Lipińska T., Justyniak I., Kaszkur Z., Lipkowski J., -„Cinchona Alkaloid–Metal Complexes: Noncovalent Porous Materials with Unique Gas Separation Properties”- Angew. Chem. Int. Ed., Vol. 49, (2010), 7035-7039. 3) V. Guillerm, D. Kim, J.F. Eubank, R. Luebke, X. Liu, K. Adil, M. Soo Lah, M. Eddaoudi – „A supermolecular building approach for the design and construction of metal–organic frameworks” - Chem. Soc. Rev. 2014, 43, 6141-6172

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SMART SYNTHETIC AZAHETEROCYCLES Ionel I. Mangalagiu “Al. I. Cuza” University of Iasi, Faculty of Chemistry, Bd. Carol 11, 700506 Iasi, Romania. Tel: +40+232 201343; fax: +40+232 201313; e-mail: [email protected]

Azaheterocycles are considered privileged structures that currently experiencing a renewed interest in medicinal chemistry, opto-electronics, agrochemicals, etc. As part of our ongoing research concerning chemistry and properties of azaheterocycles we present here some core results obtained by our group within this field, a particularly attention being given to the so called smart molecules or molecules with multiple tasks. In this respect, some target five and six member ring azaheterocycles was synthesized and tested for their potential applications as anticancer (G-quadruplex including) and antimycobacterial agents, fluorescent sensors, logic gates and molecular computers.

Acknowledgements. Authors are thankful to CNCS Bucharest, Romania, project PN-II-DE- PCE-2011-3-0038, no. 268/05.10.2011, for financial support.

L12

MAGNETIC RELAXATION AND INTERACTIONS IN LANTHANIDE COMPLEXES AND CLUSTERS.

J. Bartolomé1 and C. Turta2

1Instituto de Ciencia de Materiales de Aragón, and Departamento de Materia Condensada. CSIC-Universidad de Zaragoza. 50009 Zaragoza. Spain.

2Institute of Chemistry, Academy of Sciences of Moldova, Academiceskaya 3, MD-2028, Chisinau, Moldova

In the last decade it has been recognized that magnetic relaxation process taking place in magnetic molecules show a rich phenomenology. The renewed interest in this subject stems from the possibility of using these molecules as quantum qbits, in quantum computation, or finding new physical processes in artificial structures as model systems.

In this presentation the Single Ion Magnet (SIM) behavior of several rare earth furoate [1] and cyanoacetate [2] polymers are reported. Special emphasis is given to the competition between the SIM fast relaxation time properties, inherently caused by the ligand field interactions, on one hand, and the intermolecular interactions of exchange or dipolar origin, on the other, that tend to slow down those relaxations. These phenomena are observable at very low temperature, below 1K.

The application of an external magnetic field may compete with intramolecular interactions and cause magnetic reorientation of the submolecular magnetic moments in rare earth-transition metal clusters. By a combination of x-ray circular magnetic circular dichroism and conventional vibrating sample magnetometry it has been possible to determine the effect of the Rare earth-Fe3 interaction on the reorientation of the Fe3 moments in “butterfly” carboxylates as a function of Rare earth substitution, ranging from isotropic and anisotropic Kramers ions (Gd and Dy) [3], or anisotropic non-Kramers ions (Tb and Ho) [4] . The different thermo-magnetic relaxational behavior at very low temperatures of these molecules is described.

1.- E. Bartolomé et al. Dalton Trans. 43, 10999 (2014) 2.- A. Arauzo et al. Dalton Trans. 43, 12342 (2014) 3.- Badía et al. Phys. Rev. B 87, 184403 (2013) 4.- Badía et al. Accepted in Phys. Rev. B (2015)

L13

OPTICAL AND MAGNETIC MOLECULAR SWITCHES BASED ON METAL-TO-METAL ELECTRON TRANSFER MECHANISM

Evangelia S. Koumousi,a,b,c,d Dmitri Mitcov,a,b Ie-Rang Jeon,a,b,c,d Diana Siretanu,a,b Pierre Dechambenoit,a,b Corine Mathonière,c,d and Rodolphe Clérac*,a,b

a CNRS, CRPP, UPR 8641, Pessac, F-33600, France; b Univ. Bordeaux, CRPP, UPR 8641, Pessac, F-33600, France ; c CNRS, UPR 9048, ICMCB, Pessac, F-33600, France ; d Univ. Bordeaux, ICMCB, UPR 9048, Pessac, F-33600, France Email: [email protected]

The design of molecule-based systems displaying tunable optical and/or magnetic properties under external stimuli received a great deal of attention in the past few years. This interest is driven by the potential applications in high-performance molecule-based electronics. As an example, 3D Fe/Co Prussian blue compounds exhibit a concomitant change in magnetic and optical properties due to a temperature- or light-induced metal-to-metal electron transfer (ET). The foregoing remarkable properties in Prussian blues prompted us to design soluble molecular fragments of these coordination networks through a rational building-block approach in order to mimic their properties on a single molecule.[1-4] With a judicious choice of the ligands for metal ion precursors, we prepared a octanuclear,[1] tetranuclear[2] and recently dinuclear[3] cyanido-bridged Fe/Co complexes. In the solid state, while an intramolecular ET is observed for [1,2] the [Co4Fe4] and [Co2Fe2] complexes, the Co ion of our first dinuclear complex exhibits a III II spin crossover (SCO) involving a [Fe LS-CN-Co LS] ground state and a thermally populated III II [3] [Fe LS-CN-Co HS] state. To our knowledge, this compound is the only example of a II heterobimetallic complex exhibiting a Co SCO. Remarkably, our studies of these [ConFen] complexes in solution reveal important optical and magnetic changes induced by an intramolecular metal-to-metal ET triggered and modulated by a controlled protonation of the complex, by the solvent nature or by temperature. Therefore, these molecules act as different molecular switches depending on their physical state and external stimuli.[3] These results motivated us to design new dinuclear [FeCo] complexes exhibiting both thermally and light induced electron transfer in solid state. Learning from these previous systems, new dinuclear complexes[4] have been designed by a rational building-block approach. Combined structural, spectroscopic, magnetic and photomagnetic studies reveal that a metal-to-metal electron transfer that can be triggered by light, temperature and lattice contents is observed for the first time in solid state for a dinuclear cyanido-bridged Fe/Co complex (See figure).[4]

[1]. D. Li et al., J. Am. Chem. Soc. 130, 252-258 (2008). [2]. Y. Zhang et al., Angew. Chem. Int. Ed. 49, 3752-3756 (2010); D. Siretanu, et al., Chem. Eur. J. 17, 11704-11708 (2011) ; Y. Zhang et al., J. Am. Chem. Soc. 136, 16854-16864 (2014). [3]. I.-R. Jeon, et al., Chem. Sci. 4, 2463-2470 (2013). [4]. E. S. Koumousi et al., J. Am. Chem. Soc. 136, 15461-15464 (2014).

L14

SUPRAMOLECULAR COMPOUNDS BASED ON THE DINUCLEAR COMPLEX 2+ [MO2O2S2] : FROM SYNTHESIS TO PROPERTIES AND APPLICATIONS

Sébastien Floquet and Emmanuel Cadot

Institut Lavoisier of Versailles, University of Versailles, 45 avenue des Etats-Unis, 78035 Versailles, France. [email protected], [email protected]

Current activity in the chemistry of Polyoxometalates (POM) is widely driven by potential applications in catalysis, magnetism, materials sciences and in Biology. During the last fifteen 2+ years, we used the dimolybdic complex [Mo2O2S2] as precursor or as linker to build new families of polyoxo(thio)metalates (POTM) compounds exhibiting a large variety of size, charges and properties. In this contribution, we will give an overview of the supramolecular systems based on this fragment, from coordination complexes, to cyclic systems resulting from 2+ the self-condensation of some [Mo2O2S2] units and finally to giant supramolecular systems based on the combinations of this unit with molybdates or tungstates.[1,2] A particular attention will be paid on the experimental conditions used for the preparation of these systems, their characterizations in solution by various NMR techniques and their properties respectively in biology,[3] in electro-catalysis for the production of hydrogen [4] and in materials science [5].

[1]. E. Cadot, M.N. Sokolov, V.P. Fedin, C. Simonnet-Jégat, S. Floquet, F. Sécheresse, Chem. Soc. Rev., 2012, 7335-7353. [2]. J.-F. Lemonnier, S. Duval, S. Floquet and E. Cadot. Isr. J. Chem., 2011, 51, 290-302. [3]. S. Floquet, E. Cadot, A. Hijazi, A. Gulea, V. Tapcov, V. Bulimaga, L. Zosim. Patent N° 4319 MD, MD - BOPI 1/2015 p33. [4] A. Hijazi, J.C. Kemmegne-Mbouguen, S. Floquet, J. Marrot, J. Fize, V. Artero, O. David, E. Magnier, B. Pégot, E. Cadot, Dalton trans., 2013, 42, 4848-4858. [5] N. Watfa, S. Floquet, E. Terazzi, M. Haouas, W. Salomon, V.S. Korenev, F. Taulelle, L. Guénée, A. Hijazi, D. Naoufal, C. Piguet, E. Cadot, Soft Matter., 2015, 11, 1087-1099.

L15

CHIRALITY AND ITS ROLE IN COORDINATION CHEMISTRY – THE JEKYLL AND HYDE BEHAVIOUR OF METAL IONS IN SEPARATING THE LEFT AND RIGHT SIDES OF THE WORLD

Annie K. Powell

Institute of Inorganic Chemistry and Institute of Nanotechnology, Karlsruhe Institute of Technology, 76131 Karlsruhe Germany. Email: [email protected]

The concepts of coordination chemistry developed by Alfred Werner at the beginning of the 20th century were finally substantiated by the realisation that a metal centre can invoke chirality by providing a central anchor-point to fix achrial ligands into a chiral structure. This is demonstrated easily with bidentate ligands which form tris-chelates, adopting either left- or right-handed propeller structures. On the other hand, a metal centre can provide an activation point for the inversion of the implied chirality of both pro-chiral and chiral ligands and lead to racemisation processes. Thus metal centres play an important role in terms of influencing the potential chirality of a given system.

This lecture will take examples from some of our recent work to illustrate these fascinating, but sometimes challenging, points. For example, intriguing chiral separations can be achieved when racemates of chiral ligands are used.[1] Furthermore, in addition to structural chirality induced by the presence of metal ions,[2] we can consider the implications for the fourth dimension in terms of time-reversal symmetry with a particular perspective on magnetic behaviour.[3]

[1] Ringing the changes in FeIII/YbIII cyclic coordination clusters, A. Baniodeh, C. E. Anson, A. K. Powell, Chem. Sci., 2013, 4, 4354–4361. [2] [LnNa(PhCO2)4] (Ln = Ho, Dy): The first examples of chiral srs 3D-networks constructed using the monotopic benzoate ligand, Z. Majeed, K. C. Mondal, G. E. Kostakis, Y. Lan, C. E. Anson, A. K. Powell, Chem. Comm., 2010 46, 2551-2553 (b) Spontaneous resolution in homochiral helical [Ln(nic)2(Hnic)(NO3)] coordination polymers constructed from a rigid non-chiral organic ligand, I. Mihalcea, N. Zill, V. Mereacre, C. E. Anson, A. K. Powell, Crystal Growth & Design, 2014, 14, 4729–4734. [3] (a) Spin chirality in a molecular dysprosium triangle. The archetype of the noncollinear Ising model, J. Luzon, K. Bernot, I.J. Hewitt, C. E. Anson, A. K. Powell, R. Sessoli, Phys. Rev. Lett., 2008, 100, 247205; (b) Heterometallic CuII/DyIII 1D chiral polymers: chirogenesis and exchange coupling of toroidal moments in trinuclear Dy3 single molecule magnets, G. Novitchi, G. Pilet, L. Ungur, V. V. Moshchalkov, W. Wernsdorfer, L. F. Chibotaru, D. Luneau, A. K. Powell, Chem. Sci,, 2012, 3, 1169-1176; (c) Ligand field variations: tuning the toroidal moment of Dy6 rings, A. Baniodeh, N. Magnani, S. Bräse, C. E. Anson, A. K. Powell, Dalton Trans. 2015, 44, 6343-6347.

L16

COMBINED TIME-REVERSAL TRANSFORMATION IN MAGNETIC DIMER CLUSTERS OF COORDINATION COMPOUNDS

Ion I. Geru

Institute of Chemistry of the Academy of Sciences of Moldova 3 Academy str., MD-2028 Chisinau, Moldova E-mail: [email protected]

The coordination compounds of ions with unfilled up 3d- and 4f-shell containing dimer magnetic clusters in a weak or intermediary crystalline field are considered, taking into account that the distance between clusters is more that the distance between ions forming the clusters. In this case it is possible to neglect the exchange interaction between electrons of different clusters and the structure of ground state of separate dimer is determined by intracluster exchange, spin- orbit, magnetic dipole-dipole and hyperfine interactions. Supplementary simplification consist in neglecting effects of covalency, conditioned by overlapping of the electrons orbitals of cation and electrons of neighboring diamagnetic ions or atoms. By this we exclude from consideration complexes of 4d- and 5d-groups, as well as cyanides of 3d-groups and complexes containing ions with partially filled up 5f-shell (actinides). However, even after these restrictions the number of complex compounds satisfying above mentioned demands is sufficiently large. It is also required that for considered 3d- and 4f-shells the effects of interconfigurational interaction are sufficiently weak. In these conditions the wave function of the hole in unfilled up shell of paramagnetic ion may be obtained from the wave function of electron of the same shell with the help of antiunitary time reversal operator. Within the framework of this approach by introduction of so-called “combined time-reversal transformation” it will be shown the possibility for transformation of antiferromagnetic type of exchange interaction in dimer cluster into ferromagnetic one. Let us imagine to ourselves for an instant that under the action of time-reversal operator on the wave functions of paramagnetic ions of dimer, being in coupled state due to exchange interaction between them, the reversion of signs of the spin projections operators takes place only to one of centers, for example, to the ion with spin S1, and no changes take place to spin projections operators of the second ion (that is not true). Such a transformation will be called a ”partial time-reversal”. It is clear that under the action of the partial time-reversal operator T1 the spin Hamiltonian of the isotropic exchange interaction between paramagnetic ions of the magnetic dimer cluster

H = −JS1S2 (1)

-1 does not remain invariant, but changes its sign (T1HT1 = - H). To restore the time-reversal invariance of the spin Hamiltonian it is necessary to perform the additional transformation -1 (T2HT2 = - H). Then the time-reversal operator T can be presented in the form T = T1T2 and the time-reversal symmetry will be restored (THT-1 = H). However, it is a trivial result. If instead of T2 to introduce the operator of isomorphic substitution O2 which change in the cluster the second 3dn ion by 3d10-n ion (or the second 4fm ion by 4f14-m ion), then the time- reversal invariance of the spin Hamiltonian (1) also will be restored

-1 -1 T1O2HO2 T1 = H. (2)

The analogical relationship take place if change T1 by T2 and O2 by O1. The role of operators O1 and O2 can be performed by chemist experimenter (!). The experimental data confirming actuality of the unusual definition of combined time-reversal transformation will be presented.

X-RAY STUDY ON THE STRUCTURAL, MAGNETIC AND CATALYTIC PROPERTIES OF FePc FILMS

F. Bartolomé and J. Bartolomé

Instituto de Ciencia de Materiales de Aragón, and Departamento de Materia Condensada. CSIC-Universidad de Zaragoza. 50009 Zaragoza. Spain.

Metal Phthalocyanines (MPc) are robust planar organic molecules with interesting electronic, magnetic, and transport properties. MPc's have been suggested as building blocks for nanodevices, spintronics or surface catalysis. We have performed an extensive experimental and theoretical study of several FePc films on Au(111) and Ag(110). The study includes a series of x-ray spectroscopy experiments (XAS, XMCD, XLPA) at the Fe K and L2,3 as well as N-K absorption edges, which is complemented with magnetization measurements and STM investigation of the films.

In the solid phase, FePc molecules form linear chains by columnar stacking. We have refined the structure of the film, showing a particular columnar stacking, different to that of the bulk phases [1].

2+ Fe L2,3 XMCD on the FePc textured thin films shows that the Fe ions present an unusually large, highly unquenched mL ≈ 0.5 μB orbital component, with planar anisotropy. The mL/mS = 0.83 ratio is the largest measured in 3d complexes and compounds. The origin of this unusually high orbital moment is the incompletely filled eg level lying close to the Fermi energy. This explains the unusually large and positive hyperfine field detected by Mössbauer spectroscopy in FePc. The FePc film strong planar anisotropy inferred from XMCD experiments is fully confirmed by magnetization measurements [2]. The observation of a quadrupolar signal in x-ray magnetic circular dichroism at the Fe K-edge has been crucial to the determination of the FePc electronic ground state. Indeed, all ground states previously suggested for FePc are incompatible with the experimental data [3].

Finally, some consequences of the evolution of the active site in the oxygen reduction reaction (ORR) catalyzed by iron phthalocyanine (FePc) submonolayers deposited on the Ag(110) surface will be shown. The capacity of reversibly and sharply switching the magnetic state of FePc molecules by chemical means has been conclusively evidenced by XMCD at the Fe L2,3 absorption edges. FePc on Ag(110) acts as a reversible bifunctional chemical−magnetic switch at the atomic monolayer scale [4].

[1] F. Bartolomé, et al., Journal of Applied Physics, 117(17), 17A735 (2015). [2] J. Bartolomé, et al., Phys. Rev. B 81, 195405 (2010) [3] J. Bartolomé, et al., Physical Review B, 91 (22), 220401 (2015). [4] J. Bartolomé, et al., J. Phys. Chem. C, 119, 12488 (2015).

POROUS STRUCTURES GENERATED BY CLUSTER BASED POLYMERS OR DISCRETE BINUCLEAR Co(III) BIS-DIOXIMATES

V. Ch. Kravtsov1, G. Duca2

1Institute of Applied Physics, Academy of Sciences of Moldova, Academiei 5, MD2028, Chisinau, R. Moldova 2 Academy of Sciences of Moldova, MD-2001, Chisinau, R. Moldova

Metal–organic materials (MOMs) represent an emerging class of materials that have attracted the imagination due to highly functional character and significant contributions in numerous applications areas including, but not limited to, catalysis, sensors, separations, transport of hydrogen, and drug delivery. MOMs are comprised of metal moieties and organic ligands and are exemplified by a diverse group of discrete (e.g. metal–organic clusters) or polymeric structures (e.g. coordination polymers or metal–organic frameworks (MOFs)). Polymeric MOMs demonstrate how crystal engineering holds great promise for control of the arrangement of atoms in space due to the ability to target specific molecular building block (MBB) with given geometry and directionality prior to the assembly process as well their inherent modularity and prototypal for a diverse range of structures. Recently more attention has been paid to the multinuclear metal-clusters as supermolecular building blocks (SBBs), which can be used as nodes with enhanced variety of coordination algorithms and size compare with a single metal ion and give rise to a family of cluster-based polymers. Apart from design perspective, multinuclear clusters may introduce their inherent extraordinary physical properties to the polymeric structure. The cluster-based polymers may be assembled from pre-designed and pre-synthesized SBBs. In the report will be demonstrated how the tri-, and hexanuclear metal carboxylate clusters linked by spacer organic ligands, lead to porous polymeric MOMs. The versatile polymeric architecture has been achieved with μ3-oxo trinuclear homo- and heterometalic type clusters. In combination with spacer ligands the 1D chains, 2D sheets polymers as well as a 3D highly porous MOM (Fig.1) with a large total potential solvent area of 44.1% of unit cell volume have been obtained. The 1D and 2D polymers have been also constructed from nanoscale II III hexanuclear manganese carboxylate clusters featuring the {Mn 4Mn 2(µ4-O)2} core with different spacer ligands. Some of them revealed the porous structure. The discrete binuclear Co(III) bis-dioximates with wheel-and–axle topology may also afford porous supramolecular MOM (Fig.2) with hourglass-like channels of diameter ca 0.6  1.3 nm and solvent area of 19.6% of unit cell.

Fig. 1 Fig.2

Authors acknowledge the financial support from the State Program of R. Moldova (Project 14.518.02.04A)

PREPARATION OF MIXED-OXIDE MATERIALS FROM HETEROMETALLIC COORDINATION COMPOUNDS

I. Bulimestru1, Olivier Mentre2, Nathalie Tancret2, N. Cornei3, S. Sova4, N. Popa1, A. Gulea1

1Department of Chemistry, Moldova State University, Chisinau, Moldova 2 Université Lille Nord de France, UCCS, BP 90108, 59652 Villeneuve d’Ascq cedex, France 3Department of Chemistry, Al. I. Cuza University, Iasi, Romania 4 Institute of Macromolecular Chemistry “Petru Poni”, 700487, Iasi, Romania

The increasing demand for heterometallic oxides is associated with the broad spectrum of their valuable properties. The performance of many oxide materials is extremely sensitive to the synthesis conditions [1, 2]. A convenient way of getting mixed-oxides is the single source molecular precursor (SSMP) method [3]. Ideally, a SSMP contains the required metal atoms in the ratio that corresponds to the stoichiometry of the desired multimetallic oxide. However, the synthesis of heterometallic compounds, which can act as SSMPs, represents an ambitious challenge because of the frequently divergent electronic and coordination requirements of the different metals. Aminopolycarboxylate (APC) complexes are promising SSMP candidates due to a wide variety of available ligands with high coordination capacity and variable charge which afford an easy adjustable stoichiometry of the target metals. Moreover, the composition of the precursors can be readily adjusted by using appropriate aminopolycarboxylates or additional ligands to achieve an optimal amount of combustible material. Along this line, we have started a systematic investigation of the influence of APC ligands, of the intermetallic distances, of the combustible material, of the heating rate and of the working atmosphere on the thermal degradation processes of heterometallic precursors and on the composition and microstructure of the final residue. For this purpose, two series of 2+(3+) 2+ heterometallic complexes of general formula Ba{M(APC)}X∙nH2O (M = Co , Mn ; X = no + - 2+ 2+ 3+ specie, H or CH3COO ) and M(L)y{Bi(APC)}znH2O (M = VO , Cu , Cr ; L = 2,2'-bipyridine or urea; y = 0, 1, 2 or 6; z = 1 or 2; n = 5 – 16) have been synthesized and probed as SSMPs for the preparation of Ba-Co(Mn)-O or Bi-V(Cu,Cr)-O mixed-oxides. As APC ligands we have successfully used nitrilotriacetate (nta3-), ethylenediaminetetraacetate (edta4-), 1,2- cyclohexanediaminetetraacetate (cdta4-) or diethylenetriaminepentaacetate (dtpa5-). It was found that the cumulative effect of short intermetallic separations and appropriate amount of combustible material from the precursors combined with heating in flowing air or oxygen at low rates can produce pure heterometallic oxides. The conditions required to prepare the oxide materials from SSMP are significantly milder than what has been previously reported for other methods. The differences observed in the grain size and morphology between the considered residues demonstrated that the nature of the initial organic ligands and heating rate can affect the microstuctural properties of the final bimetallic oxides.

References: 1. J. Gopalakrishnan. Chem. Mater., 1995, 7, 1265 2. S. Tokunaga, H. Kato, A. Kudo. Chem. Mater. 2001, 13, 4624. 3. M. Veith. J. Chem. Soc., Dalton Trans. 2002, 2405.

This work has been carried out with the financial support of Erasmus Mundus Ianus II project.

TEM and SEM DIFFRACTION METHODS IN THE STUDY OF COORDINATION AND SUPRAMOLECULAR COMPOUNDS

Sharali Malik

Karlsruhe Institute of Technology, Institute of Nanotechnology, Hermann von Helmholtz Platz 1, D-76131 Karlsruhe, Germany. E-mail: [email protected]

Electron diffraction via the transmission electron microscope is a powerful method for characterizing the structure of materials, including perfect crystals and defect structures. The advantages of electron diffraction over other methods, e.g., x-ray or neutron, arise from the extremely short wavelength (≈2 pm), the strong atomic scattering, and the ability to examine tiny volumes of matter (≈10 nm3). The use of electron diffraction to solve crystallographic problems was pioneered in the Soviet Union by B. K. Vainshtein and his colleagues as early as the 1940s [1]. In the elektronograf, magnetic lenses were used to focus 50 keV to 100 keV electrons to obtain diffraction with scattering angles up to 3° to 5° and numerous structures of organic and inorganic substances were solved. The elektronograf is very similar to a modern transmission electron microscope (TEM), in which the scattered transmitted beams can be also recombined to form an image. As the result of numerous advances in optics and microscope design, modern TEMs are capable of a resolution of 1.65 Å for 300 kV (and below 1 Å for 1000 kV) electron energy-loss combined with chemical analysis (through x-ray energy and electron-loss energy spectroscopy) and a bright coherent field emission source of electrons. Routinely in TEM, selected area diffraction (SAED) has been used to obtain spot diffraction patterns from crystals. However, the volume that can be sampled using this technique is defined by the size of the aperture inserted in the image plane of the objective lens. This leads to an effective probe size of a few hundred nanometers, which makes SAED unsuitable for obtaining diffraction information from individual nanostructures, within a dense cluster of such structures. Improvements in spatial resolution have been achieved by limiting the area of illumination on the specimen. In TEM mode, a quasi-parallel nanobeam (TEM/nanobeam diffraction – NBD) or a convergent beam (TEM/convergent beam electron diffraction – CBED) may be produced on the specimen. The TEM/NBD technique enables the formation of spots in the diffraction pattern and subsequent easy indexing. The TEM/CBED method gives rise to discs at the diffraction plane. The convergent incidence of the beam may also result in dynamical effects, such as Kikuchi lines in the diffraction pattern. Electron backscatter diffraction (EBDS) is usually used with a SEM and can provide quantitative microstructural information about the crystallographic nature of most inorganic crystalline materials. A TEM technique similar to EBDS-SEM is ASTAR (NanoMEGAS) but has nanometer resolution. The technique utilizes Precession Electron Diffraction patterns [2] which can be obtained automatically and indexed via pattern identification software.

[1] B. K. Vainshtein, Structure Analysis by Electron Diffraction, Pergamon Press, Oxford (1964). [2] R. Vincent and P. A. Midgley, Ultramicroscopy, 53, 271, 1994.

RATIONAL DESIGN OF SINGLE MOLECULE MAGNETS WITH THIOSEMICARBAZONE LIGANDS

O. Palamarciuc1,*, M. Secu1, T. Palamarciuc1, E. Stratulat1, S. Sova1,2, R. Clerac3,4

1Moldova State University, Chișinău, Republic of Moldova; 2Petru Poni Institute of Macromolecular Chemistry, Iași, Romania; 3CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Laboratory for "Molecular Materials and Magnetism", Pessac, F-33600, France; 4Université de Bordeaux, UPR 8641, Pessac, F-33600, France. *E-mail: [email protected]

In memoriam to Prof. Mihail Revenco

The coordination chemistry of the transition metal complexes containing thiosemicarbazide derivatives are investigated due to their attractive chemical, physical and biological properties. Using various thiosemicarbazide derivatives and different metal ions with a in different oxidation states, allows the preparation of a large number of coordination compounds with original structures and properties. In this work we present a new area of activation of the thiosemicarbazide fragment and its condensation product with salicylaldehyde - thiosemicarbazone by coordination with manganese metal ions. It is known that the manganese chemistry with thiosemicarbazide-based ligands is not so much investigated. Recently we described an original template reaction of salicylaldehyde S-alkyl-isothiosemicarbazones with 2-formylpyridine molecules which opens an original synthetic approach to design new families of ligands derived from thiosemicarbazide and, hence, new metal-ion coordination complexes [1]. Manganese(II) is not know to be an efficient templating ion for this type of condensation. Nevertheless using Mn(II) precursors, we were able to successfully synthesize polynuclear manganese complexes. The single crystal X-ray study of these compounds shows the formation of deca- and hexanuclear manganese species containing two different ligands: one initial ligand, and the second is the additional product between 2-formylpyridine and salicylaldehyde S-methyl-isothiosemicarbazone. The non alkylated salicylaldehyde thiosemicarbazone in strongly alkaline solutions allows the formation of the compounds with composition Mn(L)·3H2O. The X-ray investigation of its structure demonstrated the formation of a binuclear complex of the composition [(MnL2)(Mn(H2O)4)]·2H2O. The investigation of the magnetic properties of the manganese(II) dimer shows antiferomagnetic interactions between paramagnetic centers. The compound is not soluble in any solvent in inert atmosphere. In the presence of the air oxygen, in methanol solutions the oxidation of the of Mn(II) to Mn(III) and an oxidative dimerization of the coordinated salicylaldehyde thiosemicarbazonate anion were detected. As a result, the formation of a new hexadentate bicompartimental ligand coordinated to two different manganese(III) ions by O2N4 donor atoms has been observed. The manganese(III) units [(Mn2L)(CH3O)2(CH3OH)2] are assembled in polymer via µ2-oxo bridges provided by methoxy groups coordinated to the metal ions. Low-temperature magnetic investigations of the polymer indicates a ferromagnetic interaction and a slow relaxation in ac susceptibility, confirming the SMM behavior of the complexes.

[1] Mihail D. Revenco, Oleg V. Palamarciuc, Paulina N. Bourosh, Janusz Lipkowski, M.Gdanec, Yurii A. Simonov, Rodolphe Clérac, Inorganica Chimica Acta 368, 2011, p. 157–164.

SYNTHESIS, CRYSTAL STRUCTURE, AND PROPERTIES OF COPPER(II) COMPLEXES WITH 1,4,7-TRIS(2-AMINOETHYL)-1,4,7- TRIAZACYCLONONADECANE

Masahiro Mikuriya,a Mayu Hamagawa,a Natsuki Tomioka,a Daisuke Yoshioka,a Naoko Uehara,a Rika Fujimori,a Hiroki Yamamoto,a Yoshinari Ando,a Shoichi Hori,a Taro Kuriyama,a Ryoji Mitsuhashi,a and Makoto Handab

a Department of Applied Chemistry for Environment and Research Center for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan b Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan *e-mail: [email protected], TEL: +81-79-565-8365, FAX: +81-79-565-9729

Small macrocyclic ligand, 1,4,7-triazazcyclononane (tacn), is one of most studied ligands among macrocyclic ligands because of its unique chemistry [1]. Previously, we reported on metal complexes with cyclam-based octadentate ligand having four 2-aminoethyl groups as pendant arms, 1,4,8,11-tetrakis(2-aminoethyl)-1,4,8,11-tetraazacyclodecane (taec) [2]. Concerning to taec ligand, tacn-based hexadentate ligand having three 2-aminoethyl pendant groups, 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane (taetacn) is interesting. Recently, we reported on nickel(II) complex with taetacn. In this study, we synthesized new metal complexes with taetacn from reactions with copper(II) perchlorate and characterized the isolated complexes by IR, UV-vis spectra, and temperature dependence of magnetic susceptibilities. Herein we report on synthesis and magnetic and spectral properties of [Cu(taetacn)](ClO4)2 (1) and [Cu(Htaetacn)](ClO4)3 (2). We also report on the crystal structure and electrochemical property of 2.

1. Wainwright, K. P. Coord. Chem. Rev. 1997, 166, 35. 2. Murase, I.; Mikuriya, M.; Sonoda, H.; Fig 1. 1,4,7-tris(2-aminoethyl)-1,4,7- Fukuda, Y.; Kida, S. J. Chem. Soc., Dalton triazazcyclononane (teatacn). Trans., 1986, 953. 3. Mikuriya, M.; Hamagawa, M.; Tomioka, N.; Fujimori, R., Yoshioka, D.; Hori, S.; Kuriyama, T.; Sakiyama, H.; Handa, M.; Mitsuhashi, R. Chem. Pap. 2015, 69, in press.

AN EXPERIMENTAL AND THEORETICAL INVESTIGATION ON PENTA- COORDINATED COBALT(III) COMPLEXES WITH AN INTERMEDIATE S = 1 SPIN STATE: HOW HALIDE LIGANDS AFFECT THEIR MAGNETIC ANISOTROPY.

Brazzolotto D., Gennari M., Yu S., Pécaut J., Rouzières M., Clérac R., Duboc C., Orio M.

Aix Marseille Université, Institut des Sciences Moléculaires de Marseille, UMR 7313, Avenue Escadrille Normandie-Niémen,13397, Marseille, France [email protected]

Understanding the factors that control the magnitude and symmetry of the magnetic anisotropy should facilitate the rational design of mononuclear metal complexes in the quest of single molecule magnets based on a single metal ion with high blocking temperatures and large energy barriers. The best strategy is to define magneto-structural correlations through investigation of series of metal complexes. Since the main contribution to the magnetic anisotropy arises from spin-orbit coupling (SOC) effect in metal ion-based systems, current studies particularly focus both on the use of ligands and metal ions possessing a large SOC. We herein report on an unique series of halide CoIII complexes, (CoX) with X = Cl, Br and I, which possess a rare intermediate S = 1 spin ground state. These CoIII complexes are attractive species as they possess a remarkable large axial zero-field splitting (D parameter). Singlecrystal X-ray structures reveal that CoBr and CoI complexes are isostructural to the previously described CoCl complex1. They display distorted penta-coordinated square pyramidal geometries with the halide located in the CoIII axial position. Large positive D values of 35, 26 and 18 cm-1 have been found for CoCl, CoBr and CoI, respectively (Figure 1). To rationalize this trend, theoretical calculations based on both density functional theory and complete active space self-consistent field methods have been successfully carried out. Both sign and magnitude of D are remarkably predicted by these theoretical approaches. DFT calculations also show that the resulting D values originates from a balance of several contributions and that many factors including structural differences and halide nature should be taken into account to explain the trend of D in this series of complexes2.

Figure 1: Complexes of interest

1. Gennari, M.; Gerey, B.; Hall, N.; Pécaut, J.; Collomb, M.-‐N.; Rouzières, M.; Clérac, R.; Orio, M.; Duboc, C. Angew. Chem. Int. Ed. 2014, 53, 5318-‐5321.

2. D. Brazzolotto, M. Gennari, S. Yu, J. Pécaut, M. Rouzières, R. Clérac, M. Orio, C. Duboc, Chemistry, 2015, submitted

METAL COMPLEXES WITH LIGANDS CONTAINING DIMETHYLSILOXANE UNITS: SELF-ASSEMBLING ABILITY

Maria Cazacu, Alina Soroceanu, Mirela Zaltariov

“Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A Iasi, Romania, 700487

The presence of strongly hydrophobic dimethylsiloxane units as part of a structure could give to its more or less amphiphilicity, depending on the nature of the rest of the molecule. The co- existence of hydrophobic and hydrophilic moieties within the same molecule of a compound essentially contributes to their self-aggregation in solution forming nano-aggregates or nanoparticles [1]. The self-assembly of amphiphiles is driven by forces, which act to minimize the contact between the solvent and the solvophobic segment of the molecule [2]. In the case of metal complexes, specific behavior may occur due to the presence of metals, which are able of additional coordination or metal–metal interactions. As a result, some novel properties can be expected from their aggregates due either to the metal presence or related to the structures of metal complexes, such as the variable bonding strength of metal coordination interactions, coordination geometry variation and metal–metal interactions [2]. The association occurring in solution may be the basis for high catalytic activity of metal complexes with siloxane-containing ligands, as has already been demonstrated [3]. The aggregation ability in DMF solution of some new metal complexes of bis(azomethines) or telechelic dicarboxylic acids containing 1,3-bis(propyl)tetramethyldisiloxane moiety have been studied [4]. The aggregation in organic solvents was studied by surface tension measurements, dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) in solution. The morphology of the drop cast or spin-coated films was studied by transmission electron microscopy (TEM) and atomic force microscopy (AFM).

Acknowledgement: This work was supported by a grant of the Ministry of National Education, CNCS – UEFISCDI, project number PN-II-ID-PCE-2012-4-0261 (Contract 53/02.09.2013). References: [1] Iwakiri, N.; Nishikawa, T.; Kaneko, Y.; Kadokawa, J. I. Colloid Polym. Sci. (2009) 287: 577–582. [2] Lanigan, N.; Xiaosong, W. (2009) Chem. Commun. 49: 8133-8144. [3] Soroceanu, A.; Cazacu, M.; Shova, S.; Turta, C.; Kožíšek, J.; Gall, M.; Breza, M.; Rapta, P.; Mac Leod, T. C. O.; Pombeiro, A. J. L.; Telser, J.; Dobrov, A. A.; Arion, V. B. Eur. J. Inorg. Chem. (2013) 9: 1458–1474. [4] Soroceanu, A.; Cazacu, M.; Racles, C.; Stoica, I.; Sacarescu, L.; Varganici, D.-C. Soft. Mater. DOI: 10.1080/1539445X.2015.1009551.

MEDICAL DIAGNOSIS AND OTHER NMR SPECTROSCOPY APPLICATIONS TO NATURAL MIXTURES

Alina Nicolescu,1,2 Natalia Uşurelu,3 Romana Vulturar,4 Calin Deleanu 1,2

1. “Costin D. Nenitescu” Centre of Organic Chemistry of the Romanian Academy, Bucharest, Romania.

2. “Petru Poni” Institute of Macromolecular Chemistry of the Romanian Academy, Iasi, Romania.

3. Institute of Mother and Child, Chisinau, Moldova.

4. University of Medicine and Pharmacy, Cluj-Napoca, Romania.

The paper describes several NMR applications on natural mixtures performed in our laboratories. We exemplify with medical applications like diagnosis of Inborn Errors of Metabolism based on urine analysis and insights on neurological metabolism based on cerebrospinal analysis. In order to ensure reproducibility, apart from the NMR parameters and pulse sequences, several additional technical problems have to be solved. Some technical aspects are also discussed in the paper.

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RING PUCKERING PHENOMENA. PSEUDO JAHN-TELLER ORIGIN OF TWISTING IN N2C4H2Y2Z2 (Y= O, S, Se; Z= H, F, Cl, Br) HETEROCYCLES

Natalia N. Gorinchoy1 and Ali Reza Ilkhani2

1Institute of Chemistry, ASM, Academiei str. 3, MD2028, Chisinau, R. Moldova 2 Department of Chemistry Yazd Branch, Islamic Azad University, Yazd, Iran

Search of cyclic compounds that could serve as analogues of graphene in electronics, is currently the trend in modern chemistry. The mechanical, electric (conductivity), and magnetic properties of such systems are directly related to their geometry in the equilibrium configuration, notably their planarity. For this reason the mechanism of distortion of the planar configurations of cyclic compounds is of special interest. In this work the pseudo Jahn-Teller effect (PJTE) is employed to explain the instability of planar C2v nuclear configurations of the series of 3,6- pyridazinedione derivatives N2C4H2Y2Z2 (Y= O, S, Se, Z= H, F, Cl, Br) with respect to the a2 out-of-plane distortions leading to the puckered structures of C2 symmetry (Fig. 1).

Fig. 1. Instability of planar nuclear configuration of C2v symmetry occurs in all the 1 1 N2C4H2O2E2 (E= H, F, Cl, Br) compounds due to the PJTE ( A1+ A2) a2 problem.

The geometry optimization and the vibrational frequency analysis in planar and equilibrium (puckered) configurations of all the considered compounds with a N2C4 six-member ring were carried out by DFT B3LYP method and Dunning’s correlation consistent basis set cc- pVTZ with the Molpro 2010 package. The cross sections of the adiabatic potentials (APES) along the twisting normal coordinates (Qa2) were calculated with the state-average complete active space self-consistent ﬁeld CAS(8,8) wavefunctions. Parameters of the PJTE (primary 2 force constants K0, vibronic coupling constants V, and resulting force constants K= K0-V /Δ) were estimated by fitting the ab initio data for the APES of the systems to the general formulas. It is shown that the instability of planar C2v nuclear configurations and the out-of-plane 1 distortions of N2C4H2O2Z2 compounds are due to the PJT interaction of the ground A1 and the 1 lowest excited A2 states. The magnitude of the distortion decreases from N2C4H2O2F2 to N2C4H2O2Cl2, N2C4H2O2Br2 and N2C4O2H4, whereas the molecules N2C4S2H4 and N2C4Se2H4 are stable in the planar nuclear configuration.

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THE BREAKING SYMMETRY PHENOMENA IN PHENOTHIAZINE DRUG AND ITS DERIVATIVES

Ali Reza Ilkhani1

1 Department of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran.

Phenothiazine is a synthetic tricyclic compound and it is related to the thiazine heterocyclic with

S(C6H4)2NH chemical formula. At first, it was used as an anti-helminthic for livestock and humans but application its derivatives revolutionized psychiatry and other fields of medicine.

Electronic structure calculations provide the chemical structure of the system and it is answering the question why the structure of molecules are puckered. The Psuedo Jahn-Teller effect (PJTE) is the only source of instability and distortions of high-symmetry configurations of any polyatomic system in nondegenerate states such as phenothiazine and its derivatives. The goals of this study is: founding the reason of the breaking symmetry phenomena, non-planarity and bending instability in phenothiazine and some its derivatives from C2v symmetry in planar configuration to Cs puckered structure by the PJTE (Fig. 1).

Fig.1: The symmetry breaking phenomena in phenothiazine from unstable high-symmetry planar (C2v symmetry) to stable Cs bent structure.

To do this, the Molpro 2010 package were carried out for optimization and frequency calculations of thiazine, phenothiazine and two S-oxygenated derivatives of phenothiazine in their planar configuration. An imaginary frequency was observed along b1 normal coordinate in all these compounds. Following the state-average complete active space self-consistent ﬁeld (SA- CASSCF) wavefunctions have been employed to calculate the APES along the bending 1 1 normal coordinates and it shown that ( A1+ B1) b1 PJTE problem is the reason of the breaking symmetry phenomena and bending of the C4NS ring in the all under consideration compounds.

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MÖSBAUER SPECTROSCOPY OF IRON COMPONDS IN THE IONIC CROSS-LINKED POLYMERS

Vasile Gutsanu

Moldova State University, 60 Mateevici str., MD 2009, Chisinau, Moldova. [email protected] Cross-linked ionic polymers are widely used in various fields of science and technology. The largest amount of polymers is used to the water treatment at thermal, thermo-electrically and nuclear power stations as ion exchangers. Ion exchange is not a selective process, while new technologies require sorbents and catalysts with selective properties. Relatively recently there were made investigation of implementation of metal compounds in the phase of polymers, that radically changes their properties. Being amorphous and cross-linked, the investigation of processes with involving of these polymers is difficult due to the limited use of research methods. One of the most informative methods in the investigation of the processes, that take place in the phase of cross-linked polymers, is the Mossbauer spectroscopy, complemented by EPR, IR spectroscopies, magnetic susceptibility method. This communication reports the results of investigation of interaction of iron ions with different classes of commercial ionic cross-linked polymers, using the Mossbauer spectroscopy. At first it was investigated the interaction of iron ions with strongly acid cation exchangers. But we, along with academician Constantin Turta, first started to investigate the complexation of iron ions with amines or carboxylic groups of the ion exchangers using Mossbauer spectroscopy. It was demonstrated that the Fe2+ cations are oxidized easily in complexes with the carboxyl groups of the polymer. As a result of the reduction of Fe3+ ions with small molecular reducing agents, complexes in the phase of carboxylic polymer are destroyed. With the use of Mossbauer spectroscopy it has been shown that the retention of Fe2+ and Fe3+ ions on weakly basic anion exchangers takes place not due to the ion exchange, but as a result of their coordination with polymers’ amine groups. The most recent and interesting works are devoted to the investigation of the formation of iron compounds in the phase strongly basic anion exchangers. As we know, strongly basic anion exchangers do not contain negatively charged or electron donors atoms in their matrix. Therefore, theoretically, they cannot interact with metal cations. But, surprisingly, we found that under certain conditions this type of polymers can interact with some metal cations. As a result of these interactions in the polymer phase are formed ultrafine particles of the jarosite mineral + type compounds: R4N[M3(OH)6(SO4)2], where R4N are functional groups of the polymer, M may be Fe3+, Cr3+, Al3+ and others cations. Synthesis of the metallic compounds in the polymer phase, change radically the physicochemical properties of the polymers. They become adsorbents and catalysts with selective properties. Selective adsorption properties are due to the exchange of ligands: 2- 2- R4N[M3(OH)6(SO4)2] + 2XO4 = R4N[M3(OH)6(XO4)2] + 2SO4 or R4N[M3(OH)6(SO4)2] 3- 2- 2- 2- 3- 2- 2- + 2XO4 = R4N[M3(OH)6(XO4)2] + 2SO4 where XO4 or XO4 are CrO4 , VO4 , 2- 3- 3- WO4 , AsO4 , PO4 , or other ions or moleculea which are able to form coorinate bonds. The polymers, containing iron compounds are good models for investigation using the Mossbauer Spectroscopy.

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FERROCENYLSILOXANE UREA: SYNTHESIS, STRUCTURE AND PROPERTIES

Mihaela Dascalu, Mihaela Balan, Sergiu Shova, Carmen Racles, Maria Cazacu

“Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41 A, Iasi 700487, Romania

The first cyclic ferrocenylsiloxane-urea, {1,1’-ferrocene-diurea-[1,3- bis(propylene)tetramethyldisiloxane]} (FSU), has been formed by reacting 1,1’- ferrocenediisocyanate with 1,3-bis(aminopropyl)-tetramethyldisiloxane in a chloroform-toluene mixture. The ferrocenylsiloxane urea was structurally characterized by FTIR and 1H-NMR spectroscopy, elemental analysis, mass spectrometry (ESI-MS), and single crystal X-ray diffraction. The asymmetric unit contains two conformers packed in one-dimensional supramolecular column through intermolecular interaction between N-H and O-H protons on the one hand with urea oxygen atoms and solvate water molecules on the other hand. The dynamic of the hydrogen bonds in solid state compound in dependence on temperature was investigated by IR-spectroscopy. 1H-NMR spectra revealed the dependence of the chemical shifts of the groups responsible on the hydrogen bond formation on concentration and solvent polarity. After the loss of crystallization water and retained solvent traces, the compound is stable up to 510 oC when the organic part is decomposed leaving a large amount of residue consisting in iron and silicon oxides. Due to the co-existence in structure of the polar (ferrocenyl-uree) and nonpolar (bis(propyl)tetramethyldisiloxane) moieties, the compound proved to be able to self-assemble in CHCl3 in quasi-spherical aggregates with vesicle-like aspect. This behavior was less obvious in polar medium (DMSO). The compound showed reversible redox processes and the shape of the voltammogram indicates the presence of essentially noninteracting iron centers in structure.

2D MANGANESE(II) NETWORKS BASED ON V-SHAPED BIS(P-CARBOXYPHENYL)DIPHENYLSILANE: SYNTHESIS, STRUCTURES AND PROPERTIES

Angelica Vlad, Mirela-Fernanda Zaltariov, Maria Cazacu, Sergiu Shova

“Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, 700487 Iasi, Romania

Two coordination networks based on V-shaped bis(p-carboxyphenyl)diphenylsilane (cpdps) ligand and Mn(II) ions: {[Mn5L(cpdps)4(HCOO)2(H2O)2(DMF)4]·6DMF}n (I) and {Mn3(μ-H2O)2(Hcpdps)2(cpdps)2(DMF)2]∙2DMF∙12H2O}n (II) were synthesized by conventional and solvotheramal methods and structurally characterized by X-ray single crystal diffraction. The pentanuclear and trinuclear manganese clusters in I and II, respectively, act as SBUs, while the V-shaped ligand links the SBUs leading to 2D coordination networks (Fig. 1).

Figure 1. Obtaining of the Mn(II) coordination networks by conventional (I) and solvothermal (II) methods

Magnetic susceptibility measurements in the 0-300 K range of both coordination networks show the existence of anti-ferromagnetic exchange interactions between the Mn(II) ions. The thermogravimetrical data revealed a good thermal stability of both complexes, while the results of the water vapor sorption capacity in dynamic regime indicated good moisture stability of the manganese(II) coordination networks

Acknowledgements: This work was supported by a grant of the Ministry of National Education, CNCS – UEFISCDI, project number PN-II-ID-PCE-2012-4-0261 (Contract 53/02.09.2013)

NMR METABOLIC FINGERPRINTING OF SOME PLANTS AND FRUITS

Alina Nicolescu,1,2 Mihaela Balan,1 Mihaela Ciobanu,1 Cristina Stavarache,2 Gabriela Ailiesei,1 Doina Dănilă,3 Camelia P. Ştefanache,3 Mihaela Silion,1 Ana-Maria Macsim,1 Alexandru Ciocârlan,4 Calin Deleanu.1,2

1. “Petru Poni” Institute of Macromolecular Chemistry of the Romanian Academy, Iasi, Romania. 2. “Costin D. Nenitescu” Centre of Organic Chemistry of the Romanian Academy, Bucharest, Romania. 3. “Stejarul” Biological Research Centre, Piatra Neamt, Romania. 4. Institute of Chemistry, Academy of Sciences of Moldova, Chisinau, Republic of Moldova

NMR spectroscopy is already established as a powerful analytical tool in plant research. The main advantage of this technique is that it provides the sample’s profile in one analysis. The chemical composition of different vegetal matrices is important for life sciences such as food science and medicine. One of the ways to characterize plants through high resolution NMR is to analyze the juice obtained by squeezing different plant components. The paper presents a feasibility study for fast and automatic discrimination of natural or processed juices from different plants (like Arnica Montana L.) and fruits (like apples, oranges, etc). The NMR data have been subjected to statistical processing in order to develop a model for plants and fruits discrimination based on metabolomic spectral fingerprinting.

Acknowledgements The authors acknowledge the financial support of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PN-II-PT-PCCA-2013-4-0791.

STRUCTURAL INSIGHTS INTO THE ZINC-MEDIATED ACTIVITY OF POLYPYRIDINECHELATORS AT THE CHEMOKINE RECEPTOR CCR5

Roxana-Maria Amarandi1,2, Stefanie Karlshøj2, Mette Marie Rosenkilde2, Aurel Pui1

1 Faculty of Chemistry, ‘Alexandru Ioan Cuza’ University of Iaşi, Bd. Carol I Nr. 11, Iaşi 700506, Romania 2 Laboratory for Molecular Pharmacology, Department of Neuroscience and Pharmacology, Faculty of Health and Medical Sciences, The Panum Institute, University of Copenhagen, Copenhagen, Denmark Metal-ion chelators are useful tools in characterizing activation patterns of seven- transmembrane helix receptors (7TMRs), and have been successfully employed in unraveling activation-inducedhelical movements at numerous rhodopsin-like receptors [1, 2].Moreover, some receptors of the chemokine subclass of rhodopsin-like 7TMRs have been found to respond to micromolar concentrations of metal ion chelators in the presence of zinc salts [3-5], exhibiting activity most likely through the formation of a coordination complex consisting of negatively charged amino acid sidechains, metal ion and chelator, stabilized by secondary hydrophobic interactions between the chelator scaffold and aromatic amino acid sidechains in the receptor structure.Not much is known, however, of the exact molecular interactions that occur in the binding site of a receptor when a chelator ligand accompanied by transition metal ions, such as Zn2+, are in contact with the receptor. For this purpose, we combined in vitro mutagenesis studies with molecular docking experiments in order to map the binding site of the aqueous in situ zinc complexes of 2,2:6’,2”-terpyridine (ZnTpy) and 4-chloro-2,2’:6’,2”-terpyridine (ZnClTpy), two polypyridine ligands which, in spite of only one structural difference, exhibit different behaviors at the chemokine receptor CCR5in the presence of ZnCl2[4]. Thus, ZnTpy acts an ago-allosteric modulator, both enhancing the binding of CCL3 and having activity on its own at CCR5, while ZnClTpy acts as a purely allosteric ligand, enhancing the binding of the chemokine alone [4]. We found that, aside the complete lack of activity of the aqueous complexes at the E283A mutant, F109 is crucial for the allosteric behavior of both aqueous complexes, while aromatic residues lining the major binding pocket exclusively impact the intrinsic activity of ZnTpy. We furthermore found that residues in the minor binding pocket are distinctively important for both aqueous complexes. Taken together, these findings suggest that both complexes are accommodated in the binding site of the receptor in a similar manner, an observation which was additionally supported by molecular docking studies, further indicating that the molecular outcome of receptor activation cannot be exclusively revealed from mutational analysis, and most likely involves changes in receptor conformation undetectable by mutagenesis or molecular docking studies.

1. Hoffmann, C., Zurn, A., Bunemann, M., and Lohse, M.J., Conformational changes in G-protein-coupled receptors-the quest for functionally selective conformations is open. Br J Pharmacol, 2008. 153 Suppl 1:S358-66. 2. Rosenkilde, M.M., Andersen, M.B., Nygaard, R., Frimurer, T.M., and Schwartz, T.W., Activation of the CXCR3 chemokine receptor through anchoring of a small molecule chelator ligand between TM-III, -IV, and -VI. Mol Pharmacol, 2007. 71(3):930-41. 3. Jensen, P.C., Thiele, S., Ulven, T., Schwartz, T.W., and Rosenkilde, M.M., Positive versus negative modulation of different endogenous chemokines for CC-chemokine receptor 1 by small molecule agonists through allosteric versus orthosteric binding. The journal of biological chemistry, 2008. 283(34):23121-8. 4. Thiele, S., Malmgaard-Clausen, M., Engel-Andreasen, J., Steen, A., Rummel, P.C., Nielsen, M.C., Gloriam, D.E., Frimurer, T.M., Ulven, T., and Rosenkilde, M.M., Modulation in selectivity and allosteric properties of small-molecule ligands for CC-chemokine receptors. Journal of medicinal chemistry, 2012. 55(18):8164-77. 5. Thiele, S., Steen, A., Jensen, P.C., Mokrosinski, J., Frimurer, T.M., and Rosenkilde, M.M., Allosteric and orthosteric sites in CC chemokine receptor (CCR5), a chimeric receptor approach. The journal of biological chemistry, 2011. 286(43):37543-54.

NEW INHIBITORS OF GLYCATION AND OF THE FORMATION OF ADVANCED GLYCATION END PRODUCTS

Andronache Lilia, Gudumac Valentin1, Gulea Aurelian2, Tagadiuc Olga1, Garbuz Olga2, Pantea Valeriana1

1State University of Medicine and Pharmacy "Nicolae Testemitanu" 2 State University of Moldova, Chisinau,Republic of Moldova

Background. The accumulation of advanced glycation end-products (AGEs) due to non- enzymatic glycation of proteins is specific for various diseases associated with aging and diabetes melitus, particularly for diabetic complications. AGEs formation changes the structure and function of long-living proteins, especially structural proteins such as collagen and elastin, which contributes to the development and worsening of chronic degenerative aging-related diseases and cancer. These products have numerous biologic effects  stimulate the secretion of cytokines and adhesion molecules, contribute to the release of growth factors, enhance the proliferation, migration and invasion of cancer cells, increase the vascular and myocardial stiffness involved in the development of chronic complications of diabetes, damage the vascular endothelium and induce the development of cardiovascular diseases [1]. These considerations have prompted the search for AGE inhibitors. Prevention and treatment strategies include prevention of AGEs cross-links formation and their destruction by cross-links breakers [1, 2]. Thus, is of great interest to study the influence on the processes of AGEs formation of the local bioactive compounds (BC) – new Schiff bases and their combination with 3d metals exhibiting important bioactive properties [3]. The aim of this study was to elucidate the biochemical mechanisms of action of local BC, in particular, to assess their capacity and effects of AGEs cross-links breakers. Methods. 120 new local BC  Schiff bases and their 3d metal compounds, synthesized at the Department of Inorganic Chemistry of the State University of Moldova were studied. In vitro screening of the different concentrations of local BC (0.01 to 100 µM/L) to identify the inhibitors of AGEs formation was based on 96-well microtiter plate fluorescence assay [2]. The fluorescence was measured in Hybrid Multi-mode Microplate Rider Synergy H1, "BioTek" (USA). Results. The obtained data showed that local BC have AGEs cross-links breaker action in the in vitro models. From 120 tested compounds the most active AGEs formation breakers were found to be the following compounds  CMA-2, CMC-6, CMJ-33, TIA-59 and TIA-70, which in concentrations of 50-100 μM/L reduce the AGE formation by 60-70%, and the compounds CMA-1, MAC-3, CMC-13, CMC-38, which reduce AGE formation by 30-50% compared with reference values. Conclusions. The new local BC  Schiff bases and their combination with 3d metals exhibit the capacity to inhibit the AGEs formation. This provides a new potential therapeutic approach for prevention of age-related chronic degenerative diseases by improving the myocardial elasticity and removal of blood vessels stiffness and skin changes related to age. This data justify the necesity for further detailed research on the therapeutic potential of BC as AGEs breakers. Bibliography. 1. Samuel Rahbar and James L. Figarola. Novel inhibitors of advanced glycation endproducts..Archives of Biochemistry and Biophysics 419 (2003) 63–79. 2. Luc Séro, et al.Tuning a 96-Well Microtiter Plate Fluorescence-Based Assay to Identify AGE Inhibitors in Crude Plant Extracts. Molecules 2013, 18, 14320-14339. 3. Gulea A., et al.. In vitro antileukemia, antibacterial and antifungal activities of some 3d metal complexes: Chemical synthesis and structure –activity relationships // Journal of Enzyme Inhibition and Medicinal Chemistry, 2008; V. 23. Nr.6, pp.806-818.

MOLECULAR DYNAMICS SIMULATIONS AND SMALL ANGLE X-RAY SCATTERING ANALYSIS OF DIFERRIC HUMAN LACTOFERRIN IN SOLUTION

Lilia Anghel1, Raul Victor Erhan2,3, Duca Gheorghe1

1Institute of Chemistry of Academy of Sciences of Moldova, 3, Academiei Street, MD-2028, Chisinau, Republic of Moldova 2Horia Hulubei National Institute for R&D in Physics and Nuclear Engineering, 30 Reactorului Street, P.O.BOX MG-6, Bucharest - Magurele, Romania 3Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, 141980, Dubna, 6 Joliot-Curie Street, Russia

Human lactoferrin is a basic (pI 9.48) glycoprotein member of the transferrin family [1]. Like other proteins members of the transferrin family, lactoferrin is involved in the control of iron levels in living organism. Lactoferrin properties derive from the structural characteristics and its main function of iron uptake. For this reason it is important to investigate the mechanism of iron binding and iron release, as well its behavior in various solutions. In the present work we have applied the performance capabilities of Molecular Dynamics simulation and Small-Angle X-ray Scattering (SAXS) technique to investigate the behavior of diferric human lactoferrin in aqueous solution. SAXS experiment was performed on a sample of lactoferrin dispersed in deionized water. To avoid the inter-particle interactions, a diluted sample of lactoferrin was used, with a concentration of 2.0 mg/mL. The value of the radius of gyration of lactoferrin calculated using Guiner approximation was Rg=41.7±0.5 Å, which was in a god agreement with the Rg in the real space value of 42.0±0.4 Å calculated from the pair-distribution function. Furthermore, it was computed the Rg values for the high-resolution 3D models of monoferric and diferric human lactoferrin (PDB codes 1LFH.pdb and 1B0L.pdb, respectively) in water using molecular dynamics simulations. It was obtained an estimation of 30 and 28.6 Å for diferric and monoferic lactoferrin, respectively. Further analysis of the SAXS scattering curve revealed that lactoferrin undergoes self-associating processes in aqueous solution forming homo- dimeric structures (Figure 1).

Figure 1. Structure modeling of the high resolution model of lactoferrin against the SAXS scattering curve (A) and the low resolution model of lactoferrin obtained from the scattering curve (B).

(A) (B)

References: [1]. Anghel L. An investigation of the protonation states of human lactoferrin iron-binding protein. Chemistry Journal of Moldova, 2015, 10(1), pp. 71-75. [2]. Baker, E.N., Baker, H.M. Molecular structure, binding properties and dynamics of lactoferrin. Cellular and Molecular Life Sciences, 2005, 62, pp. 2531-2539.

SYNTHESIS OF 8,9- BICYCLOHOMOFARNEZENIC ACID HYDRAZIDE FROM NORAMBREINOLIDE

A.N. Aricu, K.I. Kuchkova, A.N. Barba, E.C. Gorincioi, I.P.Dragalin, N.D.Ungur, P.F.Vlad

Institute of Chemistry, Academy of Sciences of the Republic of Moldova, Academiei str. 3, MD-2028, Chisinau, Republic of Moldova

Many drimane sesquiterpenoids exhibit varous types of biological activity [1]. In continuation of our investigation on the synthesis of nitrogen-containing drimane and homodrimane sesquiterpenoids [2-4], we herein describe the synthesis of 8,9- bicyclohomofarnezenic acid hydrazide (9) from commercially available norambreinolide (1), according to the scheme: O OR OR CO NHNH2 O a OH c

1 2 R=H 4 R=Ac b d 9 3 R=Ac 5 R=H i CHO CO2H COCl

e (5) f h

6 7 8 g Reagents and condtions: a) LiAlH4, Et2 2O, Py, 20°C, 2h, 99%; c) MeSO3SiMe3, CH3CN, 20°C, 5h, 85%; d) KOH, MeOH, 20°C, 2h, 99%; e) DMSO, P2O5, CH2Cl2, 0°C, 10 min, 20°C, 45 min ; Et3N, 0°C, 10 min, 20°C, 45 min, 95 %; f) NaClO2, . NaH2PO4 2H2O, 2-Me-2-butene, t-BuOH, 20°C, 2 h, 94 %; g) Jones reagent, (CH3)2CO, 0°C, 48 . h, 42 %; h) (COCl)2, C6H6 2H4 H2O (98%), CH2Cl2 65%. The structures of the newly obtained compounds were establiched on the basis of their spectral data (IR, 1H- and 13C NMR). The hydrazide (9) was synthesized in order to test its biological activity.

References: 1. B.J.M. Jansen, A. De Groot, Nat. Prod. Reports, 2004, 21, 449. 2. K.I. Kuchkova, A.N. Aricu, P. F. Vlad, C. Deleanu, A. Nicolescu, Chem. Nat. Comp., 2010, 46, 539. 3. K.I. Kuchkova, A.N.Aricu, A.N. Barba, P.F. Vlad, Ya. Lipkovskii, Yu.A. Simonov, V.Kh. Kravtov, Chem. Nat. Comp., 2011, 47, 223. 4. K. Kuchkova, A. Aricu, E. Secara, A. Barba, P. Vlad, N. Ungur, C. Tuchilus, S. Shova, Gh. Zbancioc, I. I. Mangalagiu, Med. Chem. Res, 2014, 23, 1559.

SYNTHESIS OF 11-DIHOMODRIMAN-8-OL-12-ONE DERIVATIVES WITH AZINE AND HYDRAZIDE FRAGMENTS

A.N. Aricu, K.I. Kuchkova, A.N. Barba, E.C. Gorincioi, I.P.Dragalin, N.D. Ungur, P.F.Vlad

Institute of Chemistry, Academy of Sciences of the Republic of Moldova, Academiei str. 3, MD-2028, Chisinau, Republic of Moldova

In the search of new biologically active compounds and in continuation of our work on the synthesis of nitrogen-containing drimane sesquiterpenoids [1-4], in the prezent report we describe the preparation of 11-dihomodriman-8-ol-12-one derivatives with azine (3) and hydrazide (4) fragments from norambreinolide (1), according to the scheme given below. O O O N N a OH b OH HO

1 2 3

c O O C C NH (CH ) NH N 2 4 N

OH HO 4

. Reagents and condtions: a)CH3Li, Et2O, 20°C, 15 min, 65%; b) N2H4 H2O (98%), MeOH, , 10h, 80%; c) NH2NHCO(CH2)4CONHNH2, MeOH, , 20h, 25%. . The azine (3) was obtained by interaction of hydroxyketone (2) with N2H4 H2O (98%) in methanol. The reaction of compound (2) with adipic acid dihydrazide led to the formation of N,N’-di(8-hydroxy-11-dihomodrim-12-yliden)-adipic acid dihydrazide (4). The structures of compounds (3) and (4) were established on the basis of their IR, 1H- and 13C NMR data.

References: 5. K.I. Kuchkova, A.N. Aricu, P.F. Vlad, Chem. Nat. Comp., 2009, 45, 367.

6. K.I. Kuchkova, A.N. Aricu, P. F. Vlad, C. Deleanu, A. Nicolescu, Chem. Nat. Comp., 2010, 46, 539.

7. K.I. Kuchkova, A.N.Aricu, A.N. Barba, P.F. Vlad, Ya. Lipkovskii, Yu.A. Simonov, V.Kh. Kravtov, Chem. Nat. Comp., 2011, 47, 223.

8. K. Kuchkova, A. Aricu, E. Secara, A. Barba, P. Vlad, N. Ungur, C. Tuchilus, S. Shova, Gh. Zbancioc, I. I. Mangalagiu, Med. Chem. Res, 2014, 23, 1559.

DFT STUDY OF TRANSITION STATES AND PRODUCTS ● ● OF RADICAL REACTION HO2 + HO2

Ion Arsene and Natalia Gorinchioy

Institute of Chemistry, Academy of Sciences of Moldova,Chisinau, Republic of Moldova E-mail: [email protected]

On the base of density functional theory (DFT) calculations the mechanism for the oxygen production in the radical reaction

2 ● 2 ● ● ● 1 3 HO2 + HO2 = HO2 ―HO2 = TS = H2O2―O2 = H2O2 + O2 was revealed. The DFT calculations were performed with the PRIRODA 06 program [1] using the PBE functional [2] and the implemented in the PRIRODA 06 package basis set L1 which is an analog of the Dunning’s double-zeta basis sets cc-pVDZ [3]. Since we are interested in the products of the above reaction in their electronic ground states, all the calculations for the reactants, products, intermediates, and transition states were performed for the total spin S=1. Calculations show that the most stable triplet H2O4 intermediate structure is a doubly hydrogen-bonded planar six-member ring of Ch symmetry (Scheme 1). The transition state was localized and verified by intrinsic reaction coordinate analysis. Harmonic vibrational frequency calculations indicate that the transition state is indeed a first-order saddle point, as characterized by one imaginary frequency equal to 849.78i (Scheme 1).

2 ● 2 ● 1 3 Scheme 1. Calculated energy profile of the reaction HO2 + HO2 = H2O2 + O2 (all values are in kcal/mol).

2 ● 2 ● 1 3 The reaction HO2 + HO2 = H2O2 + O2 is the exothermic process; the total energy gain is 35.14 kcal/mol, compared to the experimental value of 38.28 kcal/mol [4].

1. Laikov, D. N., PRIRODA, Electronic Structure Code, Version 6, 2006. 2. J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865. 3. T. H. Dunning, Jr., J. Chem. Phys., 1989, 90, 1007. 4. Tyndall, G. S.; Cox, R. A.; et. al., J. Geophys. Res., 2001, 106, 12157-12182.

SYNTHESIS AND CRYSTAL STRUCTURE OF CHLORO-(2-FORMYLPYRIDINE- THIOSEMICARBAZONO)COPPER DIMETHYL SULFOXIDE SOLVATE.

N.Bairac1, P. Petrenko2, Yu. Chumakov2, А. Gulea1

1 Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Moldova 2Institute of Applied Physics of Academy of Sciences of Moldova, Chisinau, Moldova e-mail: [email protected]

In the present, thiosemicarbazide’ derivatives are widely used in medicine to treat infections caused by various microorganisms. It was found that some coordinative compounds of these substances, which can be obtained at their interaction with transition metal salts, display physiologic activity, this fact allowing to examine them as preparations with biochemical and pharmacologic application. Therefore, the objective of this work consists in establishing optimal synthesis conditions, determination of the composition and structure of the Copper (II) coordinative with thiosemicarbazone 2-formylpyridine (HL) with the further determination of its biologic properties. N S HL = NH2 N NH . The aforementioned component was obtained at the interaction of boiling ethanol o solutions (55-60 C) of CuCl2 2H2O with thiosemicarbazone 2-formylpyridine with the molar ratio of 1:1. The substance in the focus was re-crystallized from the solution of ethanol - dimethyl sulfoxide (4:1). The obtained monocrystals were analyzed with X-rays.

The crystal structure contains the complex [CuLCl] and a molecule of dimethyl sulfoxide solvent. In this complex, Copper display coordination number 6 and is bonded with pyridinic nitrogen, azomethine, thiosemicarbazone sulfur and chlorine ion. Each molecule represents a dimer, where the thiosemicarbazone sulfur plays the role of the bridge and is the symmetry center of the molecule. Fig.1 Structure [CuLCl]∙DMSO

Furthermore, indentifying the anti-proliferative activity of the synthesized complexe was of high interest. It was found that this complex inhibit the growth of myeloid leukemia cells HL-60 in concentration levels between 10-4-10-5 mol/L. With the concentration level 10-6 mol/L the researched coordinative complex does not display any activity.

This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F.

P10

QUANTUM-CHEMICAL CALCULATIONS AND MECHANISTIC CONSIDERATIONS OF THE ORGANOCATALYTIC DESTRUCTION OF POLYETHYLENE TEREPHTALATE (PET) Emeric Bartha,1* Sorana Ionescu,2 Simona Nica,1 Anamaria Hanganu,1 Mihai Deleanu,1 Monica Duldner,3 Stela Iancu3

1Centre of Organic Chemistry "C.D. Nenitzescu"of the Romanian Academy, Spl. Independentei 202 B, Bucharest, Romania, *e-mail: [email protected] 2Physical Chemistry Dept., University of Bucharest, Bd. Regina Elisabeta 4 - 12, Bucharest. 3National Institute of Research and Development for Chemistry and Petrochemistry-ICECHIM, 202 Spl. Independentei, Bucharest, Romania.

Polyethylene terephtalate (PET) is a thermoplastic polyester with outstanding thermal and chemical resistance properties. Due to the fact that it is not biodegradable, the increased consumption of PET led to a significant accumulation of waste into landfields. Chemical recycling allows controlled cleavage of the polymer with isolation of the monomers that can be reused in the PET manufacture or to obtain other valuable chemicals. The most studied method for PET recycling is glycolysis with ethylene glycol and/or other glycols [1]. The reaction follows a transesterification mechanism, reason why metal salts, especially heavy metals are used as catalysts. Recently, organocatalysts and especially, bifunctional organocatalysts have been investigated and turned out to be a good choice for improving the PET destruction rate [2]. Because of their acid-base character, they activate both, the ester carbonyl group through the nucleophile component and the reactants (alcohols or amines) through their acidic part. Based on our expertise in glycolysis of PET wastes involving biomass alcohols [3], we have modeled the transesterification reaction between dimethyl terephthalate (DMT) and isosorbide (IS) in the presence of 1,5,7- triazabicyclo[4.4.0]dec-5-ene (TBD). Our goal was to determine whether the dual function of the catalysts is responsible for the occurrence of the trans-esterification reaction. In this case, two alternatives were investigated: i) the formation of the hydrogen bonds between the catalyst and the diol and ii) the acyl transfer with the formation of the amide intermediate. For this purpose, quantum chemical calculations using DFT method with a B3LYP functional and a TZVP basis set were used to investigate the reaction mechanism. These theoretical calculations were corroborated with 1H-NMR spectroscopy in solution. If methanol is present in the reaction medium, the first pathway is more likely to be followed whereas, if methanol is removed from the reaction medium, the dual function of the guanidinic catalyst is responsible for the catalytic activity.

This work was supported by UEFISCDI grant PNII-PT-PCCA-2013-4-1388, no61/2014- PERCIT.

1. G. P. Karayannidis et al. Macromol. Mat. Eng., 291, 2006, 1338. 2. J. L. Hedrick et al. J. Polym. Sci. Part A: Polym. Chem., 51, 2013, 1606. 3. E. Bartha et al. Rev. Chimie, 62, 2011, 401;E. Bartha et al. Rev. Chimie, 2015, in press.

P11

STUDY OF MAGNETIC AND ANTIOXIDATIVE PROPERTIES OF SOME BIOMETAL COORDINATION COMPOUNDS OF o-VANILLIN ISONICOTINOYLHYDRAZONE A. Gulea, V. Tsapkov, M. Birca, A. Cotovaia,V. Gudumac*, O. Garbuz, I. Petcenco, E. Malic

Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Republic of Moldova e-mail: [email protected] * Department of Microbiology, Virusology and Immunology Nicolae Testemitsanu, State University of Medicine and Pharmacy, Chisinau, Republic of Moldova

In this work some 3d-biometal coordination compounds of o-vanillin isonicotinoylhydrazone were synthesized and their properties were studied. o-Vanillin isonicotinoylhydrazone was obtained by condensation of 2-hydroxy-3-methoxybenzaldehyde with isonicotinic acid hydrazide.

H2L

It were synthesized 14 new coordination compounds of Cr3+, Mn2+, Fe3+,Co3+, Ni2+, Cu2+, 2 Zn with o-vanillin isonicotinoylhydrazone (H2L). The composition of theses coordination compounds were determined on the basis of data from elemental analysis: M(HL)2X·nH2O, 3+ 3+ 3+ - - 2+ 2+ 2+ where M = Co , Fe , Cr ; X = Cl , NO3 ; n = 1-4; M(HL)X·nH2O, where M = Ni ,Cu , Zn ; - - - 2+ 2+ , 2+ X = Cl , Br , NO3 ; n = 2-6; M(L)·H2O, where M = Ni ,Cu Zn , n = 1-5; Mn(HL)2·H2O. Magnetochemical research showed that coordination compounds of cobalt and nickel are diamagnetic. The effective magnetic moments of synthesized copper coordination compounds are close to the spin value for one unpaired electron. Therefore it can be supposed that they have monomeric structures. Chromium, manganese, and iron coordination compounds are paramagnetic and the values of their effectivetic magentic moments correspond to octahedral structures and the oxidation number +3 for chromium and iron complexes and +2 for manganese coordination compound. Antioxidants are substances capable to transform free radicals into inactive forms. They are used extensively in medical practice. The study of antioxidant activity of the synthesized coordination compounds showed that they inhibit the appearance of ion-radicals at the concentration 10-6 mol/L at the level of Trolox that is used in medical practice as a standard antioxidant. Antioxidant activity depends on the nature of the central atom and for the homotypic coordination compounds changes in the following way Co Mn Ni Zn Cr Fe Cu. Transfering of the ligand in doubly deprotonated form results in growth of the antioxidant activity. This work showed that the search of new antioxidants among biometal coordination compounds of ligands derived from isoniazid has prospects.

This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F.

P12

SYNTHESIS, STRUCTURE, AND ANTITUBERCULOUS PROPERTIES OF COPPER COORDINATION COMPOUNDS WITH 2-HYDROXY-3- METHOXYBENZALDEHYDE ISONICOTINOYLHYDRAZONE

A. Gulea1, V. Tsapkov1, M. Birca1, A. Cotovaia1, V. Crudu2, S. Eftodii2, E. Malic1

1Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Republic of Moldova 2Phthisiopneumology Institute ”Chiril Draganiuc”, Republic of Moldova e-mail: [email protected]

Isonicotinic acid hydrazide (isoniazid), known in medical practice as tubazide, is an organic compound that is used in medicine for prophylaxis and treatment of tuberculosis. This substance manifests one of the best bacteriostatic activities against Mycobacterium tuberculosis H37Rv, but it also has high toxicity and, therefore, its use as a medicine is limited. Using isoniazide as initial substance by the reaction of condensation with 2-hydroxy-3-methoxybenzaldehyde it was obtained 2-hydroxy-3-methoxybenzaldehyde isonicotinoylhydrazone (H2L). Monocrystals of H2L were obtained as a result of recrystallization from ethanol and their crystal structure was determined by X-ray analysis. Ligand H2L represents almost planar molecule except methoxy group. Also it was synthesized one coordination compound of Cu(II) with H2L. Its composition and probable structure was determined on the basis of data from elemental analysis and magnetochemistry:

N N H NH N N N O n H2O O O OH M O O CH3 X H3C H2L

The data obtained from the study of antituberculous properties is shown in the table. This research indicates that the free ligand H2L and coordination compound Cu(HL)Cl manifest bacteriostatic activity at the concentrations 10 and 20 μg/mL. These substances inhbit the growth of tuberculosis bacteria H37Rv for the first two weeks.

# Compound Dilution WK.1 WK.2 WK.3 WK.4 WK.5 10 negative negative positive positive positive 1 H L 2 20 negative negative positive positive positive 10 negative negative positive positive positive 2 Cu(HL)Cl 20 negative negative positive positive positive

Antituberculous activity of the synthesized substances is comparable with the activity of medicaments used in medical practice.

This work was fulfilled with the financial support of the Project 14.518.04.07A of the State Program.

P13

NEW USES OF BIOACTIVE PHYTOCOMPOUNDS DEPENDING ON MOLECULAR STRUCTURE

Bobeică Valentin, Covaliov Victor, Albert Ivancic, Nenno Vladimir, Olga Covaliova

State University of Moldova, Scientific Research Center of Applied and Environmental Chemistry, 60, Mateevici str., Chisinau, Republic of Moldova

It is known that plant secondary metabolites are bioactive phytochemicals, both through important vital roles which have the plant producing it, and through their effects on human and animal body at its exogenous application. Different phytochemical compounds, representatives of different phytochemicals classes exogenously applied in different systems shows stimulants plant growth, antioxidants, cells membranoprotectives, tissues regenerators and other activities. These manifestations of secondary metabolites plant bioactivity inspired the research described in this paper on stimulating activity of methanogenic microorganisms in the biochemical anaerobic fermentation processes on organic substrates with emission of biogas as an energy source. Were tested, in special conditions of a laboratory anaerobic digester (Covaliov V., Nenno V. and coauthors design) [1], biologically active substances from different phytochemicals classes: saponins, flavonoids, tannins, alkaloids, steroids, cumarins etc. A manifest intensification of anaerobic fermentation process occurred with the application of gypsoside (triterpenoid saponin), sclareol (bicyclic diterpenoid) and squalene (acyclic triterpenoid) as fermentation phytostimulators. As a substrate was used the mixture of pulp obtained after alcohol distillation and animal manure in weight ratio 3:1. The concentrations of the test compounds ranged from 10-3 - 10-5% by weight of the substrate. It is evident (Table 1) that addition of these three compounds in the reaction mixture increase biogas emission over a period of 220 hours by two times compared with control test - without addition of phytostimulator. Table 1. Emission dynamics and total biogas volume (ml) produced under the experiment conditions Time from the start of Gypsoside Sclareol Squalene Control test the experiment, h 0 0 0 0 0 2,5 50 40 30 30 5 60 50 60 40 24 83 75 81 40 27 83 80 117 40 40 150 116 160 40 43 158 125 72 25 65 50 137 38 25 70 37 137 38 25 75 50 40 35 17 144 25 20 20 15 170 20 20 20 15 195 20 20 18 12 220 12 12 12 12 Total biogas 798 756 699 333 The common element of these compounds is the isoprene structure of their molecules. All three compounds have biogenetic isoprene provenance.

References 1. Combined anaerobic bioreactor for the production of biomethane. Patent of invention MD no 4189. Inventors:COVALIOV, V., COVALIOVA, O., UNGUREANU, D., NENNO, V., BOBEICA, V., SLIUSARENCO, V., IONETS, I. Publ. BOPI, 2013, no.7, p.28-30.

P14

INHIBITION OF STEEL CORROSION IN NATURAL WATER BY CARBOHYDRAZIDE

Bologa О. А.*, Parshutin V.V.**, Sholtojan N.S.**, Koval’ А.V.**, Chernysheva N.V.** , Bulhac I.*

*Institute of Chemistry of the Academy of Sciences of Moldova, Academiei str.3, MD2028 Chişinau, R. Moldova ** Institute of Applied Physics of the Academy of Sciences of Moldova, Academiei str.5, MD2028 Chişinau, R. Moldova [email protected]

In practice, very often the use of the inhibitor is the only possible method of protection against corrosion of the metal constructions, in which water and aqueous solutions are used as working fluids. The effectiveness of the latter depends on the salt composition of water, and varies according to the time of the year and location. The selection of the inhibitors is carried out only by experiment [1, 2]. A hydrazine containing substance - carbohydrazide was used as a corrosion inhibitor for the protection of carbon steel in natural water:

. It is shown that the greatest effect can be achieved by using the inhibitor containing 0.1- 1.0 g/l of substance. Thus, when using the inhibitor with the concentration of 0.5 g/l for 8 and 24 hours the corrosion losses are reduced by 13 and 6.8 times (the level of Z protection is 92.3 and 85.4%, respectively) and with 0.25 g/l concentration, by 10.6 and 7.6 times (the level of Z protection is 90.6 and 86.9%, respectively). At the concentration of 0.75 g/l of carbohydrazide at the same exposures, the loss of corrosion decreases by 10.1 and 6.4 times, whereas at a concentration of 1.0 g/l - by 9.5 and 6.2 times. Addition of the inhibitor that is a diacid basis alkalizes slightly the medium. The nature of the influence of the inhibitor concentration at pH medium at any test time is pretty the same: with the beginning of corrosion the acidification starts, the longer the exposure time, the smaller the acidulation. The addition of carbohydrazide in water leads to an abrupt shift of the stationary potential in the negative direction, indicating that carbohydrazide is the inhibitor of a cathodic action. Anodic potentiodynamic measurements show that addition of carbohydrazide leads to the decrease of the anodic process, the higher the concentration of the inhibitor, the larger diminution. The effect of the inhibitor on the formation of the protective coating layers on the surface of the corroding metal was established. Their X-ray, IR spectral analysis were carried out, the UV spectral analysis of the solutions at various carbohydrazide concentrations and exposure time was done. The mechanism of the involvement of the inhibitor in the process of suppressing the metal corrosion was established.

1. Паршутин В.В., Шолтоян Н.С., Сидельникова С.П., Володина Г.Ф., Болога О.А., Шафранский В.Н., Гэрбэлэу Н.В. Влияние тиосемикарбазида на коррозию стали в воде. // Электронная обработка материалов. 2005. № 5. С.77-88. 2. Паршутин В.В., Шолтоян Н.С., Чернышева Н.В., Коваль А.В., Володина Г.Ф., Булхак И.И., Болога О.А., Шафранский В.Н Влияние тиосемикарбазона пировиноградной кислоты на коррозию стали Ст.3 в воде. // Ibid.,2012. № 6. Р.80-91.

P15

AN OXO-BRIDGED HEXANUCLEAR IRON(III) CLUSTER: SYNTHESIS, STRUCTURE AND PROPERTIES

Olga I. Botezat1,2, Jan van Leusen2, Victor Ch. Kravtsov1, Paul Kögerler2, Svetlana G. Baca1

1Institute of Applied Physics, Academy of Science of Moldova, Academiei 5, MD2028 Chisinau, R. Moldova 2Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

The synthesis and characterization of oxo-, hydroxo- and alkoxo-bridged 3d-metal compounds attract huge interest owing to their architectural beauty and possibilities to exhibit interesting magnetic properties such as single molecule magnets (SMMs). Furthermore, polynuclear iron(III) clusters can be used as building blocks for the construction of cluster-based coordination polymers [1] . A new hexanuclear iron(III) compound [Fe6O(thme)4Cl6](mdeaH3)2∙(MeCN) (1) has been prepared by the reaction of µ3-oxo trinuclear iron(III) isobutyrate precursor with 1,1,1- tris(hydroxymethyl)-ethane (thmeH3) and methyldiethanolamine (mdeaH2) ligands under hydrothermal conditions. A single-crystal X-ray diffraction analysis showed that 1 crystalizes in 2 the tetragonal space group I-42d and consists of an anionic [Fe6O(thme)4Cl6] cluster, two + outersphere protonated mdeaH3 and acetonitrile molecule. In the anionic cluster with C2 molecular symmetry a central oxygen atom resides on two fold axis and is surrounded by six Fe(III) centers to form an octahedron (Fig. 1). Twelve alkoxo groups of four triply deprotonated thme ligands additionally bridge the Fe(III) atoms. All six Fe(III) atom in 1 are six-coordinated and adopt an elongated octahedral O5Cl environment by one Cl atom and five O atoms: one 3 central µ6-O atom and four O atoms from two neighboring thme ligands. The long bond distances from each Fe(III) atoms to the central µ6-O atom vary from 2.223 to 2.265 Å, and other FeO bonds are in the range 1.980 - 1.995 Å. Thermogravimetric analysis showed that compound 1 is thermally stable up to 140°C and then step by step completely decomposes reaching temperature 700°C with the formation of iron oxides. The spectroscopic and magnetic measurements have been also studied and all data will be discussed.

2- Fig. 1. Structure of hexanuclear iron(III) [Fe6O(thme)4Cl6] cluster (left) and a view of 8+ {Fe6O13} core (right).

Acknowledgments. This study is supported by Swiss National Science Foundation (SCOPES IZ73ZO_152404/1) and DAAD (O. I. B).

[1] S.G. Baca, I.G. Filippova, T.D. Keene, O. Botezat, Iu.L. Malaestean, H. Stoeckli-Evans, V.Ch. Kravtsov, Iu. Chumacov, Shi-Xia Liu, S. Decurtins. Eur. J. Inorg. Chem. 3 (2011) 356-367; G. M. Dulcevscaia, I. G. Filippova, M. Speldrich, J. van Leusen, V. Ch. Kravtsov, S. G. Baca, P. Kögerler, Shi-Xia Liu, S. Decurtins. Inorg. Chem. 51(9) (2012) 5110−5117.

P16

HEXAMMINECOBALT(III) COMPLEX AS MULTIPLE HYDROGEN BOND DONOR AND ANION RECEPTOR

I. Radu1, P. Bourosh1, J. Hauser2, V. Kravtsov1, S. Decurtins2, S.-X. Liu2, S. G. Baca1

1Institute of Applied Physics, Academy of Sciences of Moldova, Academiei 5, MD2028, Chisinau, R. Moldova 2Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012-Bern, Switzerland

Anion binding is now an attractive area of investigation in the construction of supramolecular donor-acceptor complexes and in recent years more research has been devoted to employing the main principles of anion binding into practical applications such as anion sensors, catalysis, extraction of anions from mixtures, and medicinal use of transmembrane anion transport. Among various anion receptors, ammonium-based ones such as hexamminecobalt(III) 3+ [Co(NH3)6] exhibits high binding affinity and selectivity [1-3] as well as a great potential as a broad-spectrum antiviral and antibacterial drug. We have used the receptor [Co(NH3)6]Cl3 in the reaction with different N,O-donor ligands to fabricate a new series of hydrogen-bonded complexes, namely [Co(NH3)6]Cl3•2(phen)•3(H2O) (1), [Co(NH3)6](Hbdc)(bdc)•3H2O (2), [Co(NH3)6]Cl2(Hpht)•2.5(H2O) (3), and [Co(NH3)6]11[Co(pdc)3]8(OH)•84(H2O) (4), where phen = 1,10′-phenanthroline, H2bdc = biphenyl-4,4′-dicarboxylic acid; H2pht = o-phthalic acid; H2pdc = 2,5-pyridinedicarboxylic acid. All complexes have been prepared from water or water/methanol solution and have been characterized by X-ray single crystal diffraction measurements. Compounds 1 and 2 crystallize in the triclinic space group P-1, 3 in the monoclinic space group I2/m, and 4 in the trigonal space group R-3, respectively. In these III 3+ compounds Co centers are six-coordinated by NH3 molecules, forming a [Co(NH3)6] II 4 octahedron, with CoN bond distances of 1.939(3) – 1.99(1) Å. In 4, the [Co (pdc)3] anion (Fig. 1), has a distorted octahedral environment of the CoII center formed by three O atoms and three N atoms from three pdc2 residues with CoO bond distances in the range 2.079(2) – 2.093(28) Å and CoN bond distances of 2.131(3) – 2.140(3) Å. Multiple NHO, NHN, NHCl, OHCl and OHO hydrogen bonds (Fig. 2) which link the cations, anions and water molecules into a H-bonded network will be discussed.

II 4 Fig. 1. Structure of [Co (pdc)3] anion in 4. Fig. 2. Fragment of crystal structure of 1.

Acknowledgement. Financial support was provided by the project SCOPES IZ73Z0_152404/1.

[1] N. Gorska, et al., RSC Advances 2012, 2, 4283; [2] R.P. Sharma, et al., J. Mol. Struct. 2005, 748, 143; [3] R. Tian, et al., Acta Crystallogr. 2012, E68, m914.

P17

SYNTHESIS, STRUCTURE AND SPECTROPHOTOMETRIC PROPERTIES OF PALLADIUM(II) 8-QUINOLINALDEHYDE N(4)-(2,4,6)- TRIMETHYLPHENYLTHIOSEMICARBAZONE

P. Bulmaga1, P. Bouroş2, A. Sîrbu1, I. Corja1, T. Cazac3

1Moldova State University, 60 Mateevici Str., Chisinau MD 2009, Moldova 2Institute of Applied Physics of the Academy of Sciences of Moldova, MD 2028, Chisinau, Moldova 3Institute of Chemistry of the Academy of Sciences of Moldova, MD 2028, Chisinau, Moldova [email protected]

The paper reports the results of the spectrophotometric study of K2[PdCl4] interaction with N(4)-(2,4,6)-trimethylphenylthiosemicarbazone of 8-quinolinaldehyde (L) in dimethylformamide-water solution, some properties of the resulted compound and its crystal structure. Classic methods have been used to perform the UV-VIS spectrophotometric study of 2- [PdCl4] ÷ L mixture in solution. The solution of the ligand, of the same concentration as of the resulted complex, was used as reference. The results of the investigations clearly demonstrated a 1:1 ration of the reactants. The values of the molar absorption coefficient of the resulted complex in solution and its conditional stability constant have been calculated. The result of the investigation of 2- [PtCl4] ÷ L system in solution demonstrated that the reagents react much slower than its Pd(II) analogue. So the absorption electronic spectrum of the organic reagent remains nearly the 2- same after [PtCl4] is added. Only 40 minute later, the formation of a new absorption species was observed. This made possible the testation of N(4)-(2,4,6)- trimethylphenylthiosemicarbazone of 8-quinolinaldehyde as a spectrophotometric reagent for Pd(II) determination in the presence of Pt(II). Accordingly, concentrations of 0,5-11 ppm of Pd(II), containing a tenfold amount of Pt(II), could be determined with an average error of 2,5%. 2- From dimethylformamide-water solution of [PdCl4] — L system a solid compound was separated. Upon its recrystallization from dimethylformamide- isopropyl alcohol mixture a red crystalline compound of PdLCl formula is formed. Single crystal X –ray diffraction study demonstrated that the complex has a square-planar geometry. The ligand coordinates to the metal ions through quinolinic and azomethinic nitogen atoms and sulfur. The fourth coordination site is taken by Cl- ion. N(4)-(2,4,6)-trimethylphenyl fragment is positioned perpendicular to the plan formed by the metal ion and the ligand.

P18

STRUCTURE OF ONE-DIMENSIONAL COORDINATION POLYMER CATENA- {BIS[CADMIUM(II)(SUCCINATE)BIS(HYDROSUCCINATE) TETRA(NICOTINAMIDE)]}

Diana Chisca,a* Eduard B. Coropceanu,b Lilia Croitor, a Marina S. Fonaria

a Institute of Applied Physics Academy of Sciences of Moldova, Chisinau, Moldova, b Institute of Chemistry Academy of Sciences of Moldova, Chisinau, Moldova. *E-mail: [email protected]

Along with the rigid three-dimensional (3D) coordination networks, the rational design of flexible porous coordination polymers [1] is currently in focus of crystal engineers. The aliphatic dicarboxylic acids with different chain lengths and transition metals with the variable coordination polyhedra are the useful building units for this purpose [2]. Coordination bonds act in the basic framework, while conformational flexibility of the ligands’ aliphatic skeleton and hydrogen bonds direct a flexible dynamic structure [3]. Herein, we report the mixed-ligand one-dimensional (1D) coordination polymer with the composition [Cd2(suc)(Hsuc)2(nia)4]n I, where H2suc=succinic acid and nia=nicotinamide, and with the {Cd2(COO)4} binuclear cluster as the secondary building unit (SBU). Compound I crystallizes in the monoclinic space group P21/n: a=11.4313(3), b=14.6649(3), c=12.9413(4) Å, β=102.751(3) °. In the centrosymmetric SBU each Cd(II) atom is heptacoordinated in the N2O5 coordination environment. The succinate anions exist in two different deprotonated states, Hsuc– and suc2–. The Hsuc– anion, as a terminal ligand, bridges two Cd atoms in a syn-syn mode, the Cd···Cd separation being of 3.912 Å. Contrary, the suc2– anion acts as a bridge with bis- chelating mode, giving rise to the 1D coordination chain (Fig.) with the Cd···Cd separation across it of 9.124 Å. The axial positions occupy nitrogen atoms from two terminal nia ligands.

… 2 Two types of homomeric supramolecular synthons, the amide, NH O(O=C), R2 (8) and … 2 carboxylic COOH COOH, R2 (8) ones, provide the aggregation of coordination chains into 3D network. The two-fold interpenetration is achieved via amine-carboxylate heterosynthon. The pyridine rings of nia ligands in the 1D chain are separated by the distance of 4.099 Å reachable for weak π–π stacking interactions.

Acknowledgment. D.C. & L.C. acknowledge the financial support from the Grant for Young Scientists (15.819.02.03F).

1. K. Uemura, R. Matsuda, S. Kitagawa J. Solid State Chem., 2005, 178, 2420. 2. L. Croitor et al., Cryst. Growth Des. 2014, 14, 3935. 3. S. Kitagawa, K. Uemura, Chem. Soc. Rev., 2005, 34, 109.

P19

Cu(II) COORDINATION POLYMERS WITH PICOLINIC ACID AND BIPYRIDINE LIGANDS

Diana Chisca,a* Eduard B. Coropceanu,b Lilia Croitor,a Svetlana G. Baca,a Karl Krämer,c Shi-Xia Liu,c Silvio Decurtins,c Marina S. Fonaria

a Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Moldova, b Institute of Chemistry, Academy of Sciences of Moldova, Chisinau, Moldova, c Department of Chemistry and Biochemistry, University of Bern, Bern, Switzerland

Use of multifunctional ligands, bearing both neutral and anionic donor groups has attracted great attention nowadays since both donor groups of the ligand can coordinate to metal centers, and thus build in coordination polymer (CP) without counter anions. These ligands allow the generation of various coordination architectures and topologies. The picolinic acid and its derivatives are a class of such bifunctional ligands being widely used to construct various CPs not only for structural interest but also for diverse applications. Herein, we report two mixed- ligand CPs based upon Cu(II)-picolinate building unit, 2D [Cu2(pic)2(OAc)2(bpy)]n I, and 1D {[Cu(pic)(OAc)(bpe)]·x(H2O)}n II, where Hpic = picolinic acid, bpy = 4,4'-bipyridine and bpe = 1,2-bis(4-pyridyl)-ethane; and the structural diversity is achieved due to the different ratio of components. Compound I crystallizes in the monoclinic space group P21/n: a = 8.3146(3), b = 6.6250(3), c = 23.3232(10) Å, β = 92.086(4)°. The Cu(II) ion adopts a N2O3 trigonal bipyramidal coordination provided by one N atom of bpy molecule, one N atom of pic anion, one O atom from monodentate AcO anion, and two O atoms of two bidentate-bridging pic residues. The Cu···Cu separations are 5.326 Å across pic and 11.095 Å across bpy. The exo-dentate-bridging bpy and pic ligands are responsible for 2D herringbone layer.

I II Compound II crystallizes in the monoclinic space group P21/c: a = 45.460(2), b = 18.4612(8), c = 15.0365(6) Å, β = 91.738(4)°. The Cu(II) ions adopt N3O2 coordination cores derived from three N atoms of the bidentate-bridging bpe ligand and of pic residue, and two O atoms from terminal monodentate AcO and pic anions. The bpe bridge provides the zigzag-like 1D chain with the Cu···Cu separations in the range of 13.263 - 13.790 Å. This solid demonstrates the cumulative solvent uptake indicated by the 833 Å3 of the solvent accessible volume (or 6.6 % of total unit cell volume) after the guest molecules evacuation. The magnetic properties of I have been studied and will be discussed in term of known structure.

Acknowledgments. Authors thank SCOPES IZ73Z0_152404/1 for financial support. D.C. & L.C. acknowledge the financial support from the Grant for Young Scientists (15.819.02.03F).

P20

COORDINATION COMPOUNDS OF Zn AND Mo WITH MACROCYCLIC LIGANDS DERIVED FROM 2.6-DIFORMYL-4-METHYLPHENOL AND THEIR BIOLOGICAL PROPERTIES

Deseatnic- Ciloci A.A., 1Bulhac I.I., 1Bologa O.A., Tiurin J.P., Clapco S.F., Bivol C. M., Dvornina E.G., Labliuc S.V. Institute of Microbiology and Biotechnology, Aсademy of Sciences of Moldova 1Institute of Chemistry of the Aсademy of Sciences of Moldova, Chisinau, Moldova

In recent years, it was found that the complexes of transition metals play a significant role in the processes occurring in living organisms, showing a stimulatory or inhibitory (antiviral, antimicrobial, antitumor etc.) effect on their growth and development. They also serve as potential regulators of the biosynthesis of biologically active substances, including a variety of extracellular enzymes of the microorganisms. The condensation of the malonic acid dihydrazide with 2.6-diformyl-4-methylphenol in the presence of the molybdenum acetylacetonate or zinc nitrate as a result of the template reaction on the matrix of those metals, led to creation of complexes with the most simple formulas MoO2(L-2H)·2H2O and Zn(L-2H)·H2O. The IR spectra of the obtained compounds -1 showed absence of the absorption bands in the region 3400-3200 cm (ν(NH2), that in the spectrum of the malonic acid dihydrazide appeared at 3298 and 3200 cm-1. Also the absorption bands are missing in the region 1680-1640 cm-1 (ν(C=O)), but in the spectrum of the malonic acid dihydrazide were present at 1664 and 1646 cm-1 and in the spectrum of the 2.6-diformyl-4- -1 methylphenol were appeared at 1679 cm . This confirmed the condensation of the organic components. The change in position of the absorption bands (ν(C=O)) in the spectrum of the complexes at 1623 cm-1 for zinc compound and at 1618 cm-1 for molybdenum compound demonstrated that the carbonyl groups of the dihydrazide of the Schiff base coordinate the metal atoms. The lack of the absorption bands of the complexes in the spectra δ(OHphenol), which in the spectrum of 2.6-diformyl-4-methylphenol appeared at 1214 cm-1, has confirmed that this group coordinates to the metal in the deprotonated form. Evaluation of the biological properties of the obtained compounds was performed by assessing the effect of these compounds on the process of enzymogenesis of the micromycete Aspergillus niger CNMN FD-06. The strain refers to the "black aspergillus" and is an active producer of amylolytic enzymes which can hydrolyze starch as in standard conditions (at pH 4.7) and in extremely acidic conditions (at pH 2.5). This extends the possibilities of its use in the biotechnological productions. The maximal enzyme activity of the standard (pH 4.7) and acid-stable (pH 2.5) amylases of the strain was observed in the 5th day of the cultivation and in this experiment was 50.68 U/ml and 56.56 U/ml, respectively. The results showed that the complexes had an inhibitory effect at all concentrations on the activity of both types of amylases synthesized by the micromycete. With the increase of the concentration of the complexes was enhanced the inhibitory effect. Thus, using the complex №1 in the 5th day of cultivation the inhibitory effect of the standard amylase increased from 25.1% (at 5 mg/L) to 45.1% (at 15 mg/L), and for acid-stable amylase – from 37.7% (at 5 mg/L) to 52.9% (at 15 mg/L).The inhibitory effect was stronger in the case of the complex №2 and was of 35.1% (at 5 mg/L) - 55.2% (at 15 mg/L) for standard amylase and of 59.9% (at 5 mg/L) - 67.0% (at 15 mg/L) for the acid-stable amylase. Thus, it was revealed that the tested complexes have inhibitory effect on some aspects of the metabolism of micromycete Aspergillus niger CNMN FD 06, which allows to suggest the possibility of their use for controlling plant diseases.

P21

NEW ANTIFUNGAL AND ANTIBACTERIAL ACTIVITIES OF LAGOCHILIN AND ITS DERIVATIVES

Alexandru Ciocarlana, Magdalena Stronceaa, Aculina Aricua, Lidia Lungua, Nicoleta Vornicub and Michele D’Ambrosioc

a Institute of Chemistry, Academy of Sciences of Moldova, Academiei str. 3, MD-2028 Chisinau, Moldova, E-mail: [email protected] b Metropolitan Center of Research T.A.B.O.R, The Metropolitanate of Moldavia and Bukovina, Closca no. 9, RO-700066 Iasi, Romania c Universita degli Studi di Trento, Laboratorio di Chimica Bioorganica, via Sommarive 14, Povo, Italy

Naturally occurring tetraol lagochilin (1) belongs to the bicyclic diterpenoids with grindelic (9,13-epoxilabdanic) carbonic schelet [1]. Mentioned compound and some its derivatives were isolated from plants of Lagochilus genus which includes about 30 species widespread in Middle Asia [2, 3]. Plants of this genus and some pharmacological preparations based on them are used as strong hemostatics with sedative and anti-allegic affects [4]. This research was devoted to finding of new apllications for lagochilin (1) and a series of its synthetic derivatives which were prepared by known procedures. Their structure were proved using advanced NMR technics. Lagochilin (1) and some its derivatives were screened for their in vitro antifungal and antibacterial activity against pure cultures of five fungi species (Aspergillus flavus, A. niger, Penicillium frequentans, P. chrysogenum, Alternaria alternata) and against both Gram-negative (Pseudomonas aeruginosa) and Gram-positive bacteria (Bacillus polymyxa) [5]. According to these, lagochilin (1), 3,18-O-isopropyl lagohirsin (2) and 15,16- anhydrolagochilin (3) exhibited good antimicrobial/antifungal activity at following MIC values (3.2·10-2/2 µg/mL), (1.6·10-2/2 µg/mL) and (2.3·10-2/3 µg/mL) in comparison with the reference compounds Caspafungin (16·10-2 µg/mL) and Kanamycin (2 µg/mL). It must be mentioned that antimicrobial and antifungal activities of lagochilin (1) and its derivatives were reported for the first time.

References:

1. Gafner G., Kruger G.J. Rivett D.E.A. X-ray crystallographic determination of the structure of a grindelane diterpenoid from Lasiocorys capensis. J. Chem. Soc. Chem. Commun., 7, 1974, 249-250. 2. Abramov M.M. Chemistry of lagochilin. Dokl. Akad. Nauk UzSSR, 3, 1958, 41-43. 3. Delectis Florae Reipublicae Popularis Sinicae Agendae Academiae Sinicae. Flora Reipublicae Popularis Sinicae. Beijing: Science Press, 65(2), 1977, 525-532. 4. Zainutdinov U.N., Islamov R., Dalimov D.N., Abdurakhmanov T.R., Matchanov O.D. Structure-activity relationship for hemostatic lagochilin diterpenoids. Chem. Nat. Comp., 38(2), 2002, 161-163. 5. National Committee on Clinical Laboratory Standards (NCCLS), “Antimicrobial Susceptibility Standards (ATS)”, ed. 2003, for M7 (CMI) and M100.

P22

NEW NICKEL(II) COORDINATION COMPOUND BAZED ON NICOTINOYL AND ISONICOTINOYL HYDRAZONES Maria Cocu, Cristina Balan, Ion Bulhac Institute of Chemistry of ASM, MD-2028, 3, Academiei str., Chisinau, Moldova e-mail: [email protected]

Nicotinic and isonicotinic hydrazides and its derivatives have been the subject of interest to researchers of different profiles. Many of these ligands and their complexes have shown a wide spectrum of biological activity, including antibacterial and antiviral activities. Some of them have already been used in medical practice. Derivatives of isonicotinic acid and it hydrazides are well known for their highly specific antituberculous activity. In order to obtain complex compounds of this class, a new coordination compound, [NiL1L2], has been obtained as a result of the interaction of 2-hydroxi-1-naphtaldehyde nicotinoylhydrazone (L1) with 1-phenyl-1,3-butanedione isonicotinoylhydrazone (L2) in the presence of nickel acetate (in molar ratio 1:1:1) in methanol medium. The complex is less soluble in chloroform, dimethylformamide, dimethylsulfoxide, ethanol, methanol and water. Elemental analysis and the IR spectrosocopic data confirm the coordination of L1 and L2 molecules to nickel atom. The IR spectrum of the obtained ligands and coordination compound allowed making some conclusions about the composition, structure and status of the ligands in the complex. The spectrum of uncoordinated ligand L1 is characterized by a wide band with medium intensity at 3218 cm-1, which includes ν(NH) and ν(OH) associated oscillations and high intensity band at 1675 cm-1, assignable to ν(C=O) group. The band with medium intensity at 1624 cm-1 can be attributed to the ν(-CH=N-)azomet oscillations. For planar deformation oscillations of the 1,3- substituted benzene ring are assigned bands at 1082, 1162 and 1062 cm-1, and for joined three hydrogen atoms oscillations from the outside of the plane - a band at 780 cm-1. The C-H deformation oscillations of the hydrogen atom of aromatic ring from the outside of the plane were found a band at 843 cm-1, in the case of the isolated hydrogen atom. The most intensive -1 absorption bands at 740 and 685 cm in the spectra of L1 are assigned to deformation oscillations of C-H bonds of the aromatic rings. Phenol group of 2-hydroxy-1-naphthaldehyde can be identified by absorption bands ν(C-O) and δ(OH) situated in the spectrum at 1322 and 1274 cm-1. The IR spectrum of the second ligand L2 is characterized by the presence of two narrow and high intensity bands at 3220 cm-1 (ν(NH)) and 1664 cm-1 (ν( C=O)). For mono-substituted benzene ring are present bands at 738 and 714 cm-1 and for the pyridine ring, which is -1 considered 1,4- disubstituted benzene ring - a band at 833 cm . The -CH3 group are identified by -1 -1 -1 the bands at 2927 cm (νas(CH3)) and 2837 cm (νs(CH3)) and 1431 and 1379 cm - δas and -1 δs(CH3), respectively. The bands at 1595, 1574 and 1483 cm are caused by the oscillations of the pyridine ring. In the IR spectrum of obtained complex [NiL1L2], with certainty, have not been identified absorption bands ν(NH) and ν(C=O), confirming the association and coordination of these group. This fact gives the allows us to conclude that ligands coordinate to the metal atom in the enolic form. Azomethine groups occur in the region 1617 cm-1. The presence of the pyridine ring is identified by the bands at 1602, 1584, 1480 and 772 cm-1. The monosubstituted benzene ring is confirmed by the presence of bands at 741, 730 and 681 cm-1. The most intensive absorption band of spectra at 1199 cm-1 could be caused by ν(CO) oscillations, incurred due enolization of coordinated ligands and participation of oxygen atoms and these groups to achievement of metal - ligand bonds.

P23

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF PRODUCTS OF SUBSTITUTION IN SOME AZIDE-CONTAINING Сo(III) DIOXIMATES

E. Coropceanu1, О. Bologa1, I. Аrsene1, I. Bulhac1, N. Gorincioi1, A. Vitiu2, P. Bourosh2

1Institute of Chemistry, ASM, Academiei 5, MD2028, Chisinau, R. Moldova 2Institute of Applied Physics, ASM, Academiei 5, MD2028, Chisinau, R. Moldova

Introduction of various organic molecules as additional ligands into metal complexes can substantially improve their properties, because the resulting complexes can be more effective. As result of interaction of structural block [Co(N3)(DmgH)2(Н2О)] with sulfanilamide derivative the - mononuclear molecular complex [Co(N3)(DmgH)2Sda] (1) was obtained, where DmgH = dimethylglyoximate monoanion, Sda = sulfanilamide derivative with substituted radical R (NH2– C6H4–SO2–NH–R)). In order to substitute SAM (sulfanilamide derivatives) from the complexes [Co(N3)(DmgH)2SAM] they were treated with a series ligands: pyridine (Py), nicotinamide (Nia), isonicotinamide (INia), thiouree (Thio), triphenylphosphine (PPh3), isonicotinic acid (HINia), 4- pyridinealdoxime (4-paoH), 4,4′-bipyridine (bpy) and NH4NCS. Eight mononuclear molecular complexes [Со(N3)(DmgH)2(Py)] (2), [Со(N3)(DmgH)2(PPh3)] (3), [Со(N3)(DmgH)2(Thio)] (4), [Со(N3)(DmgH)2(Nia)] (5), [Со(N3)(DmgH)2(INia)] (6), [Со(N3)(DmgH)2(HINia)]·H2O (7), [Со(N3)(DmgH)2(4-paoH)]·DMF (8), [Со(N3)(DmgH)2(bpy)] (9), and two binuclear [(Со(N3)(DmgH)2)2bpy]·0.5H2O (10), [(Со(N3)(DmgH)2)2bpy]·H2O (11) polymorphs were prepared and characterized by X-ray diffraction on single crystal (Fig. 1), elemental analysis and IR spectroscopy. Compound NH4[Co(SCN)2(DH)2]·3H2O (12) represent the single ionic - - complex, which was obtained as result of substitution of both, SAM and N3 units by SCN .

(a) (b)

Molecular geometries, electronic structure and the substitution reaction energies were calculated for all the considered compounds by the DFT B3LYP method with the 6-31G basis sets. Calculations proved that preparation of new complexes by substitutions of the ligands is an energetically favorable processes. Acknowledgement. Financial support was provided by the project 14.518.02.04 A.

P24

SYNTHESIS, STRUCTURE, AND ANTIOXIDANT ACTIVITY OF SOME BIOMETAL COORDINATION COMPOUNDS OF PENTANE-2,4-DIONE BIS-(4-(PYRID-2- YL)THIOSEMICARBAZONE)

A. Gulea, V. Tsapkov, A. Cotovaia, O. Garbuz, A. Anachii, V. Gudumac*

Thiosemicarbazones of different aromatic aldehydes and ketones contain a wide range of donor atoms and form with transitional metal ions coordination compounds with various composition, structure, and properties. Many of these coordination compounds are biologically active substances. They possess antimicrobial, antifungal, antitumor, antioxidative activities. Their biological activity depends on nature of the central atom, stereochemistry of the coordination compound, composition and structure of the ligand, nature and position of the substituents in the aromatic ring. [1-2]. In order to determine the influence of the substituents’ nature in the aromatic ring on the composition, structure, and properties of the coordination compounds, it was synthesized 4- (pyrid-2-yl)thiosemicarbazide. Its structure was confirmed by NMR spectroscopy (1H and 13C). The experiments showed that hydrates of copper, nickel, manganese, cobalt, chromium, and iron salts react with acetylacetone and 4-(pyrid-2-yl)thiosemicarbazide in 1:1:2 molar ratio forming coloured coordination compounds. The composition of these compounds was . 2+ 2+ - - - determined using elemental analysis: M(H2L)X2 nH2O, (M = Cu , Ni ; X = Cl , NO3 , Br - . 2+ 2+ 2+ 3+ 3+ 3+ ,ClO4 , n = 0,1); M(L) 2H2O, (M = Cu , Ni , Mn ); and M(L)(H2O)Cl (M=Co , Cr ,Fe ), where H2L – pentane-2,4-dione bis-(4-(pyrid-2-yl)thiosemicarbazone). The magnetochemical research showed that the synthesized coordination compounds have monomeric structure. Coordination compounds of nickel and cobalt are diamagnetic. Other synthesized coordination compounds are N N HN NH paramagnetic. Azomethine H2L in these coordination compounds behaves as neutral or doubly deprotonated tetradentate ligand that HN S S NH coordinates to the central atom by azomethinic nitrogen atoms and sulfur N N atoms forming two five-membered and one six-membered H L metallacycles. 2 The synthesized compounds possess antioxidative activity at the concentration 10-6 mol/L. It was found that the nature of the central atom and the anion influences on the antioxidative activity of the coordination compounds. For the homotypic - complexes antioxidative activity changes in the following way: Cu ≈ Ni > Co > Cr and NO3 > - - - Cl > Br > ClO4 . This work showed that the search of new antioxidants among biometal coordination compounds of ligands derived from pentane-2,4-dionebis-(4-(pyrid-2-yl)thiosemicarbazone) has prospects. This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F References: 1. Leovac V.M., Jovanovic L.S., Divjakovic V., et all // Polyhedron. 2007. V. 26. P. 49.

2. Chumakov Yu. M., Petrenko P. A., Codita T. B., Tsapkov V. I., Poirier D., Gulea A. P. // Crystallography Reports. 2014. Vol. 59. No 2. pp. 207-212.

P25

COORDINATION COMPOUNDS OF COBALT, NICKEL, AND COPPER OF SOME 1,3-DIPHENYLPYRAZOLE-4-CARBALDEHYDE THIOSEMICARBAZONES

A. Gulea, V. Tsapkov, A. Cotovaia, O. Garbuz, V. Graur, A. Nicolenco, Ia. Gutsu, V. Gudumac*

Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Republic of Moldova * Department of Microbiology, Virusology and Immunology Nicolae Testemitsanu, State University of Medicine and Pharmacy, Chisinau, Republic of Moldova e-mail: [email protected]

The number of resistant pathogenic microorganisms has increased as a result of widespread use of antibiotics in medical practice. Therefore, despite some progress in the synthesis and study of biologically active compounds, preparation and study of new unconventional medical compounds, that manifest biological activity, remain actual problems. These kind of substances include many organic substances that contain in their composition atoms of sulfur, nitrogen, and oxygen. All of them are able to form coordination compounds with transition metals. In many cases coordination results in augmentation of their biological activity. Therefore, the synthesis and study of new substances of this class are of scientific interest. The aim of this work is the synthesis, determination of the composition, structure, physicochemical properties, and biological activity of cobalt, nickel, and copper coordination compounds of 1,3-diphenylpyrazole-4-carbaldehyde thiosemicarbazone (HL1), 4-allylthiosemicarbazone (HL2), and 4-phenylthiosemicarbazone (HL3). Thiosemicarbazones HL1-3 were obtained by condensation of 1,3-diphenylpyrazole-4-carbaldehyde with corresponding thiosemicarbazide. Coordination compounds of mentioned above metals were synthesized by reaction between acetates and chlorides of these metals and thiosemicarbazones HL1-3 or using template reactions. The composition of these compounds was determined using elemental analysis: 1-2 1 Cu(НL )Cl2∙nH2O, Cu(L )(CH3COO)H2O, 3 1-3 Cu(L )Cl∙2H2O, Ni(L )2Cl2, III 1-3 N S Co (L )2Cl3∙nH2O. The structures of these coordination compounds were determined using HN magnetchemistry and IR spectroscopy. N NH R Synthesized substances manifest antioxidative N 1-3 activity against cation-radical ABTS (2,2-azinobis-3- HL etilbenzotiazolină-6-sulfonat). It was determined that coordination compounds of 4-phenylthiosemicarbazone HL3 and copper and nickel chlorides doesn’t show antioxidant activity against this R=H (HL1), -CH -CH=CH (HL2), radical. Coordination compound of copper acetate with 2 2 3 -C H (HL3). HL manifests the maximum activity. This compounds 6 5 deactivates half of these free ligands at the concentration 7 μМ which is four times better than the activity of Trolox that is used in medical practice as a standard antioxidant.

This work was fulfilled with the financial support of the Project 14.518.04.07A of the State Program.

P26

SUBSTITUENT EFFECT ON HYDROGEN BONDING NETWORK IN ETHANOLAMINE SALTS OF CHLORONITROAROMATIC COMPOUNDS Manuela Crisana, Paulina Bouroshb, Yurii Chumakovc, Liliana Halipa aInstitute of Chemistry Timisoara of Romanian Academy, 24 Mihai Viteazul Blvd., 300223 Timisoara, Romania; bInstitute of Applied Physics, Academy of Sciences of Moldova, Academiei Street 5, Chisinau, MD - 2028, Republic of Moldova; cGebze Institute of Technology, Cayirova, 41400 Kocaeli, Turkey

Chloronitroaromatic compounds are widely used as important building blocks for the chemical synthesis of pesticides, herbicides, dyes etc [1]. Recently, chloronitrobenzoic acids have been listed in a novel therapy for immunodeficiency diseases [2]. In this research we investigate structural aspects of ethanolamine salts of 2-chloro-4-nitrobenzoic acid (I) and 2-chloro-5- nitrobenzoic acid (II), focusing on hydrogen bonding interactions and investigates molecular packing in crystalline salts. Compounds have been prepared in diethylether solution and crystallized in monoclinic space group P21/c, a=8.402(2), b=6.664(1), c=22.023(4)Å, β=100.72(3), with Z=4 (I) and triclinic space group P-1, a=7.019(1), b=9.512(2), c=9.740(2)Å, α=79.19(3), β=88.58(3), γ=78.42(3), with Z=2 (II). Note that even if the compounds differ only by the position of the substituents, compound II crystallized as hydrate, which changes the system of hydrogen bonds. The salt units of all compounds serve as building blocks of the supramolecular architecture. In compound I, ethanolammonium cation forms three hydrogen bonds (two N-H…O and one O-H…O) with three 2-chloro-4-nitrobenzoate anions, while in compound II, ethanolammonium cation forms only two hydrogen bonds (one N-H…O and one O-H…O) with two 2-chloro-5-nitrobenzoate anions. In addition, the two components of compound II are linked between them by a water molecule, which acts as donor in two hydrogen bonds O(W)-H…O with benzoate anion, and acceptor in a hydrogen bond N-H…O(W) with ethanolammonium cation. In both compounds, the anions, cations and water molecules (only II) form hydrogen bonded chains, which further are consolidated into layers. The present work may give some insight to the design of new molecular materials of desired architectures.

I II

References 1. F.D. Zaragoza, Nitro Compounds: Lead Optimization for Medicinal Chemists, Weinheim: Wiley‐VCH, 2012, 59–61; T.A. Gasiewicz, Handbook of pesticide toxicology Vol. 3, San Diego: Academic Press, Inc., 1991, 1191-1270; G.R. Chatwal, Synthetic dyes, Himalaya publishing House, New Delhi, 1990. 2. S. Shakoor, T. Ahsan, K. Jabeen, M. Raza, R. Hasan, Int. J. Tuberc. Lung. Dis., 2010, 14(12), 1644–1646; C.M.S. Giampaglia, M.C. Martins, E. Chimara, et al. Int. J. Tuberc. Lung. Dis., 2007, 11, 803–807.

P27

PHARMACOPHORE MAPPING AND VIRTUAL SCREENING OF GSK3 INHIBITORS

Luminita Crisan, Liliana Pacureanu

Department of Computational Chemistry, Institute of Chemistry of Romanian Academy, Timisoara, Mihai Viteazul Avenue, 24, 300223 Timisoara, Romania [email protected]

The 3D structural features of maleimide derivatives crucial for binding, were identified by 3D pharmacophore models, whereas their structural correlation with biological activity was analyzed with the help of atom-based 3D QSAR models. The hypotheses generated [1,2] were aligned against the active compounds and subsequently the hypotheses was ranked based on survival score. Initially number of 355 five-points hypotheses were generated, but only 64.03% of hypotheses were externally validated by atom-based 3D QSAR. The statistical parameters of pharmacophore models including the correlation coefficient of regression R2 = 0.904, cross validated coefficient Q2 = 0.676, Pearson coefficient R = 0.837, stability S = 0.803 indicate a robust and reliable QSAR model, represented by pharmacophore pattern – ADRRH (A = hydrogen bond acceptors; D = hydrogen bond donor; R = ring and H = hydrophobic). This hypotesis was used to screen a datset of 237 compounds from which 66 are highly selective, 83 are moderately selective, and 88 are nonselective towards GSK-3. The early enrichment is lower when highly selective and moderately selective compounds were evaluated, but increases in the case of selective towards nonselective. The overal (Area Under Curve (AUC)) and early enrichment TP (true positives (TP)) in the case of highly selective against nonselective is the highest: (i) highly selective against moderately selective compounds AUC = 0.694; TP = 1.538 (2%); 1.538 (5%); 10.769 (10%); (ii) moderately selective against nonselective compounds AUC = 0.640; TP = 8.537 (2%); 14.634 (5%); 32.927 (10%) and (iii) highly selective against nonselective compounds AUC = 801; TP = 10.769 (2%); 56.923 (5%) and 66.154 (10%).

[1] Phase, version 3.8, Schrödinger, LLC, New York, NY, 2014 [2] Dixon, S. L.; Smondyrev, A. M.; Knoll, E. H.; Rao, S. N.; Shaw, D. E.; Friesner, R. A., PHASE: A New Engine for Pharmacophore Perception, 3D QSAR Model Development, and 3D Database Screening. 1. Methodology and Preliminary Results. J. Comput. Aided Mol. Des., 2006, 20, pp. 647-671.

Acknowledgments: The authors thank Dr. Ramona Curpăn and Dr. Liliana Halip, Institute of Chemistry Timişoara of Roumanian Academy, for providing access to Schrödinger software acquired through the PN-II-RU PD_500/119/2010 and PN-II-RU PD_502/174/2010 projects funded by UEFISCDI-CNCSIS Romania. This work was supported by Project 1.2 of the Institute of Chemistry Timisoara of the Roumanian Academy.

P28

DESIGN AND STRUCTURAL CHARACTERIZATION OF POLYMERIC Mn(II), Zn(II) AND Cd(II) DICARBOXYLATES ORNAMENTED BY OXIME LIGANDS

Lilia Croitor,a* Eduard B. Coropceanu,b Marina S. Fonaria

a Institute of Applied Physics Academy of Sciences of Moldova, Chisinau, Moldova, b Institute of Chemistry Academy of Sciences of Moldova, Chisinau, Moldova. *E-mail: [email protected]

Polycarboxylate ligands are a family of organic building blocks that play an important role in coordination chemistry, and have been justified as efficient and versatile candidates for the design and synthesis of a variety of metal coordination polymers (CPs). Aromatic dicarboxylates remain the most common linking agents in this class of materials due to their structural rigidity and ability to produce porous networks for adsorptive or catalytic applications. CPs constructed from aliphatic dicarboxylate ligands, versus those built from aromatic dicarboxylate ligands, have been less studied. For searching new coordination networks herein we have combined the Mn(II)/Zn(II)/Cd(II) metal centers with two types of ligands: dicarboxylic acids including fumaric acid (H2fum), 1,3-benzenedicarboxylic acid (H2ipa), and 1,4- benzenedicarboxylic acids (H2bdc), and two oxime ligands, including pyridine-2-aldoxime (2- pyao) and pyridine-4-aldoxime (4-pyao). Nine Mn(II), Zn(II) and Cd(II) coordination polymers have been prepared, and their crystal structures have been determined by single crystal X-ray diffraction. Compounds 1-4, 6 and 7 represent the 1D coordination polymers, while compounds 5, 8 and 9 represent the laminar 2D structures (Scheme).

This “blend approach” demonstrates similarities and dissimilarities in CPs dictated by the distinctions in the metals’ and oxime ligands’ coordination capacities and preferences, and length and flexibility of the dicarboxylic linkers. In all studies dicarboxylate residues act as multidentate linkers, while the oxime ligands act as terminal ligands and restrict the further structure extensions. The samples 5-9 demonstrate an efficient water and N,N- dimethylformamide (dmf) uptake explained by the availability of the hydrophilic and hydrophobic regions in these solids.

1. Croitor, L.; Coropceanu, E.B.; Siminel, A.V.; Masunov, A.E.; Fonari, M. S. Polyhedron 2013, 60, 140.

Acknowledgments. The authors acknowledge the financial support from the State Program of R. Moldova (Project 14.518.02.04A) and Grant for Young Scientists (14.819.02.21A).

P29

SYNTHESIS OF NEW FLUORESCENT INDOLIZINE DERIVATIVES BEARING 1,2,3- TRIAZOLES WITH POTENTIAL SENSOR APPLICATIONS

Lacramioara Popovici, Ramona Danac, Ionel I. Mangalagiu

“Al. I. Cuza” University of Iasi, Faculty of Chemistry, Bd. Carol 11, 700506 Iasi, Romania. Tel: +40+232 201343; fax: +40+232 201313; e-mail: [email protected]

To the memory of Academician Constantin Turta, a great man and friend.

Indolizine derivatives have been found to possess a variety of biological activities such as anti- inflammatory, antiviral, analgesic and antitumor activities [1]. In addition, indolizine derivatives have been found to have long wavelength absorption and strong fluorescence in the visible region [2, 3]. On the other hand, 1,2,3-triazoles are able to perform a variety of important roles in sensing. Thus, they contribute to the binding of target analyte or they can act as part of a conjugated fluorophore [4]. Considering these important properties and the steadily increasing importance of fluorophores in biolabeling and environmental trace analysis, we synthesized new fluorescent indolizine derivatives with 1,2,3-triazoles as substituents. A fluorescence study of the new compounds is underway.

[1] W. Flitsch, Comprehensive Heterocyclic Chemistry; Pergamon: Oxford, 1984, Vol. 4, p 443. [2] Rotaru, A. V.; Druta, L. D.; Oeser, T.; Mueller, T. J. J. Helv. Chim. Acta, 2005, 88, 1798. [3] A. Rotaru, I. Druta, E. Avram, R. Danac, Arkivoc, 2009, 13, 287-299. [4] Y.H. Lau, P.J. Rutledge, M. Watkinson, M.H. Todd, Chem. Soc. Rev., 2011, 40, 2848-2866.

P30

AN UNPRECEDENTED MIXED-VALENCE HETEROMETALLIC NONANUCLEAR III IV III [Mn 6Mn Dy 2] CLUSTER

Mariana Darii, Lilia Croitor, Victor Ch. Kravtsov, Svetlana G. Baca

Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Moldova; [email protected]

Polynuclear carboxylate clusters of Mn(II/III/IV) are versatile building blocks, which may be used to construct a diverse range of molecular magnetic arrays and offer numerous advantages. Incorporating lanthanide ions that play a special role in the field of single-molecule magnetism in such molecular clusters provides good starting ingredients for the syntheses of 3d/4f single-molecule magnets. The reaction of manganese(II) pivalate with Dy(NO3)3·6H2O and H2dea (diethanolamine) in MeOH mixture leads to a new heterometallic nonanuclear cluster [Mn7Dy2(μ4-O)2(μ3-O)4(μ3- OMe)2(μ2-OH)(dea)2(piv)8(MeOH)2(H2O)2](NO3)·H2O (1), where Hpiv = pivalic acid. Single- crystal X-ray diffraction shows that compound 1 crystallizes in the monoclinic C2/c space group: a=19.8633(7), b = 15.4538(11), c = 28.9794(9) Å, β = 102.661(3)°, V = 8679.3(7) Å3, Z = 4. The 28+ cluster possesses C2 molecular symmetry and comprises a [Mn7Dy2] core, held together by two μ4-O, four μ3-O, one hydroxo group, six bridging pivalate moieties, two doubly 2 deprotonated dea ligands and two μ3-OMe anions. The metallic core is further surrounded by two chelated carboxylate groups and two water molecules both of them coordinated to each of the DyIII atoms, while one of the manganese atoms is additionally ligated by a methanol molecule. This finally results in all seven Mn atoms being six-coordinated with an octahedral geometry and Dy atoms are eight-coordinated having a distorted square antiprismatic geometry. Charge consideration of the cluster 1 and BVS (bond valent scheme) calculations indicate that one of the seven Mn centers is in the 4+ oxidation state, whereas the remaining six are in the 3+ oxidation state. The MnIVO and MnIIIO bond distances are in the ranges 1.885(6)–1.898(5) Å and 1.865(5)– 2.297(6) Å, while MnIIIN distances are 2.052(8) Å. The DyIIIO bond distances are in the ranges 2.330(6)–2.421(6) Å. Inspection of the central core III III reveals two distorted {Mn 3Dy O4} hetero cubane moieties sharing a common MnIV vertex as shown in Figure. Each cuban is further decorated with III Mn atom bridged by μ4-O, amino alcohol and carboxylate ligands.

Acknowledgement. The authors thank the SCOPES IZ73Z0_152404/1 project for support.

P31

APPLICATION OF MgO NANOPARTICLES CATALYZER IN EFFICIENT SYNTHESIS OF BENZYLAMINO COUMARINE

Alimohammad Dehghan and Ali Reza Ilkhani

Department of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran.

An efficient one-pot synthesis of benzylamino coumarin derivatives via a three-component condensation of 4-hydroxycoumarin, cyclic secondary amine, and aromatic aldehyde in the presence of magnesium oxide nanoparticles as a heterogeneous catalyst in water as a green solvent at room temperature.

1 2 3 O O O O O N + Ar H + N H OH Ar OH

Scheme1: Three-component reaction between of 4-hydroxycoumarin 1, secondary amine 2 and aromatic aldehyde 3 in aqueous media.

P32

DETERMINATION OF 8-ISO-PROSTAGLANDIN F2α IN HUMAN PLASMA BY GAS CHROMATOGRAPHY-TRIPLE QUDRUPOLE MASS SPECTROMETRY Mariana Deleanu1,2, Gabriela M. Sanda1, Anca V. Sima1

1 Institute for Cellular Biology and Pathology "Nicolae Simionescu" of the Romanian Academy, 8, B.P. Hasdeu Str, Bucharest RO 050568, Romania 2 University of Agronomical Sciences and Veterinary Medicine, Faculty of Biotechnology, 59 Marasti blvd, Bucharest RO-011464, Romania

F2 Isoprostanes, derived from the non-enzymatic peroxidation of arachidonic acid, are considered to be reliable biomarkers of oxidative stress in the human body [1]. In this study, we aimed to develop a sensitive and selective method for the determination of total 8-Iso- Prostaglandin F2α (8-iso-F2α) in human plasma. The plasma samples were hydrolyzed and the total lipids were extracted in ethyl acetate. The lipid extracts were purified to NH2-cartridges and then F2 isoprostanes were eluted with ethyl acetate/methanol/acetic acid (10/85/5, V/V/V) [2] and then derivatizated with N,O bis(trimethylsilyl)trifluoracetamide [3]. GC-MS/MS analysis was performed on Agilent Technologies 7000A Triple Quad and 8-iso-F2α-d4 was used as internal standard (IS). Chromatographic separation was performed using HP-5 ms 30 m × 0.25 mm x 0.25 μm film film thickness column and detection was performed on a triple quadrupole tandem mass spectrometry using electron impact ionization in positive mode and multiple reaction monitoring (MRM). The monitored MS/MS ion transitions were m/z 481→391.2 and m/z 485.4→395.2 for 8-iso-PGF2α and IS, respectively. A good linearity was observed in the concentration range 50-2000 pg/ml. The lower limit of detection (LLOD) was 15 pg/ml and the lower limit of quantification (LLOQ) was 25 pg/ml. The validated method was applied to quatification of F2 isoprostanes in human plasma from coronary artery disease (CAD) patients from the Cardiology Department, Elias Emergency Hospital Bucharest, in 4 groups with stable angina (SA), unstable angina (UA), a month after myocardial infarction (MMI) and subjects at risk for CAD without cardiac events (HR).In conclusion, we developed a sensitive, selective and reproducible method for 8-iso-F2α determination in plasma. Results showed that the levels of 8-iso-PGF2α from UA and MMI pacients plasma were not significantly increased compared to HR and SA plasma patients.

Acknowledgements. This work was supported by the project PN-II-PT-PCCA-2011-3.1-0184 and by the Romanian Academy.

References

1. Jason D. Morrow “Quantification of Isoprostanes as Indices of Oxidant Stress and the Risk of Atherosclerosis in Humans” Arterioscler. Thromb. Vasc. Biol. 2005, 25, 279-286 2. J. Nourooz-Zadeh “An Improved Procedure for the Enrichment of Plasma F2-Isoprostanes Prior to Final Determination by GC-MS/NICI” Transactions C: Chemistry and Chemical Engineering 2009, 16(2), 140-144 3. Janine Bessard, Jean-Luc Cracowski, Francoise Stanke-Labesque, Germain Bessard “Determination of isoprostaglandin F2α type III in human urine by gas chromatography–electronic impact mass spectrometry. Comparison with enzyme immunoassay” J. Chromatogr. B, 2001, 754, 333–343

P33

THE STUDY OF N1,N4- BIS(SALICYLIDENE)-S- METHYLIZOTHIOSEMICARBAZIDIUM CHLORIDE METHANOL MONOSOLVATE AS IONOPHORE FOR PVC-MEMBRANE ELECTRODES

Mariana Diru, Mihail Secu, Parascovia Morari

Moldova State University

Many analytical techniques for determination of Mn2+ are costly and required pre-sample treatment of analyte and even required very skilled person as supervisor to handle the instrument. Beside this the technique, ion-selective electrode is simple, easy to handle and very cheap to design. The present research describe the use of N1,N4-bis(salicylidene)-S- methylisothiosemicarbazidium chloride methanol monosolvate (H2L∙HCl∙CH3OH) (figure) as ionophore in PVC-based sensor for the determination of Mn2+. The synthesis of the ligand has been realized by demetallation of the NiL2 described in [1]. The structure of the H2L∙HCl∙CH3OH was determinate by single crystal X-ray diffraction.

Figure: The structure of N1,N4-bis(salicylidene)-S-methylisothiosemicarbazidium chloride methanol monosolvate

A polymeric membrane based on H2L∙HCl∙CH3OH has been prepared. Using this membrane has been confectioned electrochemical sensor for Mn2+. The parameters of the electrode have been established during their calibration in different manganese(II) concentration solutions. Ion-selective electrode exhibited a linear Nernstian response over the range 1*10-4-1*10-1 M with slope of 26 - 27 mV per decade. It shows a fast response time (20 - 60 s). The potentiometric selectivity coefficients were determined by separate interferent method. Their values show that sensor is substantially selective for Mn2+ ions over the all interfering ions studied. It was studied the influence of the anion nature of the response of sensor. Best results were recorded when calibration solutions were prepared using manganese(II) sulfate.

[1] M. D. Revenko, N. V. Gerbeleu, K. M., Indrichan, Teoreticheskaya i Eksperimental'naya Khimiya, 21, 1985, 604.

P34

CdSe COLLOIDAL QUANTUM DOTS IN THE POLYMER MATRIX OF POLY-(2- VINYLPYRIDINE): SYNTHESIS, NMR AND OPTICAL PROPERTIES

Ion Geru, Alexandr Dorif, Alic Barba

Institute of Chemistry of the Academy of Sciences of Moldova, Academiei 3 str., MD 2028, Chisinau, Moldova E-mail: [email protected] It is known that CdSe quantum dots form nanocomposites with some polymers. Particularly, CdSe colloidal quantum dots (QDs) are included in nanocomposites based on poly[2-methoxy-5-2(2’-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) [1], polymethyl methacrylate with polystyrene (SMMA) [2], poly[4-(n-aryloyloxyalkyloxy) benzoic acids] [3] and polystyrene with poly butyl methacrylate [4]. From the others advantages of quantum dots incorporation in polymer matrix is rise of photoluminescence quantum yield in comparison with non-incorporated QDs. It was found that QD introduction into polymer microparticles by impregnation in a supercritical carbon dioxide medium efficiently stabilizes them in space and significantly increases photochemical stability of their luminescence characteristics [2]. In this work a new method for preparation of polymer nanocomposite with colloidal CdSe QDs is proposed. UV-Vis and NIR absorption, photoluminescence and NMR spectra of this nanocomposite were investigated. Unlike in other known methods for polymer nanocomposite with colloidal QDs preparation, process was conducted not in the melted polymer, but in polymer solution in nonpolar hydrocarbon solvent. Conducing synthesis in solution of polymer instead of melted polymer prevents the carbonization and decomposition of polymer. As solvents were used toluene, xylenes (mix of isomers) and dodecane. CdSe QDs in poly(2-vinylpyridine) matrix with diameter about 2 nm were obtained. These QDs show very good photoluminescence. To establish if cadmium on the surface of obtained colloidal CdSe QDs form donor- acceptor bonds with pyridinic nitrogen in poly(2-vinylpyridine) matrix, NMR and NIR spectra were analysed.

[1] McCumiskey E. J., Chandrasekhar N., Taylor C. R., Nanotechnology 21(22), 1-7 (2010); doi:10.1088/0957-4484/21/22/225703. [2] Bagratashvili V. N., Vakshtein M. S., Zavorotnyi Yu. S. at al., Inorganic Materials: Applied Research 1(4), 297–302 (2010); doi: 10.1134/S2075113310040064. [3] Tselikov G. I., Timoshenko V. Yu., Leonid A. Golovan et al., ChemPhysChem, 16(5), 1071– 1078 ( 2015); doi: 10.1002/cphc.201402913. [4] Iovu M., Enachescu M., Culeac I., et al., Chemistry J. of Moldova 9(2), 74-79 (2014).

P35

GC-MS ANALYSIS OF THE FATTY ACID METHYL ESTER IN JAPANESE QUAIL FAT

Ion Dragalina*, Olga Morarescua, Maria Sedcencob, Radu Marin Roscab

a Institute of Chemistry of A.S. M., 3, Academiei str. Chisinau MD 2028, Republic of Moldova, b Î.I. ”Antoni Cristina”, 2A Stefan cel Mare str.,Gratiesti, MD 2093 Republic of Moldova *e-mail: [email protected], phone: (+373 22) 73 97 69

Fat from FARAON quail breeds [1] accumulated as production waste has been investigated for the first time in order to assess it by applying GC-MS technique [2], preventively converted it by methanolysis to fatty acid methyl esters [3]. The test results regarding the content of unsaturated fatty acids having a Z-configuration favorable to human body (77.8%), confirm their nutritional value [4] and the possibility of using this fat in cosmetic, soap, pharmaceutical, or food industries. GC-MS analysis of the methyl esters derived from quail fat has demonstrated the presence of 35 organic components in the reaction product ; the following have been identified by comparison to the mass spectra from the device database, which constitutes 98.97% of total mass (Table 1).

Table 1. The results of GC-MS analysis of the methyl esters of fatty acids (% from total mass). Rt,min Components % 1 15.045 Methyl myristoleate 0,10 2 15.124 Methyl tetradecanoate 0.42 3 15.845 Pentadecanoic acid, methyl ester 0.05 4 16.339 Methyl 7,10-hexadecadienoate 0.15 5 16.419 9-Hexadecenoic acid(Z), methyl ester 5.82 6 16.559 n-Hexadecacoic acid methyl ester 16.85 7 16.779 n-Hexadecanoic acid 0.46 8 17.686 9,12-Octadecadienoic acid(Z,Z) metyl ester 33.05 9 17.727 9- Octadecenoic acid(Z), methyl ester 36.78 10 17.828 Octadecanoic acid, methyl ester 3.00 11 17.923 Cis-13- Octadecenoic acid 1.92 12 18.859 Cis-11- Eicosenoic acid methyl ester 0.23 13 18.652 Arahidonic acid 0.14

Conditions:The analysis of the obtained fatty acid methyl esters was performed by using the GC-MS system Agilent Technologies 7890A with 5975C Mass-Selective Detector(GC-MSD) equipped with split-splitless injector (split, 250ºC, split ratio 1:50, 1 ) and HP-5ms capillary calibrated column (30mX0.5mmX0.25 ); Carrier: Helium 1,1 ml/min; Oven: 60oC-5min, 15oC/min-300oC- 10min;MSD in scan 30-300, 15min, 30-550 amu.

1. A.G.Gencev, S.S. Ribarski, G.D.Afanasjev, G.I. Blohin, Journal Central Euroean of Agriculture, 2005, V.6, Nr.4, pp. 495-500. 2. T.Seppanen-Laakso, I. Laakso,R. Hiltunen, Analytica Chemica Acta, 2002, 465, pp. 39-62. 3. T.,Lupaşcu, I.Dragalin, P.Vlad, S.Şerban, E.Stepan, Brevet de inventie MD 2382, 29.02.2004, BOPI, 2004, Nr.2, pp. 42-43. 4. R.A. El-Dengawy, A.M. Nassar, Nahrung/Food, 2001, V.45, Nr.1, pp. 50-54.

P36

(THIO)CARBOHYDRAZONES AS VERSATILE LIGANDS FOR THE SYNTHESIS OF POLYNUCLEAR COORDINATION COMPOUNDS

Diana Dragancea

Institute of Chemistry of the Academy of Sciences of Moldova, Academiei str. 3, MD-2028, Chisinau, Republic of Moldova, e-mail:[email protected]

The synthesis of polynuclear transition metal complexes continues to attract the attention of researchers. The nuclearity of clusters is difficult to control, and synthesis of such systems requires an ingenious approach to the design of the ligands used. Ligands with hydrazone groups connected by dicarboxylic acid central fragments (oxalic, malonic or phthalic) are well- documented in the literature. This work illustrates the conformational and configurational flexibility, and interesting donor properties of polydentate ligand systems, (thio)carbohydrazone of salicylaldehyde and its derivatives. In the field of hydrazone chemistry, the study of bis(thio)carbohydrazone complexes is of interest for several reasons: (1) by the presence of two hydrazone coordinating units in ditopic ligands, which may yield supramolecular architectures or coordination polymers, (2) the coordination of a metal ion by one unit may induce changes in the coordinative properties of the other unit, and (3) binuclear complexes of these ligands are suitable for weak spin–spin exchange interaction studies. The coordination versatility of this kind of polydentate ligand system arises from the tautomeric equilibrium between (thio)keto and (thio)enol forms. The enol and thioenol tautomers can also exist as syn or anti isomers as a consequence of the double bond character of the central N-C linkage. The anti configuration provides two contiguous tridentate pockets, each of which can accommodate one ion. The leading structural pattern is an azine-bridged dinuclear unit. Formation of various type of copper(II), vanadium(V), vanadium(IV, V) and nickel(II) complexes, e.g. metallic cyclic arrays, 1D chain and mixed-valence complexes along with their properties will be presented [1,2]. The acid-base properties of discussed two groups of ligands (oxygen or sulfur-based) differ markedly leading to triply or fully deprotonated chelators, respectively. The counterion of the starting salts and the solvent mixture used for the synthesis of complexes have a significant impact on both their composition and packing. The coordination chemistry of (thio)carbohydrazone is basically established, but there are still exciting synthetic challenges (such as construction of multinuclear systems with 4f metals or heteronuclear clusters) that remain to be explored.

References

1. D. Dragancea, V.B. Arion, S. Shova, E. Rentschler, N.V. Gerbeleu. Angew. Chem. Int. Ed., 44, 2005, 7938-7942. 2. D. Dragancea, S. Shova, Éva A. Enyedy, M. Breza, P. Rapta, L. Carrella, E. Rentschler, A. Dobrov, V. B. Arion. Polyhedron, 80, 2014, 180-192. 3. D. Dragancea, A.W. Addison, A.D. Hunter, M. Zeller, L. Carella, E. Rentschler. The XVII-th International conference “Physical Methods in Coordination and Supramolecular Chemistry, 24-26 October, 2012, Chisinau, p. 104.

P37

SYNTHESIS, STRUCTURE AND MAGNETIC PROPERTIES OF NEW BINUCLEAR COPPER(II) COMPLEXES WITH THIOSEMICARBAZONE LIGANDS

E. Stratulat1, S. Sova1,2, R. Clerac3,4, O. Palamarciuc1*

In memoriam to Prof. Mihail Revenco

Thiosemicarbazones are now well established as an important class of sulfur donor ligands particularly for transition metal ions. The coordination compounds of copper(II) metal ions are most related as mono or dinuclear systems [1-2]. Copper(II) coordination compounds with thiosemicarbazone ligands continues to attract the attention of researchers due to their structural, biological, magnetic and catalytic properties. The investigated tiosemicarbazone ligands were prepared by refluxing imidazole- carbaldehyde with tiosemicarbazide for 2-3 hours and reaction mixtures were kept overnight. The formed solid products were isolated by filtration, washed several times with cold alchohol and dried in air. The complexes with the formula [Cu(HL)X]X, X = CHCl2COO- and HL - imidazol thiosemicarbazone derivatives were synthesised and structurally characterised (Figure 1a).

(a) (b) Fig. 1. Cristal structure (a) and magnetic properties (b) of [Cu(HL)CHCl2COO]CHCl2COO}2

The crystal structure investigation show that the copper(II) complexes is formed. Copper(II) ions is coordinated via NNS donor atoms at the thiosemicarbazone fragment and O from carbaxylate ligand. The mononuclear unit is assembled in dimer via O from carboxylate ligand. The complexes have pyramidal geometry. To compensate the charge of compound one carboxylate ion is placed in the extern shape of the complex and forme two O...H bonds with NH grups from the coordinated thiosemicarbazone ligand. The magnetic investigation show that at rom temperature the value of χT product is 0.75 cm3K/mol according to two ions with spin 1/2. At low tempreture the χT product increase, confirming a feromagnetic coupling between two Cu(II) ions.

References: 1. Sain, S.; Saha, R.; Mostafa, G.; Fleck, M.; Bandyopadhyay, D. Polyhedron 2012, 31, 82. 2. Blomenkemper, M.; Schroder, H.; Pape, T.; Hahn, F. E. Inorg. Chim. Acta 2012, 390, 143.

P38

SUPRAMOLECULAR ORGANIZATION OF MONONUCLEAR Cu(II), Co(II) AND Ni(II) PHTHALATE CLUSTERS I.G. Filippova, S.G. Baca

Institute of Applied Physics, ASM, Academiei str. 5, MD2028, Moldova

o-Phthalic acid (H2pht) is successfully used for creating an extensive range of coordination compounds with different dimensionalities: monomers, clusters, and coordination polymers. The phthalate ligand can adopt 54 coordination modes with metal atom in complexes [1]. Monodentate coordination mode of phthalate residue leads to formation of mononuclear complexes. The presence of an uncoordinated COOH group in the complexes, coordinated and uncoordinated water molecules as well as hydrogen-bond donors in aromatic amines creates conditions to form various kinds of supramolecular networks. The combinations of the phthalate ligand and N-donor aromatic amines result in organization of a series of mononuclear complexes with the common formula [M(pht)(amine)(H2O)3] · n(H2O), where M = Co(II), Ni(II); amine = (py)2, (2-MeIm)2, (-Pic), bpy, and phen; n = 0, 1, 3 [2]. In these compounds the discrete complex molecules are found to be of a very similar shape. The phthalate ligand occupies only one place in the metal octahedron, and the coordination sphere is completed by N-atoms of aromatic amines and oxygen atoms of water molecules. Discrete complexes in all these compounds are connected by hydrogen bonds in double-chains. Depending on the nature of aromatic amines, the arrangement of these chains differs between crystals. Another example of a mononuclear complex is [Ni(Hpht)2(H2O)4]·2(H2O), where the  Ni(II) ion is coordinated by two oxygens of monodentate Hpht and four oxygen atoms of H2O forming a fairly regular octahedron [3]. The coordination octahedra are linked by intermolecular … H2O Ocarb hydrogen bonds organizing a layer structure. Here we report new mononuclear complexes [M(pht)2(H2O)4](H2pip)∙8(H2O), where M = Cu(II), Co(II) or Ni(II), pip = piperazine). These structures are assembled from the same moieties 2 ([M(pht)2(H2O)4] anion, the protonated piperazine molecule and 8 solvate water molecules, crystallize in the same space group P-1 but have different unit cell parameters. Three crystallographically non- equivalent Co atoms and Ni atom in corresponding compounds have a slightly distorted octahedral coordination alike in [3] with average distances of 2 2.09 Å for CoO and 2.06 Å for NiO. In complex anion [Cu(pht)2(H2O)4] six oxygen atoms situate in the vertex of squared bipyramid. The mean CuO in base plane is in the region of 1.97 Å and the corresponding distances are 2.41 Å in apical positions. The presence of numerous hydrogen atom results in extensive and similar intramolecular and intermolecular hydrogen bonding in these compounds. Coordinated water molecules form strong hydrogen bonds with the oxygen atoms of the carboxylate group of adjacent complexes to generate the chain. The chains are packed via N-H…O and O-H…O in a 3D network as shown on Figure. It is necessary to note that solvate water molecules organize water clusters with alternation of 4- and 6-membered rings. Acknowledgement. Financial support was provided by the project SCOPES IZ73Z0_152404/1. [1]. S.G. Baca, S. Decurtins, Phthalate-Based Coordination Polymers, in Phthalates: Chemical Properties, Impacts on Health and the Environment, 2012, Nova Publishers, USA, 1-59. [2]. I.G. Filippova, et al. Polyhedron, 29, 2010, P. 1102-1108. [3]. G. Adiwidjaja, H. Kuppers, Acta Crystallogr., Sect. B32, 1976, P.1571-1574.

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TWO ONE-DIMENSIONAL {Cu(II)(PYRIDINE-4-ALDOXIME)(MALONATES)}: IMPACT OF PYRIDINE-4-ALDOXIME LIGAND IN THE ACENTRIC STRUCTURE

Lilia Croitor, Eduard B. Coropceanu,a Alessandra Forni,b Stefania Righetto,c Elena Cariati,b,c Marina S. Fonari

Institute of Applied Physics ASM, Academy str 5, MD2028, Chisinau, Moldova; aInstitute of Chemistry ASM, Academy str 3, MD2028, Chisinau, Moldova; bISTM-CNR, Institute of Molecular Sciences and Technologies of CNR and INSTM UdR, Milano, Italy, and cDepartment of Chemistry, Università degli Studi di Milano, Milan, Italy

Nowadays in spite of tremendous success in the synthesis of acentric networks, the reported so far metal−organic framework (MOF) materials constructed from the achiral ligands with SHG efficiency are still rare, since the factors responsible for construction of efficient noncentrosymmetric MOFs are not completely understood and remain the subject of active study in the crystal engineering field [1]. We have recently reported Zn/Cd acentric coordination polymers (CPs) whose asymmetry was intuitively attributed to the synergetic effect of the tetrahedral sulfate anion and conformationally non-rigid oxime ligands coordinated to the metal centers [2]. These solids demonstrated modest SHG response [3]. Our supposition of the crucial impact of the pyridine-4-aldoxime ligand (pya) in the acentricity of the final CPs is based on its donor (N=OH) −acceptor (Py) structure whose polarization, intensified by metal−ligand coordination, can be responsible for the enhancement of the SHG response. The two one- dimensional Cu(II) CPs here reported justify in favor of this supposition. One-pot co- crystallization of CuF2 with pyridine-4-aldoxime (pya) and malonic acid (malH2) in dmf solution . + yielded two crystalline forms, plates of the solvent-free [Cu(mal)]n n(pyaH) (1) with the pyaH cations accommodated in the crystal lattice, and needles of the dmf solvate . [Cu(mal)(pya)2]n n(dmf) (2) with two neutral pya molecules coordinated to the metal center. Compound 1 crystallizes in the centrosymmetric triclinic P-1 space group. The structure contains anionic malonate-bridged copper(II) chains isolated by pyaH+ cations. The copper atoms reside on inversion centers in the symmetrical O6 octahedral coordination environment arisen from the two bidentate and two monodentate-bridging malonate residues. Compound 2 crystallizes in the noncentrosymmetric orthorhombic Pna21 space group in the form of neutral chains (Fig.). The Cu(II) ions adjust the distorted N2O3 square-pyramidal environment with two pya molecules occupying the neighboring vertexes in the Cu(II) basal plane. The uniformly oriented polar chains are separated by the rows of dmf molecules. Preliminary modified-Kurtz powder SHG measurements exhibited modest SHG efficiency for this solid.

Acknowledgement. The authors thank the bilateral Moldo-Italian project, 15.820.16.02.01/It for support

[1] C. Wang, T. Zhang, W. Lin, Chem. Rev. 2012, 112, 1084. [2] (a) L. Croitor, E.B. Coropceanu, A.V. Siminel, V.Ch. Kravtsov, M.S. Fonari, Cryst. Growth Des., 2011, 11, 3536; (b) L. Croitor, E. B. Coropceanu, A.V. Siminel, A.E. Masunov, M.S. Fonari, Polyhedron, 2013, 60, 140; (c) L. Croitor, E.B. Coropceanu, A.E. Masunov, H.J. Rivera-Jacquez, A.V. Siminel, M.S. Fonari, J. Phys. Chem. C., 2014, 118, 9217. [3] A. Forni, S. Righetto, E. Cariati et al., unpublished results

P40

CONVENIENT SYNTHESIS OF METHYL (8S,9R,13S,14R)-4,4,8,9,13- PENTAMETHYL-20(109)-ABEO-ENT-ISOCOPALA-5(10),11(12)-DIEN-15β-OATE

Marina Grinco, Vladilena Gîrbu, Alic Barba, Elena Gorincioi, Nicon Ungur

Institute of Chemistry, Academy of Sciences of Moldova, Chisinău, Moldova e-mail: [email protected]

Methyl (8S,9R,13S,14R)-4,4,8,9,13-pentamethyl-20(109)-abeo-ent-isocopala- 5(10),11(12)-dien-15β-oate 1, an analog of natural highly ichthyotoxic1,2 verrucosins -A and -B, has been successfully synthesized, starting from the methyl ent-isocopalate 2, according to the Scheme 1. HO 12 H 11 16 17 13 1 1. mCPBA, DCM, 98% pTsOH, CHCl3 9 CO Me CO Me H H 2 2 CO2Me H H , 4 h, 62% 20 H 15 2. Al(OiPr)3, 52% 3 4 5 7 H H 2 3 18 19 1 Scheme 1 The stereochemical structure of compound 1 has been established by NMR spectroscopic data. Assignments of 1H and 13C signals in spectra are made on the basis of 1D: (1H, 13C, DEPT- 135o) and 2D: homo- (1H/1H COSY-45o, NOE) and heteronuclear (1H/13C HSQC and HMBC) experiments. The presence of two double bonds in the skeleton is ascertained by long-range C-H correlation experiments (HMBC). The assignment of the configuration of diterpenoid 1 was proposed on the basis of its NOE-spectra. NOE interactions between H-1eq/H3-9 and H3-9/H-7ax support the suggested (9R)-configuration of compound 1, while NOEs between H-1ax/H-6ax and H-6ax/H-14 are indicative for the (R) relative stereochemistry at C-14. 13S-Configuration of final methyl ether has been determined by the absence of NOEs between H3-16/H3-17 that has been additionally corroborated by weak NOEs between H-13/H3- 15 and H3-15/H3-8 in the corresponding spectra. Since no evidence was found in the literature, concerning the preparation of verrucosine - A and –B derivatives with the rearranged isocopalane diterpene skeleton, the present report paves the way for such type of potentially endowed with promising biological properties compounds.

Reference [1] Cimino, G.; Gavagnin, M.; Sodano, G.; Puliti, R.; Mattia, C. A.; Mazzarella, L. Tetrahedron, 1988, 44 (8), 2301-2310. [2] Zubia, E.; Gavagnin, M.; Crispino, A.; Martinez, E.; Ortea, J.; Cimino, G. Experientia, 1993, 49 (3), 268-271.

P41

FUNCTIONALIZED POLYMER ANTIOXIDANT USED IN THE DRUG NITROSATION

Şavga Cristina1, Duca Gheorghe2, Gonţa Maria1

1Moldova State University, 60, Alexei Mateevici str., Chisinau, MD-2009, Republic of Moldova, 2Academy of Sciences of Moldova, 1, Stefan cel Mare blvd., Chisinau, MD-2001, Republic of Moldova

Nitrosocomposites (NNC) are a major class of chemicals carcinogenic, mutagenic, teratogenic, and immunotoxic agents, posing a serious threat to human health [1-3]. A large number of drugs contain nitrosatable groups such as secondary amines, tertiary amines, amides, which can produce NNC through interaction with nitrite [4]. The stomach provides a suitable enviroment with low pH level of interaction favoring amines with nitrite. NNC formed from nitrosating process of drugs can lead to colorectal cancer, bladder, stomach and. a. Thus, there is currently a strong interest in potential toxicity study of orally administered drugs which contain secondary amine group [2-4]. It conducted the study process of diclofenac sodium nitrosating so after diclofenac variation in the system as well as nitrite. Inhibition was studied by using the nitrosation process natural anti-oxidants (such as dihidroxifumaric acid (DFH4), resveratrol), as well as polymers functionalized with antioxidants. Functionalization was conducted DNA-DFH4 at different mass ratios. The complex obtained was used further in the inhibition of nitrosating process of diclofenac sodium. With an increase in the concentration of the dihidroxifumaric acid in the complex, increases the inhibitory activity of the complex. The use of functionalized polymer antioxidants in inhibiting the nitrosation process is more efficient than the use of pure antioxidants, which has demonstrated the inhibitors ability and antioxidant activity. Conclusions: By increasing concentration of nitrite ion in the system increases the rate of consumption of the DCF as the formation of N-nitrosocompounds depends on the nitrite ion concentration. The speed of the nitrosating process of diclofenac sodium with nitrite ions in the presence of natural antioxidants (DFH4, Resveratrol) depends on the concentration of these inhibitors; the higher their concentration in the system is, the lower nitrosation process takes place. The inhibitory activity of the complex obtained DNA: DFH4 increases as the concentration of antioxitant increases, respectively mass ratio DNA: DFH4 = 1: 3, inhibition is maximal, which also shows that the antioxidant activity of functionalized polymer DFH4 is higher than of free antioxidant.

Bibliography: 1.John S Griesenbeck, Jean D Brender, Joseph R Sharkey, Michelle D Steck, John C Huber Jr, Antonio A Rene,Thomas J McDonald, Paul A Romitti, Mark A Canfield, Peter H Langlois, Lucina Suarez,the National Birth Defects Prevention Study, Maternal characteristics associated with the dietary intake of nitrates, nitrites, and nitrosamines in women of child-bearing age: a cross-sectional study. Environmental Health 2010, 9:10 2.Veeran Gowda Kadajji and Guru V. Betageri Water Soluble Polymers for Pharmaceutical Applications Polymers 2011, 234-241. 3.G.S. RAO, J.C. OSBORN, and M.R. ADATIA, Drug-Nitrite Interactions in Human Saliva: Effects of Food Constituents on Carcinogenic N-Nitrosamine Formation, 2011, 768-776. 4.Tze-chen Hsieh and Joseph M. Wu. Resveratrol: Biological and pharmaceutical properties as anticancer molecule. International Union of Biochemistry and Molecular Biology, Inc. Volume 36, Number 5, 2010, Pages 360–369.

P42

DFT STUDY OF THE HOST-GUEST COMPLEX (HGC) BETWEEN γ – CYCLODEXTRIN AND cis-OLEIC ACID

M. Yu. Gorbachev, N. N. Gorinchoy, I. Arsene, and I. I. Geru

Institute of Chemistry, Academy of Sciences of Moldova, Academic 3 Str., Kishinev MD-2028, Republic of Moldova [email protected], [email protected]

In order to reveal the nature of the intermolecular binding between the parts of the title HGC, the DFT B3LYP calculations were performed with the use of GAUSSIAN09 program package [1] and 6-31G basis sets. The schematic view of the optimized geometry of the HGC is presented in Fig. 1. The distance R between the centre of symmetry of γ-cyclodextrin (γCD) and the carbon atom of the end methyl group of cis-oleic acid (COA) equals to 11Å (R = R0). The value of R was varied from R0 up to R = ∞ when the molecules forming the HGC are considered as free. Fig. 2 show of the functional dependence of the energy difference E=E(R) - E(R0) for the HGC on R.

Fig.1 Fig.2

One can see from Fig. 2 that the energy release connected with the formation of the HGC is equal to 0.0907 a.u. or 56.9 kcal/mole. However, the HGC does not contain any intermolecular (between γCD and COA) hydrogen bonds. Moreover, the minimal distance between the atoms of γCD and those of COA is 2.86Å. At the same time, the calculated value of the dipole moment (DM) of the HGC is 5.56 D; the values of DMs of γCD and COA are 4.95 D and 0.61 D respectively. It means that the value of DM of the HGC is the sum of the values of the DMs of its parts. Thus, the formation of the HGC is exclusively caused by the dipole-dipole interaction (of the type ‘head to tail’) between the molecules of γCD and COA.

[1]. M.J.Frisch, G.W. Trucks, H.B.Schlegel et al., Gaussian 09, Revision B.01, Gaussian, Inc., Wallingford, CT, 2009.

P43

PHOTOINDUCED TRANSFORMATION OF PROCYMIDONE BY ITS ADSORPTION ON TiO2 SURFACE

M.Yu. Gorbachev, N.N. Gorinchoy, and I. Osipov

Institute of Chemistry, Academy of Sciences of Moldova, Academiei str., 3, Kishinev MD-2028, Republic of Moldova

The detoxication of pesticides after their application is very important from the environmental, human health and economical points of view. The use of additives that can enhance degradation of the applied pesticides could be useful to clean pesticide residues from fruit surface. As a model we choosed fungicide procymidone and titanium dioxide as additive. Chromatography and spectroscopic techniques were used for identification of phototransformation products and phototransformation pathway with addition of TiO2. Results obtained from experimental research were confirmed by quantum-chemical calculations. Also, quantum-chemical research gave a more detailed information regarding phototransformation pathway of free molecule of procymidone and its molecular complex with surface of TiO2. All the calculations were performed by means of the DFT (B3LYP functional) method using the basis set 6-31G from GAUSSIAN-09 package [1]. Our main results presented in Figures 1 and 2, show that the exited molecule of procymidone is coordinated trough of its Cl* atom to the Ti* atom of the molecular system H2Ti4O9 and interacts with one of the hydroxyl groups that results from water photodecomposition on TiO2 surface. It was found that during this process Cl* is substituted with one OH- group, thus the photoexited molecule of procymidone transforms into its lover toxic phenol derivative.

Fig. 1 The initial geometry of the reacting Fig. 2 The final optimized geometry of system: Procymidone x H2Ti4O9 x hydroxide the reacting system under investigation. anion

[1] M. J. Frisch, et. al., Gaussian 09, revision B.01; Gaussian, Inc.: Wallingford, CT, 2009.

P44

SURFACE TENSION OF NONPLANAR HYPERCONJUGATED ORGANIC LIQUIDS: DFT STUDY

M. Yu. Gorbachev, Ion Arsene, Natalia Gorinchioy

Institute of Chemistry, Academy of Sciences of Moldova, Chisinau, Republic of Moldova E-mail: [email protected], [email protected]

In the work [1] it is shown that the equation (1), σ = ξ C* + γ, holds for surface tension σ of liquids with π-conjugated planar molecules. In Eq. (1) C* = V-2/3 (1 - T/Tc) ΔE × 10-5 (Nm-1mol-1/3), where the values V, T, and Tc are molar volume, temperature and critical temperature of a liquid, respectively. ΔE is the calculated (by the DFT B3LYP method with the 6-31G basis set) binding energy per one of the two molecules forming dimmer and belonging respectively to the surface liquid layer and the nearest neighboring one. It was found that the values of ξ and γ are equal to 0.893 (mol1/3) and 26.01 (Nm-1) respectively. The quantity γ describes the attraction between the molecules of the surface layer (due to the formation of the planar surface π-conjugated electronic system). In the present work we consider the influence of πσ*-hyperconjugation arising when σ* MOs of the CH bonds of the methyl groups (see the compounds presented in the Table) conjugate (and enter) the above surface π-electronic system. The main results of our study are given in Figure 1. One can see that the mentioned hyperconjugation leads to the parallel shift the linear dependence (see Eq. (1)) towards the region with the new lower value of γ. 3 -3 Nos. Compound σ×10 Tc ∆E×10 C* (N/m) (K) (J/mol) (N m-1 mol-1/3) 1 2-Methyl-2-butene 19.70 273.15 1.576 3.01 2 2-Methylpropene 24.08 203.15 2.102 5.77 3 Toluene 28.50 293.15 3.678 8.27 4 p-Xylene 28.54 293.15 4.992 10.56 5 m-Xylene 28.63 293.15 3.678 7.81 6 o-Xylene 30.30 293.15 4.466 9.79 7 2-Methylpyridine 33.62 293.15 7.356 18.2 8 3-Methylpyridine 35.04 293.15 7.356 18.96 9 4-Methylpyridine 35.43 293.15 7.356 18.95 10 p-Nitrotoluene 36.90 328.15 9.195 19.84 11 m-Nitrotoluene 41.30 293.15 8.670 21.6 12 o-Nitrotoluene 41.75 293.15 10.771 26.53

Fig. 1. Correlation between the experimental values of σ and the calculated values of C*

[1]. M.Yu.Gorbachev, O.Budei, I.Arsene, N.N.Gorinchoy, - Journal of Molecular Liquids, 2014, v. 190, pp. 50-53.

P45

SYNTHESIS OF MONODISPERSE IRON OXIDE NANOPARTICLES BY THERMAL DECOMPOSITION OF IRON SALYCILATES COMPOUND

GorinchoyViorina a, Pushcashu Borisa, Indricean Constantina, Sârbu Corneliub, Lozan Vasilea*

aInstitute of Chemistry of the Academy of Sciences of Moldova, 3, Academiei str., Chisinau MD2028, Republic of Moldova bNational Institute of Materials Physics, Bucureşti-Măgurele, România *e-mail: [email protected]; phone: (+373 22) 73 97 55 In recent years, the development of metal oxide nanocrystals has been intensively pursued because of their useful applications in catalysis, energy storage, magnetic data storage, sensors, and ferrofluids. In this communication we wish to present nanoparticles based on heteronuclears salicylates complexes. The nanocrystals were synthetized in a three-neck flask equipped with condenser, magnetic stirrer and heating mantle. In a typical procedure, a mixture 1 of heteronuclears salicylates complexes {[FeSr2(Sal)2(SalH)2(NO3)(DMAA)4]}n , 2 [Fe2CoO(SalH)6(CH3OH)2(H2O)]·DMFA·2,5H2O , {Fe3O}) fine powder, oleic acid and 1- octadecene was heated under stiring to 320oC, under an argon atmosphere. The TEM micrographs of these nanocrystals demonstrate the high quality The figures 1a and 1b shows TEM images of nanoparticles of monodisperse FeSr2 and Fe3O evidence obtained microscope JEM - 200CX. It can be seen that the nanoparticles FeSr2 and Fe3O have a regular cubic form. In the case of the sample FeSr2, nanoparticle size, to a great extent, are homogeneous, the side of the cube in the art (8-10) nm. The sample size of the nanoparticles is homogeneous Fe3O (2-10) nm, particle size predominantly in the range (2-4) nm.

a b

Fig.1. TEM micrograph of the nanoparticle FeSr2 (a) and Fe3O (b)

______

[1]. Gorinchoi V. V., Turte K. I., Simonov Yu. A., Shova S. G., Lipkovskii Ya., and Shofranskii V. N., Russ. J. Coord.Chem., 2009, Vol. 35, nr.4, pp. 283–290. [2]. Gorinchoy V. V., Zubareva V. E., Shova S. G., Szafranski V. N.,. Lipkowski J, Stanica N., Simonov Yu. A., and. Turta C. I., Russ. J. Coord.Chem., 2009, Vol. 35, № 10, pp. 743–751.

P46

INHIBITION OF STEEL CORROSION BY IRON-STRONTIUM SALICYLATE COMPLEX IN WATER

Gorinchoy V.*, Lozan V. *, Parshutin V.V. **, Sholtuian N.S. **, Covali A.V. **, Cernisheva N.V. **

*Institute of Chemistry of the Academy of Sciences of Moldova, Chisinau, Moldova; 3 Academiei Str., Chisinau MD2028; **Institute of Applied Physics, Academy of Sciences of Moldova, 5 Academiei Str., Chisinau MD2028, E-mail: [email protected]

To inhibit the corrosion of carbon steel in water and aqueous solutions various organic compounds including salicylic acid and its derivatives have been successfully used. However, - 2- - their protective properties in solution in the presence of Cl , SO4 , and NO3 ions are greatly reduced, since the latter have harmful effect on the protective film formed on the corroding surface in the presence of inhibitors. Additionally, known inhibitors are used in high concentrations along with other components, thus making them difficult to use. In this comunication we present a heteronuclear salicylate complex - - 2- [FeSr2(SalH)2(Sal)2(NO3)(DМАА)4], where SalH = C6H4OHCOO (mono deprotonated), Sal - - =C6H4(O )COO (bi deprotonated), DMAA= dimethylacetamide (C4H9NO), at a concentration of 0.05-0.75 g/L, that was used as a corrosion inhibitor for closed steel pipe with the water supply. By means of various physical methods (gravimetric, electrochemical, X-ray, UV and IR spectral analysis) the mechanism of inhibition was discovered. It was shown the effect of time and concentration of complex on the interaction process of the inhibitor and its degradation products with the ionized iron and on the formation of protective coating layers on the deteriorated surface. It was found that even small concentrations of the substance reduce the corrosion rate more than 11 times, providing a degree of protection Z, equal to 91%. The advantage of the presented inhibitor is that it provides a uniform corrosion inhibition in time.

P47

SYNTHESIS OF SOME N’-n-DIMETHYLPHENYL-N,N-DIMETHYLTHIOUREAS WITH ANTIPROLIFERATIVE PROPERTIES

Tatiana Guțu1, A.Barba2, V.Prisacaru3

1 Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici st.,Chisinau, MD2009, Moldova, [email protected] 2 Institute of Chemistry, Academy of Science of Moldova, Chisinau, Moldova 3 University of Medicine and Pharmacy „N.Testemiteanu”, Chisinau, Moldova

Methods for synthesis of newcompounds of thioureeaderivatives are described. Thesecompounds are of both theoretically and practically interest through heir aplications in various fields, as they posses valuable biological activit ysuch as antifungal, antitumour, antiviral, antibacterial, pharmacological, herbicidal, and insecticidal properties. Thioureas have suitable C=S function groups, and they can be considered as useful chelating agents due to their ability to encapsulate into their coordinating moiety metal ions[1]. 3 3 R R 4 2 4 2 R R CH3 S R R + N S C CH3 H3C C S N 5 1 5 1 R R R R CH S CH3 3 HN NH2 N CH3 1 2 3 4 5 1 3 2 4 5 1 4 2 3 5 R ,R =CH3 R ,R ,R =H (1) R ,R =CH3 R ,R ,R =H (2) R ,R =CH3 R ,R ,R =H (3) S 1 5 2 3 4 2 3 1 4 5 2 4 1 3 5 R ,R =CH3 R ,R ,R =H (4) R ,R =CH3 R ,R ,R =H (5) R ,R =CH3 R ,R ,R =H (6) An efficient method for the synthesis of unsymmetrical substituted thiourea derivatives by means of simple condensation between available building blocks such as amines and carbon disulfide in aqueous medium, but this method uses a toxic reactive as carbon disulfide so we tried to substituteit with the accessible and nontoxic reactive as tetramethyldithiocarbamate (DTMT). Synthesis ofN1-n-dimethylphenyl-N, N- dimethylthioureas was carried between n- dimethylaniline and (DTMT). The ends of the reactions were checked by thin layer chromatography (TLC). N1-n-dimethylphenyl-N, N-dimethylthioureas presents white crystalline products, their structure was confirmed by 1H and 13C NMR Spectra and are presented in table below: Nr. Name Melting point, °C H1NMR C13NMR DMSO-d6 DMSO-d6 1 N1-2,3-dimetilfenil-N,N- 170-172 8.8(s.1H,NH),7-6.8(m, Ar-H), 3.45(s, 14.7, 20.6, 41.1, 125.3, dimetiltiourea N-CH3), 127.2, 128.0, 134.7, 137.1, 2.03, 2.24(s, CH3-Ar) 140.0, 181.9 2 N1-2,4-dimetilfenil-N,N- 160-162 8.76(s.1H,NH),7.01-6.9(m, Ar-H), 18.3, 21.05, 41.1 126.9, dimetiltiourea 3.26(s, N-CH3), 129.3, 131.0, 135.7, 135.8, 2.27,2.12(s, CH3-Ar) 137.7, 182.07 3 N1-2,5-dimetilfenil-N,N- 145-147 8.75(s.1H,NH),7.12-6.8(m, Ar-H), 17.9, 20.8, 41.1, 127.0, dimetiltiourea 3.45(s, N-CH3), 129.0, 130.0, 133.0, 135.0, 2.26, 2.12(s, CH3-Ar) 140.0, 181.9 4 N1-2,6-dimetilfenil-N,N- 140-142 8.80(s.1H,NH),7.72-7.48(m, Ar-H), 19.0, 40.6, 125.6, 126.7 dimetiltiourea 3.42(s, N-CH3),2.27(s, CH3-Ar) 128.3, 128.8, 129.6, 131.5, 176.8 5 N1-3,4-dimetilfenil-N,N- 180-182 8.88(s.1H,NH),7.2-6.8(m, Ar-H), 19.32, 19.9, 41.2, 123.0, dimetiltiourea 3.25(s, N-CH3), 127.0, 129.0, 132.0, 135.0, 2.18(s, CH3-Ar) 139.0, 181.8 6 N1-3,5-dimetilfenil-N,N- 190-192 8.80(s.1H,NH),6.89-6.74(m, Ar- 21.4, 41.4, 123.0, 126.1, dimetiltiourea H),3.25(s, N-CH3), 2.24(s, CH3-Ar) 126.4, 136.0, 137.0, 141.0, 181.6 These compounds were tested as anti proliferative agents.

1. Gulea A., Poirier D., Roy J., Stavila V., Bulimestru I., Ţapcov V., Bârcă M., Popovschi L. In vitro antileukemia, antibacterial and antifungal activities of some 3d metal complexes: Chemical synthesis and structure – activity relationships // Journal of Enzyme Inhibition and Medicinal Chemistry, 2008; V. 23. Nr.6, pp.806-818. 76

P48

SYNTHESIS, CRYSTAL STRUCTURE AND PROPERTIES OF IRON(III) COMPLEX WITH 2-(2-IMIDAZOLYL)PHENOLATE LIGAND

Ryoji Mitsuhashi,a Satoshi Hosoya,a Takayoshi Suzuki,b and Masahiro Mikuriyaa

aDepartment of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan bDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530 *e-mail: [email protected], TEL: +81-79-565-8365, FAX: +81-79-565-9729

The construction of self-aggregated metal-organic frameworks via π-π or hydrogen- bonding interactions is receiving much attention in supramolecular and host-guest chemistry, crystal engineering, material science and molecular magnetism [1,2]. Hydrogen-bonding interaction is especially important to design supramolecular structure owing to its directed bond formation. Among spin-crossover compounds, such weak interactions give rise to an abrupt spin state transition by cooperative effect. On the other hand, we have previously reported the redox properties of Ru(II/III) complex with 2-(2-imidazolyl)phenolate (Himl–) ligand [3]. Since the complex with Himl– as a bidentate ligand has non-coordinating N–H bond that directed to outer sphere, such complexes can be aggregated via intermolecular hydrogen bonds. In this study, we report the synthesis, crystal structure and magnetic properties of iron(III) complex with Himl– ligand. The reaction of Fe(II) salt and Himl– (3 eq.) in methanol under atmosphere afforded red crystals. The X-ray analysis of the crystal indicated that formation of mononuclear Fe(III) complex, fac-[Fe(Himl)3]·3CH3OH (Fig. 1). The bond distances around Fe center and the magnetic susceptibility measurement suggested high spin ground state of Fe(III) center. Furthermore, the solvent of crystallization, methanol, mediates multiple intermolecular hydrogen bonds between enantiometric pair of fac-[Fe(Himl)3].

Fig. 1. ORTEP of fac-[Fe(Himl)3] (50% probability level).

1. Reger, D. L.; Horger, J. J.; Smith, M. D.; Long, G. J.; Grandjean, F. Inorg. Chem. 2011, 50, 686. 2. Sunatsuki, Y.; Ikuta, Y.; Matsumoto, N.; Ohta, H.; Kojima, M.; Iijima, S.; Hayami, S.; Maeda, Y.; Kaizaki, S.; Dahan, F.; Tuchagues, J.-P. Angew. Chem. Int. Ed. Engl. 2003, 42, 1614. 3. Mitsuhashi, R.; Suzuki, T.; Sunatsuki, Y. Inorg. Chem. 2013, 52, 10183.

P49

SUPERPARAMAGNETIC IRON OXIDE NANOWIRES SELF-ASSEMBLED INTO SMECTIC CRYSTAL

Mihail Iacob, Codrin Tugui, Dumitru Sirbu, George Stiubianu, Maria Cazacu

aInstitute of Chemistry of ASM, Chisinau, Republic of Moldova b“Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania

The research in the field of nanoparticles presents both theoretical and practical interest. A special attention is given to magnetic materials due to a wide range of applications, such as magnetic resonance images (MRI), contrast agents and hyperthermia [1]. Iron oxides are one of the most commonly used and well-studied magnetic materials. The magnetic properties are highly dependent on the size, shape and structure of the particles, that’s way the establishment of efficient procedure to obtain nanoparticles with controlled morphologies and shape is one of the most important missions in nanotechnology. Due to their large aspect ratios resulting in high surface areas, the nanowire morphology is attractive for many applications, such as magnetic refrigeration, electronics, catalysts, Li-ion batteries, pigments, gas sensors, etc. [2]. For example, the magnetorheological performance of nanowire fluid is better than the spherical particle fluid, in terms of yield stress, compression displacement, and creep recovery ratio. The aim of this study was to obtain iron oxides nanowires using an iron coordination compound as precursor. The nanoparticles with different morphologies were obtained through thermal decomposition of μ3-oxo trinuclear iron (III) acetate in presence of oleic acid and dodecylamine, in trichloroacetic acid as a solvent. The preparation procedure was optimized to obtain iron oxide nanowires where the amount of oleic acid was used as a control parameter. The obtained materials were characterized using different techniques: transmission electron microscopy, thermogravimetrical analysis, infrared spectroscopy, Mössbauer spectroscopy, magnetic measurements. The self-assembling of prepared materials was investigated using wide angle X-ray diffraction, small angle X-ray scattering and polarized optical microscopy.

Acknowledgement:

This work was supported by a grant of the Ministry of National Education, CNCS – UEFISCDI, project number PN-II-ID-PCE-2012-4-0261 (Contract 53/02.09.2013). References: [1] S. Laurent, D. Forge, M. Port, A. Roch, C. Robic et. al., Chem. Rev. 108, 2064 (2008). [2] J. Wang, M. S. Gudiksen, X. Duan, Y. Cui and C. M. Lieber, Science, 2001, 293, 1455– 1457.

P50

STUDY OF THE THERMODYNAMICS OF FORMATION OF COPPER (II) COMPLEX COMPOUNDS WITH N-[(E)-PYRIDINE-2-ILMETHYLIDENE]-4H-1,2,4 - TRIAZOL- 4 –AMINE

T. Isac-Gutul1, A. Paholinitcaia1, E. Tutovan1, C. Dorogoncean1

1 Laboratory of Advanced materials in biopharmaceutical, Department of Chemistry, Moldova State University, 60, Mateevici str. Chisinau, MD 2009, Moldova, e-mail: [email protected]

At prezent for the elimination of cationes of some metales from various systems with special properties and in order to maintain these importante ptroperties, more often there are used different ligands. These ligands used in biological and idustrial systems should have the following properties: selectivity, excretion, metabolic integration, etc. For example, copper metabolism disorders lead to some diseases such as Menkes and Wilson diseases. Synthesis of N-[(E)-pyridine-2-ilmethylidene]-4H-1,2,4-triazol-4-amine ligand was realized according to the following scheme: O NH2 N N H N N N N + H2O + N N N

The complex compound was obtained by mixing of ligand and Cu(NO3)2 aqueous solutions of concentration 0,03 M. Spectrophotometric method was used for the determination of the composition and stability constants of forming complex compounds. There was used the solution of copper nitrate and the exact concentration of copper was determinated by iodometric method. It was established that the maximum of absorption of the complex compound is at  = 700 nm and the value of pH at which the absorbtion is maximal at all wave lenghs is equal to 5,1. By Ostromislensky-Job method it was determinated that the composition of complex compounds of copper with the obtained ligand corresponds to the following ratio of components: Cu(II):L= 1:1 (table I). The value of stability constant of complex compound was determinated by graphical method Bennesi-Hildebrand and by clasic method Komari. Table I. Determination of composition of complex compound CuL

N V(Cu(NO3)2, ml V ligand, ml VM/(VM+VL) A 0,5 4,5 0,1 0,108 2 1 4 0,2 0,157 3 1,4 3,6 0,28 0,208 4 1,7 3,3 0,34 0,218 5 2 3 0,4 0,231 6 2,5 2,5 0,5 0,219 7 3 2 0,6 0,159 8 4 1 0,8 0,08 9 4,5 0,5 0,9 0,007 10 5 0 1 0

Stability constant of complex compound of copper (II) with N-[(E)-pyridine-2-ilmethylidene]- 4H-1,2,4-triazol-4-amine in aqueous solution at pH = 5,1 is equal to  = 562.34 l ∙ mol-1.

P51

DETERMINATION OF COMPOSITION AND OF APARENT STABILITY CONSTANT OF COMPLEX COMPOUND OF Cu(II) WITH 4- MORPHOLYNTHIOSEMICARBAZIDE T. Isac-Gutul1, E. Tutovan1, A. Paholinitcaia1, C. Triboi1

1 Laboratory of Advanced materials in biopharmaceutical , Department of Chemistry, Moldova State University, 60, Mateevici str. Chisinau, MD 2009, Moldova, e-mail: [email protected]

Chemistry of coordination compounds of 3-d metals with thiosemicarbazides and thiosemicarbazones has developed intensively lately. This is a result of the increasing interest of chemists and physicians towards bioinorganic chemistry, an important part of which is preparation of efficient medicinal substances by using different organic ligands and biometals and determination of their therapeutic properties in cells. The work deals with synthesis of 4-morpholynthiosemicarbazide, determination of composition and of apparent stability constant of complex formed between mentioned ligand and Cu (II) ions in homogeneous solutions. The structure of the mentioned substanse was established with NMR (C13 şi H1) and X-ray difraction. The thermodynamics of formation of compounds of copper(II) with 4- morpholynthiosemicarbazide in homogenious medium was studied. In the examined system the optimal value of pH for the formation of complexes was found to be pH = 5,5-6. It was established that the maximum of absorption of the complex compound is at  = 670 nm (fig. 1). On the basis of the experimental data, using Ostromislensky-Job spectrophotometric method it has been established that in the formed compound the ratio of the components is Cu(II) : 4-morpholynthiosemicarbazide = 1:2 at the both temperatures used. The stability constants of the coordination compounds has been calculated at t = 20 C and t = 36,6 C at pH = 5, using Benesi - Hildebrand graphic method (fig.2).

  Fig.1. Electronic spectrum of complex Fig.2. The dependence СМ/ A = f( A ) of Cu(II) with 4-morpholynthiosemicarbazide. at t = 20 C, pH = 5. Bennesi-Hildebrand method is based on utilzation of equation (1) and on the basis of the linear form of equation (1) – ecuation (2):

 [ML] C A 1   (1) M   (2) 2    (cM [ML]) A     there is plotted the graphical dependence СМ / = f( ) from which extinction coefficient  and stability constant  are determined. It has been established that the values of stability constants are: lg   2,84 (t= 20 C); lg   2,19(t= 36,6 C).

P52

PROBLEM OF GRAFTING OF ANTITUBERCULOSIS DRUGS TO THE HIGH MOLECULAR COPOLYMERS BASED ON N-VINYLPYRROLIDONE

Albert Ivancic1, Gherciu Irina1, Robu Ştefan1

1State University of Moldova, Industrial and Ecological Chemistry Department, 60, Mateevici str., Chisinau, Republic of Moldova

Nowadays the problem of pharmaceutical preparations with prolonged effect, which would release in the human body a sufficient amount of bioactive compound over an extended period of time, is the current one. In this work we set purpose to graft antituberculosis (anti-TB) drugs such as norfloxacin and others to N-vinylpyrrolidone with methacrylic acid copolymer. [1,2] Medicinal copolymer was synthesised based on N-vinylpyrrolidone with methacrylic acid copolymer (50:50 mol%) obtained after block copolymerization with characteristic viscosity ≈ 0,15Dl/g. Norfloxacin and its analogs grafting was performed according to the scheme: O O F C OH

CH CH3 3 O HN N N Cl C O C2H5 N COOH OC H N O 2 5 O norfloxacin O - HCl - C2H5OH C O - CO2 H5C2O O O F C O O OH CH3 F C HN N N OH N C H O 2 5 O N N N - C H OH 2 5 C2H5 - CO2 medicinal copolymer Obtained copolymers were purified by recrystallization from hexane, then diethyl ether. Chemical structures of copolymers were determined by IR spectroscopy: the occurrence of new absorption bands at wave numbers: 3200 cm-1 (group -NH-CO-), 1720 cm-1 ( = C=O from norfloxacin) and 750 cm-1 (≡C-F) demonstrates norfloxacin grafting. Preventive tests for antimicrobial activity of obtained copolymer, showed an activity comparable to that of norfloxacin. Studies of the prolongation effect of medicinal copolymer, by dialysis method, showed that the drug traverses the semipermiable membrane for 4-5 h, compared to 0,5-1 h for the control experiment (only norfloxacin). In conclusion we can mention that a macromolecular medicinal compound with noticiable antibiotic and potential anti-TB properties was obtained.

References 1. Plate N.A., Vasilev A.E. „Physiologically active polymers”, Moscow, Khimiya, 1986 2. Kirsh Y.E., „Water soluble poly-N-vinylamides: Synthesis and physicochemical properties”, Chichester, Wiley, 1998, p. 233

P53

PREPARATION AND PROPERTIES OF SORBENTS BASED ON NANOSIZED MANGANESE OXIDES

A.I. Ivanets1, V.G. Prozorovich1, T.F. Kuznetsova1, A.V. Radkevich2, A.M. Zarubo2

1Institute of General and Inorganic Chemistry of The National Academy of Sciences of Belarus 220072 Minsk, Surganov str. 9/1 2The joint Institute for Power and Nuclear Research - Sosny 220109 Minsk, Academician A.K.Krasin str. 99 [email protected] Composite materials based on layered and channel manganese oxides are widely used as adsorbents, molecular sieves and ion exchangers for the removal of toxic metal ions from aqueous solutions. The present work is devoted to the synthesis of nanoscale oxides of manganese with developed porous structure obtained by the sol-gel method, and the study of their selective sorption properties towards Sr (II) ions. Non-template sol-gel synthesis was carried out using manganese dioxide hydrosols which were obtained by the reduction of potassium permanganate by hydrogen peroxide, and manganese chloride (II). Obtained sols were characterized by containing MnO2 0,05 wt. %, pH 10,8, ζ-potential of -21.9 mV, and the content of MnO2 0,02 wt. %, pH 4,4, ζ-potential of -17.5 mV, respectively. Using scanning electron microscopy and adsorption-structural and X-ray analysis, it is studied the influence of the parameters of the porous structure, phase composition (Table) and morphology (Figure) on the sorption- selective properties of nanoscale oxides of manganese ions relative to Sr (II). a b

Microphotograph of manganese dioxide obtained by Based on Physicoreduction-chemical of KMnO and selective: a – H O adsorptio, b– MnCln properties of manganese oxides. 4 2 2 2 Phase The composition of the background solution T, S , composition sp Н О NaCl CaCl 0C m2/g 2 2 -2 3 -2 3 -2 3 S, % Кd·10 , cm /g S, % Кd·10 , cm /g S, % Кd·10 , cm /g 80 amorphous 32 94 96.7 17 1.1 7 0.4 α-MnO + γ- 200 2 188 95 105.5 19 1.2 10 0.6 MnO2 β-MnO +γ- 400 2 189 100 3669.1 99 474.2 22 1.5 MnO2 600 β-MnO2 49 98 273.3 95 106.5 47 4.6 80 amorphous 120 71 12.8 41 3.5 11 0.6

200 MnO+α-MnO2 204 86 30.6 45 4.1 12 0.7

400 α-MnO2+Mn2O3 212 96 210.6 63 1.2 19 8.7

600 α-MnO2+Mn5O8 131 99 724.7 75 15.6 18 1.1 The data of table it is established that the process of sorption of Sr (II) on the synthesized samples is highly selective (degree of sorption (S) of the aqueous solution is 71-100%, of the solution with NaCl and CaCl2 - 17-99% and 7-47 %, respectively) due to a combination of a certain type of crystal structure and developed porous structure.

P54

EFFECT OF THE PHASE COMPOSITION AND POROUS STRUCTURE ON THE ACTIVITY OF MANGANESE AND COPPER OXIDES CATALYSTS

A.I. Ivanets, E.A. Voronets, T.F. Kuznetsova, and T.A. Azarova

Institute of General and Inorganic Chemistry of the National Academy of Sciences of Belarus 220072 Minsk, Surganov str. 9/1

[email protected]

Individual and mixed oxides of copper and manganese are effective catalysts for various oxidation-reduction reactions, e.g., oxidation of carbon monoxide, decomposition of ozone, oxidation of organic compounds, etc. In this case, phase composition and porous structure parameters are largely determining their catalytic properties in each specific chemical process. The present work is devoted to study the influence of phase composition and adsorption- structural properties of individual and mixed copper - and manganese-containing catalysts deposited on dolomite substrate on the catalytic activity in the oxidation of Fe (II) by atmospheric oxygen in the aquatic environment. The actuality of development a highly active catalyst for this process is due to their wide practical application for the purification of groundwater from iron compounds for drinking purposes. Applied catalysts were obtained by impregnation of previously heat-treated at 800 °C natural dolomite fraction 0,63-1,0 mm aqueous solutions of chlorides of manganese (II) and/or copper (II), followed by drying at 80 °C and heat treated in the temperature range 200-600 °C. The ratio of Cu:Mn in the impregnating solution of the oxide precursor was 1:1 and 1:2, which according to literature data allows to obtain the most active mixed phase oxides of copper and manganese with a spinel structure. Samples of catalysts were characterized using low- temperature sorption-desorption of nitrogen (ASAP 2020, Micromeritics, USA) and X-ray diffraction (diffractometer D8 Advance, Germany). Evaluation of the catalytic activity of the synthesized samples was carry out by the degree of oxidation of Fe(II) to Fe(III) in a model solution for the installation of a flow-type reactor volume of 300 cm3, a linear speed of 20 m/h, initial concentration of Fe(II) 50 mg/l, pH of 6.0- 6.5. The concentration of dissolved oxygen in the model solution was at the level 8.0 to 9.0 mg/L. The results demonstrate that the highest catalytic activity is offered by the catalysts prepared through impregnation with solutions containing 0.2 M CuCl2, 0.2 M CuCl2 + 0.4 M MnCl2, and 0.2 M CuCl2 +0.2M MnCl2 and calcination at 600°C (Fe2+ to Fe3+conversion of 66, 67, and 75%, respectively). The copper–manganese mixed oxide catalysts consist of CuO, MnO2, Ca2Mn3O8, Ca3CuMnO6, and Cu1.5Mn1.5O4, and the copper oxide catalyst contains CuO. In contrast to the other materials, the most active catalyst contains Cu1.5Mn1.5O4 (spinel structure) and has a unimodal mesopore volume–diameter distribution, with the most likely mesopore diameter of 26 nm. These factors seem to be responsible for its enhanced catalytic activity.

P55

THE Ag-CONTAINING FILM STRUCTURES ON THE POROUS SILICATE CERAMIC AND THEIR BIOCIDE PROPERTIES

G.A. Branitskiy2, T.A. Azarova1, S.M. Azarov1, A.I. Ivanets1

1Institute of General and Inorganic Chemistry of the National Academy of Sciences of Belarus 220072 Minsk, Surganov str. 9/1 2Scientific Research Institute of Physico-Chemical Problems of BSU, 220030, Minsk, Leningradskaya str. 14 [email protected]

This paper presents the results of investigations of Ag-containing biocidal layers, produced by sol-gel method, on the surface of the silicate filtrating materials. Given a comparative evaluation of the effectiveness of various technological approaches (treatment in aqueous solutions of compounds of silver and titanium, silver and stannic; impregnation in solutions of silver and stannic in organic solvents) in order to create active, strongly fixed on the filter surface silver complexes. It is found that on the surface of silicate ceramic materials by treatment in solutions of SnCl2 and AgNO3 microheterogeneous film structure formed of stannic oxyhalides, nanosized silver particles and it lowly soluble compounds, which impart antimicrobial properties of samples. The silver ions as a strong oxidant of many organic compounds are biologically active agent for antimicrobial protection of silicate ceramics. At film structures the source of biologically active agent is silver and lowly soluble compounds stabilized by stannic oxyhalides. It is shown that by treating the silicate ceramics in the solutions of SnCl2 and AgNO3, dissolved in organic solvents (dimethylacetamide or isopropyl alcohol) or by treatment in sols, prepared by mixing the solutions, and using the subsequent UV exposure on the sample surface can be formed microheterogenous film compositions of the hydrolysis products of SnCl2 in combination with nanoparticles AgCl and Ag. The obtained film structures impart microbicidal properties to the materials in test-cultures against various microorganisms: Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), Bacillus subtillis (Bacil. s) и Candida rubrum (Cand. r). In addition, film structures deposited by impregnation from solutions of stannum, titanium and silver in organic solvents effectively inhibit process of biofouling on silicate filtering surface. Experimentally was established that the application of modifying film coatings of solutions of inorganic substances in organic solvents with investigated compositions have no significant effect on the filtration characteristics of silicate material. The research results should be seen as evidence of the possibility of using organic solutions SnCl2 and AgNO3 to form on the surface of ceramic silicate microheterogeneous film Ag-containing compositions that protect the material from exposure of microorganisms.

P56

SYNTHESIS AND ANTIPROLIFERATIVE ACTIVITY OF THIOSEMICARBAZONE AND 4-PYRIDIN-2-YL THIOSEMICARBAZONE OF FLUORENE-9-ONE AND THEIR COORDINATION COMPOUNDS

Jalbă Svetlanaa, Barba Alicb, Gulea Aureliana aLaboratory of Advanced Materials in Biopharmaceutics and Techniques, Center of Applied and Ecological Chemistry, Moldova State University bInstitute of Chemistry, Academy of Sciences of Moldova

It’s known that coordination compounds of thiosemicarbazones with transition metals exhibit a number of important biological activities such as antibacterial, antifungal, antiviral and antitumor activities. It is very important to study and discover the mechanism of interaction between antiproliferative agent and DNA in the cancer cells. This monitoring is possible to realise using anticancer molecules which have fluorescent properties Researchers are trying to monitor the location of these compounds by developing fluorescent analogues to probe their behaviour in cells[1], including cancer cells. This compounds are as potential anti tumour imaging agents[2]. This kind of coordination compounds are obtained by addition of a fluorophore molecule to the initial thiosemicarbazide for further investigations by fluorescent methods. In our case we have obtained two thiosemicarbazones according the method of condensation reaction of a thiosemicarbazide or a derivative of thiosemicarbazide with fluorophore fluoren-9- one:

Thiosemicarbazones were prepared by the following way: equivalent parts of ketone and thiosemicarbazide were added to the reaction mixture which contained alcohol and a few drops of glacial acetic acid and then refluxed under heating for 2 hours then cooled products were filtered and washed with cold ethanol. A small amount of products were also isolated from the filtrate after concentration of the solution. Thiosemicarbazones yield were between 80-95%. The final products were analyzed by NMR Spectroscopy Structure of 2-(9H-fluoren-9-ylidene)hydrazinecarbothioamide was confirmed by NMR spectra 1 investigations in DMSO-d6. The H NMR spectra, chemical shifts, ppm: 7.34, 7.42, 7.82, 8.45,

7.36, 7.44, 7.89, 8.06(aromatic, rings), 8,45 (S, 1H, NH2); 8.76 (s,1H,NH2), 10,86(s,1H,NH) The 13C NMR spectra, ppm: 120.66, 121.16, 122.86, 127.67, 128.54, 128.58, 129.57, 130.74, 131.76, 137.08, 139.81, 141.90(12 C,aromatic rings) 145.95(C=N); 180.6(C=S). Some coordinative compounds of Cu (II), Co (II), Ni (II) were obtained and their antiproliferative activity on HeLa cervical cancer cells was investigated.

References: 1. J. Chan, A. L. Thompson, M. W. Jones and J. Peach, Inorg. Chim. Acta, 2010, 363, 1140 2. L. Wei, J. Easmon, R. K. Nagi, B. D. Meugge, L. A. Meyer, and J. S. Lewis, J. Nucl. Med., 2006, 7, 2034 85

P57

MIXED-METAL COMPLEXES OF DINUCLEAR RUTHENIUM(II,III) CARBOXYLATE AND TETRACYANIDOPLATINATE(II)

Masahiro Mikuriya,a Kenta Ono,a Shun Kawauchi,a Daisuke Yoshika,a Ryoji Mitsuhashi,a and Makoto Handab

Dinuclear ruthenium carboxylates are unique compounds, showing paramagnetic properties irrespective of the lantern-type (or paddlewheel-type) dinuclear core with metal-metal bonding (Fig. 1) [1]. Especially, interesting feature is that mixed-valent dinuclear ruthenium(II,III) carboxylates have three unpaired electrons in the metal-metal bonding orbitals with large zero-field splitting and can be considered to be useful as building block for constructing magnetic materials. We reported magnetic properties and crystal structures of some molecule-assembled complexes from dinuclear ruthenium complexes to one-dimensional polymeric chain compounds with bidentate linking ligands L. In these compounds, magnetic interaction between the dinuclear units depends on the linking ligands and mostly antiferromagnetic [1,2]. Ferrimagnetic behavior was observed for mixed-metal systems of dinuclear ruthenium with hexacyanidoferrate(III) and octacyanidotungstate(V) [1,3]. We extended these systems to mixed-metal complexes with dicyanidoargentate(I) [4] and tetracyanidonickelate(II) [5] . In this study, we prepared new mixed-metal complexes by using 2– tetracyanidoplatinate(II) [Pt(CN)4] in order to obtain further information. Herein, we report on the magnetic properties of these complexes.

Fig. 1. Dinuclear ruthenium carboxylates.

1. Mikuriya, M.; Yoshioka, D.; Handa, M. Coord. Chem. Rev. 2006, 250, 2194. 2. Ishida, I.; Handa, M.; Hiromitsu, I.; Mikuriya, M. Chem. J. Moldova 2009, 4, 90. 3. Mikuriya, M.; Yoshioka, D.; Borta, A.; Luneau, D.; Matoga, D.; Szklarzewicz, J.; Handa, M. New J. Chem. 2011, 35, 1226. 4. Mikuriya, M.; Tanaka, Y.; Yoshioka, D.; Handa, M. J. Supercond. Nov. Magn. 2015, 28, 1013. 5. Mikuriya, M.; Tanaka, Y.; Yoshioka, D.; Handa, M. Chem. J. Mold. 2014, 9(1), 93.

P58

THE PRODUCTS OF SO2 INTERACTION WITH AQUEOUS SOLUTIONS OF METHYLAMINE, BENZYLAMINES, 1,2-DIAMINES AND MORPHOLINE

1,2 3 2 Ruslan E. Khoma , Vladimir O. Gelmboldt , Alim A. Ennan , Vyacheslav N. Baumer4,5, Aleksander V. Mazepa6, Tatiana V. Koksharova1

1Mechnikov Odessa National University, Dvoryankaya St., 2, Odessa, 65082, Ukraine 2Physico-Chemical Institute of Environment and Human’ Protection, Preobrazhenskaya St., 3, Odessa, Ukraine 3Odessa National Medical University,Valikhovskiy lane, 2, Odessa, Ukraine 4Institute of Single Crystals, National Academy of Sciences of Ukraine, Kharkov, Ukraine 5Karazin Kharkov National University, Kharkov, Ukraine 6Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa, Ukraine E-mail: [email protected]

The new method of preparation of sulphur oxoanions “onium” salts via interaction in the SO2–L–H2O–O2 systems (L is methylamine, benzylamines, 1,2-diamines, and morpholine) has been developed. “Onium” sulfates have been obtained from methylamine, benzylamine, α-phenylethylamine, N,N-dimethylbenzylamine, dibenzylamine, 1,2-ethylenenediamine, morpholine, N,N,N’,N’- tetramethylethylenediamine; sulphites monohydrates – from I piperazine and N-(hydroxyethyl)ethylenediamine; dithionate – from piperazine and N,N,N’,N’-tetramethylethylenediamine. The compounds were characterized by elemental analysis, X-ray diffraction, IR, Raman spectroscopy, mass spectrometry, and differential thermal analysis. The crystal structures of new salts methylammonium sulphate (I), α- II phenylethylammonium sulfate (II), piperazinium sulphite monohydrate (III) and dithionate (IV), morpholinium sulphate monohydrate (V) have been determined by X-ray diffraction. The structures I – V are stabilized by numerous H-bonds NH∙∙∙O, OH∙∙∙O. New examples of stabilization of sulfate anion in the form of alkylammonium salts prepared in the SO2–L–H2O–O2 systems (L were amines) have been demonstrated. The formation of “onium” sulfates is the result of interaction following the formal scheme: III 2SO2 + 4RnNH3–n+ 2H2O + O2 →2(RnNH4–n)2SO4. The fact the structurally studied organic sulfites are exhausted by tetramethylguanidinium hydrosulfite (I) [1] and aminoguanidinium sulfite monohydrate [2], N-(2-hydroxyethyl)ethylenediammonium sulfite monohydrate [3] seems to be due to the ease for the sulfites to convert into dithionates and sulfates as a result of “autooxidation” [4].

IV 1. D.J. Heldebrant, C.R. Yonker, P.G. Jessop, L. Phan, Chem.-Eur. J. 15, 7619 (2009). 2. R.E. Khoma, V.O. Gelmboldt, V.N. Baumer, et al., Russ. J. Inorg. Chem. 58, 843 (2013). 3. R.E. Khoma, V.O. Gelmboldt, O.V. Shishkin, et al., Russ. J. Inorg. Chem. 59, 541 (2014). 4. R.E. Khoma, A.A. Ennan, V.O. Gelmboldt, et al., Russ. J. Gen. V Chem. 84, 637 (2014).

P59

SYNTHESIS AND STRUCTURAL STUDY OF 1-METHOXYCARBOMETHYL-3- ARYLAMINO-1,2-DIHYDRO-3H-1,4-BENZODIAZEPINES-2-ONES WHICH POSSESS THE ANALGESIC ACTIVITY

V. Ch. Kravtsov,1 M. S. Fonari,1 J. Lipkowski,2 V. I. Pavlovsky,3 I. Yu. Ushakov,3 T. A. Kabanova,3 E. I. Halimova,3 S. A. Andronati3

1Institute of Applied Physics, Academy of Sciences of Moldova, Academy str, 5 MD2028, Chisinau, Moldova, e-mail: [email protected] 2 Cardinal Wyszynski University in Warsaw, School of Sciences, Warsaw, Poland 3 A.V. Bogatsky Physico-Chemical Institute of NASU, Odessa, Ukraine

The need in safe and highly effective analgesic medications to prevent and treat acute and chronic pains is accompanied by search of antidepressants and anxiolytics to suppress the convoyed depression, anxiety and insomnia. Among the 3-substituted 1,4-benzodiazepine-2-ones analgesic activity exhibit antagonists of bradykinin, a powerful natural algogen [1,2].We have synthesized 1-methoxycarbonylmethyl-3-arylamino-1,2-dihydro-3Н-1,4-benzdiazepine-2-ones I- VI and disclosed their high analgesic activity. № R ED50 (mg/kg) I о-NO2 0.12±0.03 II м-NO2 0.25±0.12 III p-NO2 0.54±0.08 IV о-COOCH3 0.47±0.15 V м-COOCH3 0.0070±0.0018 VI p-COOCH3 0.030±0.008

The structures of I, III, IV and VI were confirmed by single crystal X-ray diffraction. In the molecules with o-position of NO2 (I) or COOCH3 (IV) group in arylamino fragment only the intramolecular H-bond was found, while in the cases with p-position of these groups (III, VI) the molecules associate in centrosym metric dimers via a couple of N-H···O (III) and N-H···N(VI) hydrogen bonds. The further aggregation of molecules in crystals is achieved via stacking interactions and weak hydrogen bonds including CH···Br, and CH···O contacts acting through the different association patterns and combining the molecules in different packing motifs.

I III VI

1. С.А. Андронати, Т.А. Кабанова, В.И. Павловский и др., Ж. орг. та фарм. химии., 2009, 7, 70. 2. V.I.Pavlovsky, O.V.Tsymbalyuk, V.S. Martynyuk, et al, Neurophysiology 2013,45,427.

The financial support from bilateral Moldova-Ukraine project 14.820.18.04.05/U and No M/161- 2014 is acknowledged

P60

d-f MIXED-METAL ASSEMBLY WITH 2,3-PYRIDINEDICARBOXYLATE LIGAND

Ana Lazarescu1, Duane Choquesillo-Lazarte2, Natalia Terenti1, Vasile Lozan1

1 Institute of Chemistry, Academy of Sciences of Moldova, Academiei, str.3, MD 2028-Chisinau, Moldova 2 Laboratorio de Estudios Cristalográficos, IACT, CSIC-UGR, Avenida de las Palmeras 4, E-18100, Armilla (Granada), Spain

The synthesis of metal-organic coordination frameworks is of great attention for their potential to exhibit useful bulk properties and due to their intriguing variety of architectures and topologies [1]. The selection of multifunctional ligands and metal ions are important in the construction of specific supramolecular architectures with multi-nodal topological nets [2]. The present work has been dedicated to the preparation of 3d-4f mixed metal extended structure of complex [Co(2,3-pdc)]3La(H2O)3 (1) using 2,3-pyridine-dicarboxylic acid (2,3-H2pdc ) as ligand. The structure of complex 1 was determined by single crystal X-ray diffraction. The complex 1 (trigonal, space group P3) has been synthesized using metalloligand approach at ambient conditions, that is isostructural with the reported Co,Gd mixed metal complex [3], synthesized by hydrothermal method. The structure comprises a network of LaO9 and CoO3N3 units connected through pyridine-2,3-dicarboxylate anions where the La+3 ions adopt a tricapped trigonal prismatic coordination arrangement (by contribution of three coordinated water molecules and carboxylate oxygens from three 2,3-pdc ligands) and the Co3+ ions are octahedrally coordinated by three oxygen and three nitrogen atoms from 2,3-pdc ligands. Both polyhedral units and dicarboxylate anions are connected and give rise to a 2D-layered structure running parallel to the plane ab (figure 1). The supramolecular architecture is Figure.1. View of the crystal structure of 1 showing built by stacking of layers that generates a channels along the c-axis. 3D network with pores extending along the c axis (aperture ca. 7 Ȧ). The complex was investigated by thermogravimetric analysis. The thermal behaviour of complex shows a several decomposition stages. In the first stage, endothermic removal of the three water o o molecules occurs up to 200 C. The anhydrous complex is thermally stable up to about 300 C. o The last stages in the temperature range of 300-560 C are related to the decomposition of 2,3- pdc ligands are by 2-3 superposed exothermic effects. The residue after decomposition constitute ~ 35%. The assembly of coordination polymer is of perspectives to use for the application in gas storage and ceramic material.

References: [1]. W.L.Leong, J.J.Vittal, Chem.Rev., 2011, 111, 688; [2]. Y.-L.Liu, J.F.Eubank, A.J. Cairns, J. Eckert, V.Ch.Kravtsov, R.Luebke, M.Eddaoudi, Angew.Chem., Int. Ed. 46 (2007) 3278; [3]. P. Mahata, G. Sankar, G. Madras, S. Natarajan, Chem. Comm. 2005, 5787.

P61

THE MICROSTRUCTURE AND ELECTRIC PROPERTIES OF NANOSTRUCTURED BaCoO2.6 PEROVSKITE BY MOLECULAR PRECURSOR DECOMPOSITION

A. Lazarescu1, V.Fruth2, S.Preda2, C.Munteanu2, A.Nicorici3,

1Institute of Chemistry, Academy of Sciences of Moldova, Academiei, str.3, MD 2028-Chisinau, Moldova 2Institute of Physical Chemistry I.Murgulescu, 060021 - Bucharest, Romania 3 Institute of the Electronic Engineering and Nanotechnologies "D. Ghitu", MD 2028-Chisinau, Moldova

The family of transition metal mixed oxides has received considerable attention due to the large number of structural phases, which exhibit attractive properties including complex magnetic phenomena, superconductivity or phase separation [1, 2]. A facile preparation route of BaCoO2.6 perovskite oxide from a solid heterometallic (Co-Ba) 2,3-pyridinedicarboxylate precursor [3 ] has been achieved. In the present paper we report on the characterization of BaCoO2.6 mixed oxide synthesized from molecular precursor by thermal decomposition method, a way which increase the control of the composition and microstructure features of the end products [4]. The synthesized sample has been identified by powder X-ray diffraction (XRD) and characterized by SEM-EDX spectroscopy. From XRD pattern all diffraction peaks were perfectly indexed to a cubic phase of BaCoO2.6 perovskite with lattice constants (a=5.659(5), b=5.659(5), c=28.45(4) ) (JCPDS Nr. 01-071-2453) and no other peaks for impurities were detected. SEM-EDX images of BaCoO2.6 annealed sample (figure 1) shows a well crystallized material, with a regular layered morphology and with a high content of pores, resulting from the organic part released during the annealing treatment.

Figure 1. SEM images of the BaCoO2.6 annealed sample at different magnitudes: a) top view b) cross view The electrical properties of ceramic oxide pressed pallet has been revealed. The temperature dependence of dc electrical conductivity has a rising temperature-activation character and its value varied from 10-2 Ohm-1cm-1 at 300 K down to 10-6 Ohmcm-1 at 80 K with calculated activation energy in the range 0.16-0.24 eV. Such behaviour indicates that the conductivity obeys the rule of semiconducting materials. Thus, the study show the suitability of heterometallic 2,3-pyridinedicarboxylate coordination polymer as precursor to mixed oxide preparation with potential applications in catalysis, sensor applications, etc.

References: [1] Cava R.J. Dalton Trans. 2004, 2979; [2] Schaak, R.E. Mallouk T.E. Chem.Mater., 14, (2002), 1455; [3] L.G. Hubert-Pfalzgraf, Inorg.Chem. Commun. 6 (2003), 102; [4] A. Lazarescu, S.Shova, J.Bartolome, et.all.Dalton Transactions, 40, (2011), p.463. 90

P62

1D COPPER(II) COORDINATION POLYMER DERIVED FROM NEW THIOSEMICARBAZONE LIGAND: STRUCTURE AND MAGNETIC PROPERTIES

Ana Lazarescu1, Marilena Ferbinteanu2, Natalia Nedelko3 , Anna Ślawska-Waniewska3

1Institute of Chemistry, Academy of Sciences of Moldova, Academiei, str.3, MD 2028-Chisinau, Moldova 2University of Bucharest, Dumbrava Rosie 23, Bucharest 020462, Romania 3Institute of Physics, Polish Academy of Sciences, al. Lotników 32/46, Warszawa 02-668, Poland

Thiosemicarbazones and their metal complexes have became the subject of intensive study due to their wide range of biological activity, analytical applications and interesting chemical and structural properties [1, 2]. Usually, thiosemicarbazones act as chelating ligands through the phenolate oxygen, azomethine nitrogen and sulphur atoms to form mononuclear complexes. In this work we report a polynuclear copper(II) - thiosemicarbazone compound 1 {[Cu(HL )(DMSO)] 0.5DMSO}n (1), where the N(2) nitrogen coordinates to a neighbour site, forming the 1D pattern (fig. 1).

) 1

0.4 -

1 -

0.3 mol

(cm T T

0.2 

0.1

T (K) 0 0 100 200 300 Fig. 1. A sequence of the 1D structure of the Fig. 2 Magnetic susceptibility compound 1 as T vs. T curve. (circles=experimental, line=fitted)

The single X ray diffraction analysis shows a monoclinic crystal with the P21/c space group and a = 9.67(2) Å, b =19.27(3) Å, c= 21.04(3) Å and = 95.25(11) o cell parameters. The Cu(II) is pyramidally coordinated, with the apical position occupied by the solvent. The equatorial subsystem is almost planar, made of the {OSN2} set of donors. The chain is developed along the N-Cu-N average trans axis, with very little asymmetry in Cu-N bond lengths (2.081 Å and 2.010 Å) and in the Cu…Cu long range distances (4.937 Å and 4.939 Å). Interpreting the chain as effectively homogenous, the magnetic susceptibility, fitted with Fisher’s formula, yields the g=2.19 gyromagnetic factor and the J=-130.2 cm-1 rather strong antiferromagnetic coupling (fig. 2). At low temperatures, a feature assignable to inter-chain interactions is visible.

References: [1] D.X.West, S.B. Padhye, P.S. Sonawane, Struct.Bonding, 1 (1991).p. 76. [2] A.Gomez-Quiroga, C.Navarro-Ranninger,Coord.Chem.Rev. 248 (2004) p. 119.

P63

SYNTHESIS AND IR SPECTROSCOPY STUDY OF IRON AND COBALT COORDINATION COMPOUNDS WITH 2,3-BUTANEDIONE BIS{(ISO)NICOTINOYLHYDRAZONE}

Cuba Lidia, Mitina Tatiana, Mirzac Alexandra, Bulhac Ion

Institute of Chemistry of the Academy of Sciences of Moldova, Academiei str.3, MD 2028 Chisinau, Republic of Moldova. [email protected]

Schiff bases 2,3-butanedione bis{(iso)nictonioylhydrazone} were obtianed by 2,3- butanedione condensation with hydrazides of nicotinic or isonicotinic acids. Iron and cobalt coordination compounds were synthesized by interaction of metal salts with Schiff bases respectively, as well through template reaction between metal salts, 2,3–butanedione and nicotinic or isonicotinic acides hydrazides. High lability of NH groups hydrogens of Schiff bases molecules and pH value of the reaction medium determines the composition of obtained complexes. Iron(III) forms compounds of type [Fe(H2L)X2]X∙nY and [Fe(H2L)(H2O)2]X3∙nY (X - - - - = NO3 , ClO4 , NCS , N3 ; Y=H2O, HNO3) in acidic medium. Infrared spectra of coordination compounds with iron are distinguished by the presence of bands at 3194 cm-1, ν(NH) and at ~1632 cm-1, coordinated ν(C=O). If NCS- groups are present then the high intensity band of ν(C≡N) appears at ~2055 cm-1 and are assigned as oscillations of those groups in coordinated - ligands through nitrogen atom or anions in external coordination sphere. N3 anions display a -1 - singular band of high intensity at ~2050 cm , which corresponds to N3 anions oscillations coordinated monodentate to metal or anions from external coordination sphere. Several absorption of high intensity bands were observed in the IR spectra of iron(III) complexes with - -1 - NO3 groups, in the range 1400-1200 cm , indicating the presence of NO3 groups, possessing different potential functions: coordination to iron atom, as anions in the external coordination sphere and as nitric acid. - The IR spectra of complexes which contain ClO4 group present absorption bands: ν(NH) peaked at ~3200 cm-1, ν(C=O) coordinated at ~1616 cm-1 and a wide and very intensive -1 -1 - band in the range 1150-1000 cm with absorption maximum at 1080 cm , assigned to the ClO4 group oscillations. The wide band of average intensity in the range 2800-2300 cm-1 is assigned to oscillations of C=NH+ groups, constituted by protonated heterocyclic nitrogen atoms. Thus iron(III) complexes have most likely an octaedric structure, which ecuatorial plane is constituted by Schiff base molecule coordinated through N2O2 sets of atoms and the axial coordinate is - - located along oxygen (water, nitrate) or nitrogen (NCS , N3 ) atoms. In cobalt coordination compounds with Schiff bases, the metal has mostly oxidation state +2, octaedric structure and forms complexes of non-electrolyte type – [Co(H2L)X2] - - - - (X=OH , NCS , N3 , NO3 ). The spectra of cobalt complexes synthesized in acidic medium contain distinct bands ν(NH) at ~3196 cm-1, and ν(C=O) coordinated at ~1630 cm-1. Absorption - - - -1 bands of NCS , N3 , NO3 groups appear in spectra as two bands in the range 2114-2075 cm , 2075-2018 cm-1 and 1306 cm-1, respectively. High value of ν(C≡N) suggests that NCS- groups less likely form anions in the external coordination sphere, however the coordination mode, through nitrogen or sulfur atoms is impossible to confirm, since absorption bands appear in the overlap region, in which we could identify these two coordination modes of NCS- groups, specifically M-NCS or M-SCN. In alkaline medium, Schiff bases coordinate in enolic form. In the spectra of iron(III) and cobalt(II) complexes, absorption bands ν(NH) and ν(C=O) could not be identified, however a very intensive band appears at ~1384 cm-1, which presumably contains ν(C−O) oscillations generated by enolization of Schiff bases.

P64

SYNTHESIS, BIOLOGICAL ACTIVITY AND X-RAY ANALYSIS OF 11,12-p-TOLYL-PYRIDAZONYL-DRIM-5(6),8(9)-EN-7-ONE

Lidia Lungua, Aculina Aricua, Alexandru Ciocarlana, Sergiu Shovaa, Gheorghita Zbanciocb, Ionel Mangalagiub, Nicoleta Vornicuc

a Institute of Chemistry, Academy of Sciences of Moldova, Academiei str. 3, MD-2028 Chisinau, Moldova, Email: [email protected] b “Alexandru I. Cuza” University, Faculty of Chemistry, Organic Chemistry Department, Bulevardul Carol I-11, 700506 Iasi, Romania c Metropolitan Center of Research T.A.B.O.R, The Metropolitanate of Moldavia and Bukovina, Closca no. 9, RO-700066 Iasi, Romania

The results of investigations devoted to the synthesis of new drimanic compound containing heterocyclic structural units are reported. The 11,12-p-tolyl-pyridazonyl-drim- 5(6),8(9)-en-7-one 3 was prepared by interaction of bromide 1 with p-tolyl-pyridazone 2 under depicted conditions.1 As result of “in vitro” biological assessment tested compound 3 showed exceptional activity against five strains of fungi (Aspergillus flavus, Fusarium solani, Penicillium chrysogenum, P. frequentans, Alternaria alternata) and against both Gram-positive (Bacillus polymyxa) and Gram-negative (Pseudomonas aeruginosa) bacteria at MIC values 510-3 µg/mL and 3.210-2 µg/mL, respectively.2

O H3C-C6H4 O N HN N Br O N + Br N N O O C H -CH 1 6 4 3 2 3 CH3 Scheme 1. Reagents and conditions: K2CO3, DMAA, r.t., 24h, 77%.

The structure and stereochemistry of the compound 3 was confirmed unambiguously by X-ray diffraction on monocrystal (Figure 1). According to single crystal X-ray study compound 3 crystallizes in C2 space group of monoclinic system comprising two crystallographic asymmetric but chemically equivalent molecular entities (denoted A and B). One of the azaheterocyclic fragments in molecule A, as well as the whole molecule B, were found to be disordered into two resolvable 3 positions in 1:1 ratio. Figure 1. The X-ray molecular structure of compound 3. H atoms are omitted for clarity. References: [1] Mantu D., Moldoveanu C., Nicolescu A., Deleanu C., I. Mangalagiu I. ”A facile synthesis of pyridazinone derivatives under ultrasonic irradiation”, Ultrasonics Sonochemistry, 16, 2009, p. 452–454. [2] National Committee on Clinical Laboratory Standards (NCCLS), “Antimicrobial Susceptibility Standards (ATS)”, ed. 2003, for M7 (CMI) and M100. [3] Crystallographic data for the structure 3 have been deposited at the Cambridge Crystallographic Data Centre as Supplementary Publication No. CCDC - 1411058.

P65

STRUCTURE ELUCIDATION OF SEVERAL HETEROCYCLES WITH QUINOXALINE AND BENZIMIDAZOLE SKELETONS

Alina Nicolescu,1,2 Emilian Georgescu,3 Florentina Georgescu,4 Ana-Maria Macsim,1 Cristina Stavarache,2 Calin Deleanu.1,2

Pyrrolo[1,2-a]quinoxaline skeleton is a constituent of several bioactive compounds that demonstrated anti-HIV and anticancer activities. Pyrrolo[1,2-a]benzimidazole derivatives exhibit activity against a variety of cancer cell lines and were found to be useful in treating central nervous system disorders These properties lead to a constant interest in developing more efficient ways for the synthesis of these heterocyclic systems. We report here several new pyrrolo[1,2-a]quinoxaline and benzimidazole derivatives obtained through an one-pot three component reaction. The structures of newly synthesized derivatives were assigned by NMR spectroscopy using several 1D and 2D experiments.

The authors acknowledge the financial support of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PN-II-ID-PCCE-2011-2-0028.

P66

NOVEL 1D COORDINATION POLYMER BASED ON HETERONUCLEAR 12+ {Ce2Fe2Na2O2} CARBOXYLATE CLUSTERS

Iurie L. Malaestean1, Arkady Ellern2, Paul Kӧgerler3

1Institute of Chemistry, ASM, Academiei Str. 3, MD-2028 Chisinau, Moldova 2Ames Laboratory, Iowa State University, Ames, IA 50011, USA 3Institute of Inorganic Chemistry, RWTH Aachen University, 52074 Aachen, Germany

Recently we have explored the magnetic functionalization of polynuclear zirconium(IV) and cerium(IV) oxide coordination clusters with paramagnetic 3d ions, motivated by their structural similarities with classical polyoxometales [1,2]. Continuing these studies, we present the synthesis and structural characterization of the novel coordination polymer

{[Ce2Fe2Na2O2(ib)8(bda)2]·MeCN}n (Hib = isobutyric acid; H2bda = N-butyldiethanolamine) constructed from hexanuclear clusters (Figure).

Single-crystal X-ray diffraction revealed that this 1D chain polymer is constructed from 12+ hexanuclear heterometal [Ce2Fe2Na2O2(ib)8(bda)2] clusters. The {Ce2Fe2Na2O2} core 2– comprises two edge-sharing CeO9 coordination polyhedra, each containing a central 4-O ion which bridges peripheral Fe3+ and Na+ centers. Peripheral ligation is provided by eight isobutyrate ligands. The bda2– ligands are assumed to be fully deprotonated and act as bridging ligands via one bidentate OH group between the hexanuclear clusters. Within the core, the two central Ce centers are in the oxidation state +IV, while the two of the four terminal Fe atoms are +III. Cerium and iron oxidation states are consistent with charge balance and bond parameters, this was also confirmed by bond valence sum (BVS) calculations, which are 4.849 for Ce +IV and 3.088 for Fe +III. The magnetic properties of the compound will be discussed in an upcoming full paper.

[1] I. L. Malaestean, et al., Dalton Trans., 2011, 40, 331.

[2] I. L. Malaestean, et al., Eur. J. Inorg. Chem., 2013, 1635.

P67

A NEW MANGANESE(II) ISOBUTYRATE 2D COORDINATION NETWORK

Iurie L. Malaestean1, Arkady Ellern2, Paul Kӧgerler3

Our recent research focused on the synthesis and investigation of 1D and 2D coordination polymers mostly based on stable hexanuclear building blocks of the type III II [Mn 2Mn 4O2(RCOO)10] (R=CHMe2, CMe3) [1,2]. Most of these compounds were synthesized by the reaction of manganese(II) isobutyrate, [Mn6(CHMe2)12(OCCHMe2H)6] [3]. Herein we demonstrate that by using the same hexanuclear manganese(II) precursor, it is possible to obtain a discrete 2D coordination polymer that for the first

time is not based on {Mn6} building blocks, namely

[Mn(CHMe2)2(bpe)(H2O)]n (bpe = 1,2- bis(4-pyridyl)ethane). Single-crystal X- ray diffraction analysis shows that each manganese(II) center is coordinated by two bridging bidentate isobutyrates, one deprotonated monodentate isobutyrate (as evident from the short C=O bond length of 1.246 Å), and one coordinated water molecule resulting in 1D zigzag chains. Two additional bpe ligands at each manganese(II) center interlink the 1D zigzag chains into a 2D network structure (Figure). The magnetic studies will be presented in a full paper.

[1] I.L. Malaestean, et al., CrystEngComm.,2014, 16, 6523. [2] I.L. Malaestean, et al., Inorg. Chem.,2010, 49, 7764. [3] I.L. Malaestean, et al., Eur. J. Inorg. Chem., 2013, 1635.

P68

SYNTHESIS AND STUDY OF NEW HETEROPOLYNUCLEAR MANGANESE- CALCIUM POLYMERS

Silvia Melnic1, Sergiu Shova1, Maria Gdaniec2, Constantin Turtă1 1Institute of Chemistry, Academy of Sciences of Moldova, Academiei street 3, MD-2028, Chisinau, Moldova 2Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznan´, Poland

Nowadays the laboratory synthesis of an artificial oxygen-evolving complex (OEC) has been the objective of many synthetic chemists. Particular attention has been given to mixed manganese- calcium compounds aimed to shed light on the tetranuclear arrangement of the manganese centers in the OEC [1]. The discovery of a rational synthetic route to accurate structural/electronic analogues of the OEC will be an important scientific breakthrough, hopefully leading to a deeper understanding of the PSII function. As a part of our systematic study here we describe results of synthesis and investigation of two heterometallic coordination compounds with general formula {[Mn2Ca2(hmp)6(L)2(H2O)2](ClO4)2}n, where L = 3-Cl-benzoic (1) or benzoic (2) acids. In efforts to construct them our attention focussed on using pre-organised [Mn3O(L)6Py2(H2O)] complexes [2] with the intention of forming clusters with Ca(ClO4)2 and 2-(hydroxymethyl)pyridine (hmp). Cluster 1 represents a polymer that crystallizes in the monoclinic space group P-1.

Structure of {[Mn2Ca2(hmp)6(3-ClPh)2(H2O)2](ClO4)2}n (1). Methyl groups are omitted for clarity.

II 8+ The manganese and calcium ions of the [Mn2 Ca2] core are bridged by six moieties of 2- (hydroxymethyl)pyridine and two acid moieties. The coordination of each Ca atom is completed by one water molecule. The Ca and Mn atoms are seven and six coordinate, respectively. The distance Mn….Mn is 3,2967 Å but Mn….Ca – 3,403 Å. Complexes were characterised by different physical-chemical methods: IR, cyclic voltammetry, UV-visible spectroscopy.

Acknowledgements This work was supported by the Moldova State Programe Project 14.518.02.05A.

References [1] Science, 2015, 348, 690. [2] Inorg. Chem., 1997, 36, 2352.

P69

SYNTHESIS AND STRUCTURE OF A NEW MANGANESE-CALCIUM CARBOXYLATE Silvia Melnic1, Sergiu Shova1, Maria Gdaniec2, Constantin Turtă1 1Institute of Chemistry, Academy of Sciences of Moldova, Academiei street 3, MD-2028, Chisinau, Moldova 2Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznan´, Poland

Interest to manganise clusters is actual in the last decades due to their important role in photosynthetic process. Particular attention has been given to mixed manganese-calcium compounds aimed to shed light on the tetranuclear arrangement of the manganese centers in the the oxygen-evolving complex (OEC) of photosystem II (PSII) [1]. In the present work we demonstrate the use of pivalic acid for the preparation of a heteropolynuclear manganese-calcium complex. The reaction of [Mn3O((CH3)3COO)6Py3] with Ca(NO3)2 in MeOH in the presence of triethanolamine forms the complexes [Mn2O2Ca4((CH3)3COO)10(Py)3][Mn2O2Ca4(CH3)3COO)10(CH3)3COOH)4] (1), in a very good yield. According to X-ray crystallography complex 1 has a molecular crystal structure comprising III two neutral hexanuclear units: [Mn 2O2Ca4((CH3)3COO)10(Py)3] and III [Mn 2O2Ca4(CH3)3COO)10(CH3)3COOH)4] in 1:1 ratio. The coordinated pivalic acid exhibits different level of deprotonation, as well as various types of coordination functions. The distances Mn…Mn separations are of 2,820 Å and 2,810 Å for a and b, respectively.

a b

Fig. 1. Molecular structure of [Mn2O2Ca4((CH3)3COO)10(Py)3] (a); [Mn2O2Ca4(CH3)3COO)10(CH3)3COOH)4] (b). Methyl groups are omitted for clarity.

Acknowledgements This work was supported by the Institutional project 11.817.08.22F.

References [1] Science, 2015, 348, p. 690 - 693.

P70

SYNTHESIS AND CRYSTAL STRUCTURES OF OXALATO- AND SULFATO- BRIDGED COPPER(II) COMPLEXES WITH 2,3-BIS(2-PYRIDYL)PYRAZINE

E. Melnic, S. G. Baca, V. Ch. Kravtsov

Institute of Applied Physics, Academy of Sciences of Moldova, Academiei str. 5, MD2028 Chişinau, R. Moldova, e-mail: [email protected]

Interest in the design and development of coordination networks reveals permanent growth due to wide range of their potential practical applications. On this line, novel N-donor chelating and bridging ligand systems attract attention as molecular based magnetic materials [1, 2]. Recently, we have shown that 2,3-bis(2-pyridyl)pyrazine (dpp) may coordinate to metal ions in several modes, and thus has the ability to form mono- and dinuclear complexes as well as coordination polymers [3]. In continuation of this investigation we have reported here a novel copper(II) dimer [Cu2(Hdpp)2(ox)(Cl)2(H2O)2]Cl2•6(H2O) (1) and 1D coordination polymer {[Cu(dpp)(SO4)(H2O)2]}n (2), both involving dpp as a protonated cationic or neutral chelate ligand and oxalate or sulfate di-anions as bridges, respectively. The compound 1 crystallizes in the triclinic space group P-1: a = 8.6798(10), b = 10.294(3), c = 12.243(4) Å, α = 69.64(2), β = 72.54(2), γ = 84.33(2)°, whereas the compound 2 crystallizes in the monoclinic space group P21/c: a = 14.4096(4), b = 7.0000(2), c = 21.0565(7) Å, β = 132.193(2)°. In both structures, the metal atoms adjust the square-bipyramidal coordination cores in contrast to previously studied compounds [3], where copper atom adopts square-pyramidal surrounding. The N2O3Cl coordination sphere of Cu(II) atom in 1 (Fig. 1) is composed by two N atoms of chelating monoprotonated Hdpp ligand, two O atoms from oxalate bridging ligand, chlorine anion and a weakly coordinated water molecule (Cu1O1w = 2.757(4) Å). The oxalate bridges two Cu(II) atoms in dimer with Cu···Cu intramolecular separation of 5.174(1) Å. In 1D coordination polymer 2 N2O4 surrounding of Cu(II) atom is completed in basal plane by two N atoms of 2 chelate dpp ligand, a water molecule and oxygen of SO4 di-anion. Another water molecule and 2 oxygen atom of two-fold screw axis symmetry related SO4 occupy the apical positions. Thus, sulfate anions serve as bridges and unite the neighboring Cu(II) atoms in zigzag-like chains along the b crystallographic axis (Fig. 2). The Cu···Cu separation along the chain equals 5.1237(9)Å. The OH···O hydrogen bonds additionally link monomeric units within polymer. The π–π stacking of interdigitated aromatic moieties of adjacent chains unite them in supramolecular layers parallel to the ab crystallographic plane.

Fig.1 Fig.2 [1] S. Decurtins, H. W. Schmalle, Ph. Schneuwly, et. al, Inorg. Chem., 1995, 34, p. 5501. [2] J. Carranza, H. Grove, J. Sletten, et. al, Eur. J. Inorg. Chem., 2004, p. 4836. [3] E. Melnic. The 7th International Conference on Materials Science and Condensed Matter Physics, 2014, Chisinau, Moldova. DSCM 21P, p. 155

Acknowledgement. Authors thank SCOPES IZ73Z0_152404/1 and State Program of R. Moldova 14.518.02.04A for financial support.

P71

X-RAY STRUCTURES OF MONONUCLEAR AND POLYMERIC Cu(II) ACETYLACETONATE COMPLEXES WITH BIDENTATE LIGANDS CONTAINING NITROGEN DONOR ATOMS

E. Melnic

Institute of Applied Physics, Academy of Sciences of Moldova, Academiei str. 5, MD2028 Chişinau, R. Moldova, e-mail: [email protected]

The engineering of metal-organic materials with specific properties using molecular building blocks approach is possible by understanding the interplay of different interactions involved in self-assembly processes. The interest in copper complexes of 1,10-phenanthroline and its derivatives is stemming from their potential application as antimicrobial, antiviral, anti- inflammatory, antitumor agents, enzyme inhibitors, or chemical nucleases [1].The discrete coordination compounds can be extended in coordination polymers by using the exo-bidentate N,N-bipyridyl-based ligand involving pyridine rings linked by aliphatic chain, such as 1,2-bis(4- pyridyl)ethane and other similar ligands. Here, we report the crystal structures of three new Cu(II) complexes: two mononuclear [Cu(acac)(phen)Cl]CH3OH (1) and [Cu(acac)(phen)(NO3)]CH3OH (2), and 1D coordination polymer {[Cu(acac)(bpe)(NO3)]}n (3), where phen = 1,10-phenanthroline; acac = acetylacetonate and bpe = 1,2-bis(4-pyridyl)ethane (Fig.1).

a b Fig.1. View of mononuclear complex 2 and fragment of polymeric chain in 3 Crystals of both mononuclear compounds are triclinic, for 1: P-1, a = 8.9974(7), b = 9.2215(7), c = 12.0605(10)Å, α = 102.498(7), β = 97.666(7), γ=106.561(7)°,V=915.84(13)Å3; for 2: P-1, a = 8.6096(9), b = 10.2314(7), c = 12.1027(13)Å, α = 105.200(7), β = 104.230(9), γ = 108.009(7)°, V= 914.24(15)Å3. In the structures 1 and 2, the Cu atom adjusts the square- pyramidal coordination surrounding composed by two phen nitrogen atoms, two oxygen atoms of acac mono-anion in the basal plane and the apical position is occupied by the chloride or the nitrate anion (Fig.1, a). The molecular packing reveals the intermolecular π–π stacking interactions between the chelate phen aromatic moieties. The interplanar separation between the adjacent center symmetry related phen moieties and centroid···centroid distances between the nearest overlapping six-membered rings are 3.434Å and 3.797Å in 1, and 3.360Å and 3.701Å in 2. The addition of exo-bidentate bpe ligand in reaction which leads to complex 2 results in the one-dimensional coordination polymer 3 without phen chelate ligand. Compound 3 crystallizes in the orthorhombic space group Pbca, a=15.5250(8), b=14.5784(5), c=15.7358(7)Å, V= 3 3561.5(3)Å . The copper(II) ion exhibits again a distorted square-pyramidal N2O3 geometry formed by nitrogen atoms of two bpe ligands in cis-positions, two oxygen atoms from acac chelate, and nitrate anion in apical position. The Cu···Cu separation along the polymeric zigzag chain is 13.208Å and Cu···Cu distance between the next to nearest metals equals 15.736Å.

[1] S. Chandraleka,K. Ramya, G. Chandramohan, et.al, Journal of Saudi Chemical Society ,2014, 18(6), p.953 Acknowledgement. Financial support was provided by the project 15.819.02.03F

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PROBING THE MAGNETIC ANISOTROPY AND SPIN STRUCTURE OF Fe-4f COMPOUNDS BY 57Fe MÖSSBAUER SPECTROSCOPY

V. Mereacre, A. K. Powell

Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstr. 15, 76131, Karlsruhe, Germany

The magnetic anisotropy of some lanthanide ions can hamper reversal of the molecular magnetic moment and in recent years there has been growing interest in including lanthanides in transition metal magnetic materials in order to modify their properties. The main impact to anisotropy in magnetic materials comprising lanthanides results from the effects of the crystal field on the rare earth's 4f wavefunction. Using 57Fe Mössbauer spectroscopy we have investigated the magnetic interaction between the DyIII ion and 57Fe nuclei in several Fe-Dy containing clusters [Fe2Dy2(OH)2(teaH)2(R- C6H4COO)6] [1]. The central [Fe2(OH)2] unit is antiferromagnetically coupled and thus has an S = 0 ground state. This was proved by measurement of the Mössbauer spectra in an external magnetic field of isostructural yttrium(III) containing compounds [Fe2Y2(OH)2(teaH)2(R- C6H4COO)6]. This means that even under an applied field there is no orientation of the zero spin of the cluster and each antiferromagnetically coupled dimer is still relaxing fast on the Mössbauer time scale. Since the dysprosium derivatives are isostructural with the yttrium ones, then we conclude that the interaction between Fe-Fe in compounds [Fe2Dy2(OH)2(teaH)2(R-C6H4COO)6] should also be antiferromagnetic. This raises the question: - Why the internal field experienced by the iron nuclei is so big giving a magnetic sextet? (see Figure 1 (zero field)) The only impact to the internal hyperfine field at iron nuclei in compounds [Fe2Dy2(OH)2(teaH)2(R-C6H4COO)6] can result from the magnetic interaction with the anisotropic DyIII ions, which provide sufficient magnetic anisotropy to “block” the hyperfine field

Figure 1: 57Fe Mössbauer spectra of experienced by the iron nuclei. But what is more unexpected is [Fe2Dy2(OH)2(teaH)2(R-C6H4COO)6], that when an external magnetic field is applied, then the (R=2xNO2) in zero- and applied external magnetic fields 0.03 – 4 T at 3.0 K. magnetic onsets in spectra of [Fe2Dy2] compounds vanish with increasing field and the Mössbauer spectra at high fields (> 1 T) exhibit patterns typical of a diamagnetic complex (Figure 1, down). Here again emerges a question: - Why when a dc field is applied in Mössbauer spectra the sextets are vanishing? On applying an external magnetic field, it appears that the applied field affects the ground state of DyIII by a slight mixing of the excited state wave functions into the ground state lowering the energy of the system and resulting in a change of its direction of polarization. In this way the anisotropy of the DyIII ions is suppressed and no more interaction with iron ions occurs. Remarkably, the observed effects on the magnetic anisotropy and relaxation are dependent not only on the nature of the substituents, but also their position in the benzoic ring – para or meta [2]. In addition, they show a simple correlation to the Hammett constant of the ligand widely used for the study and interpretation of organic reactions and their mechanisms. These and several other results are analyzed in combination with ac magnetic susceptibility measurements and ab-initio calculations.

1. JACS, 133, 15335 (2011). 2. Chem. Commun. 49, 9666 (2013).

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SYNTHESIS, SPECTRAL CHARACTERIZATION AND STRUCTURE OF SOME NOVEL COPPER(II) COMPLEXES WITH THIOSEMICARBAZONES DERIVED FROM PYRIDOXAL

Reka-Ștefana Mezeya, Modrea Valentina Mihaelaa, Aurelian Guleab, Tudor Roșua

aInorganic Chemistry Department, Faculty of Chemistry, University of Bucharest, 23 Dumbrava Rosie Street, 050107 Bucharest, Romania bCoordination Chemistry Department, Moldova State University, Chisinau, Republic of Moldova

Thiosemicarbazones and their corresponding complexes represent a very interesting category of compounds which possess a wide spectrum of applications in bioinorganic chemistry and medicine [1, 2]. Due to their coordination capacity thiosemicarbazones are excellent reagents for the design of transition metal complexes [3]. As a continuation of our previous researches in the field of complexes with azomethine ligands derived from pyridoxal we prepared new ligands from the thiosemicarbazones category. The structures of ligands were characterized by elemental analysis, IR and 1H and 13C NMR spectroscopy. Using the new thiosemicarbazone type ligands we designed several copper(II) complexes. In order to evaluate the influence of the anions on the geometry of the complexes a series of inorganic copper(II) salts were used. The complexes were studied based on multiple physico-chemical techniques like IR and electronic spectroscopy, magnetic studies, thermal studies and single crystal X-ray diffraction. A direct relation between the nature of the contraions from the metal salts and the stereochemistry of the complexes can be observed.

[1] V.M. Leovac, V.S. Jevtovic, L.S. Jovanovic, G.A. Bogdanovic, J Serb Chem Soc. 70, 2005, 393; [2] T.S. Lobana, S. Indoria, A.K. Jassal, H. Kaur, D.S. Arora, J.P. Jasinski, Eur J Med Chem. 76, 2014, 145; [3] K. Jayakumar, M. Sithambaresan, A.A. Aravindakshan, M.R. Prathapachandra Kurup, Polyhedron 75, 2014, 50.

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INFLUENCE OF LOCAL BIOACTIVE COMPOUNDS ON SPLEEN LYSOSOMAL ENZYMES ACTIVITY IN ETHYLENE GLYCOL INTOXICATION

Mihalciuc Olga1, Garbuz Olga2, Pantea Valeriana1, Bernic Valentin1, Gulea Aurelian2

1State University of Medicine and Pharmacy "Nicolae Testemitanu" 2 State University of Moldova, Chisinau, Republic of Moldova

Background. The high prevalence of various diseases with a tendency to chronicity is caused by the difficulty of choosing optimal and safe methods of treatment and/or prevention, which is one of many problems of modern medicine. Several recent finding demonstrate the central role of the lysosome as crucial regulators of cell homeostasis and lysosomal dysfunction thus appears as a comon hallmark in many pathological conditions [1]. In connection with this of particular interest are local bioactive compounds (BC)  Schiff bases, their combination with 3d metals, that exhibit important biologic activity [2,3]. Nevertheless, their influence on the functional state of cellular lysosomal apparatus in spleen in ethylene glycol (EG) intoxication was not studied. The aim of the study was to elucidate the functional status of the lysosomal apparatus in ethylene glycol intoxication and to elucidate the influence of local bioactive compounds (BC) on spleen lysosomal enzyme activity. Methods. Ethylene glycol was administered per os. The main spleen tissue lysosomal enzymes activity  cathepsins (Cat) B, D, G, H, leucyl aminopeptidase (LAP), acid phosphatase (AP), β-galactosidase (β-Gal), β-glucosidase (β-Glu), N-acetyl-β-D-glucos-aminidase (NAG), arylsulfatases A, B and C, was determined by spectrophotometric micro method adapted to the Hybrid Multi-mode Microplate Rider Synergy H1, "BioTek" (USA). After ethylene glycol poisoning animals were treated with local BC: Schiff bases and their combination with 3d metals  CMD-4, CMD-8, CMJ-23, and the cyanobacterial remedy  BioR-Ge with enhanced content of organically bound Ge. Results. Local BC administration in ethylene glycol intoxication exerted significant influence on the studied enzymes activity, manifested by the suppression of the Cat D and G, inhibition of LAP, NAG, ß-Gal and AP. It is obvious that studied compound had selective action on lysosomal enzymes that depends on their degree of engagement at different stages of the disease process. CMD-4 inhibited Cat B, arylsulfatase A and B, LAP, NAG and ß-gal, kept low the levels of Cat D and H, and induced the AP activity. CMD-8 inhibited elastase and Cat B, kept low the LAP and ß-Gal activity, and induced the ß-Glu and arylsulfatase C activity. CMJ-23 inhibited Cat H, kept low NAG and LAP activity, and increased AP. Conclusions. The ability of studied BC to modulate the lysosomal acid hydrolases activity and to modify the functional status of spleen lysosomal apparatus in ethylene glycol intoxication was established. Further research in this area would enable the development of new effective and harmless treatment for immune system disorders, which will provide high curative and prophylactic effect, prevention and elimination of complications.

Bibliography. 1. Boya P. Lysosomal function and dysfunction: mechanism and disease. Antioxidants&Redox signaling, 2012; 17(5): 766-774. 2. Gulea A., et al. In vitro antileukemia, antibacterial and antifungal activities of some 3d metal complexes: Chemical synthesis and structure – activity relationships // Journal of Enzyme Inhibition and Medicinal Chemistry, 2008; V. 23. Nr.6, pp.806-818. 3. Roşu T., Gulea A., Nicolae A., Georgescu R. Complexes of 3dn Metal Ions with Thiosemicarbazones: Synthesis and Antimicrobial Activity // Molecules 2007, 12, p.782-796.

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INFLUENCE OF POLY(N-VINYLPYRROLIDONE) IN SYNTHESIS OF MAGNETITE (Fe3O4) NANOPARTICLES. Gutsul T.1, Mironic T.1, Nicorici A.1, Petrenko P.2 1Ghitu Institute of Electronic Engineering and Nanotechnologies, Academy of Sciences of Moldova, Academiei str. 3/3, Chisinau, MD-2028 Republic of Moldova. 2Institute of Applied Physics, Academy of Sciences of Moldova, Academiei str. 5, Chisinau, MD- 2028 Republic of Moldova Nanoparticles may provide advanced biomedical research tools based on polymeric or inorganic formulations or a combination of both. They have the potential to be used in many different biological and medical applications as in diagnostic tests assays for early detection of diseases, to serve as tools for noninvasive imaging and drug development, and to be used as targeted drug delivery systems to minimize secondary systemic negative effects [1]. The influence of poly(N-vinylpyrrolidone) (PVP) with different molar mass on the synthesis of magnetite (Fe3O4) nanoparticles was studied in the present work. The resultant material was studied by the X-ray diffraction method using a DRON-UM diffractometer (-2 method, =1.93604 Å). (Fig. 1). Furthermore, by using the Scherrer’s equation, the crystalline grain diameters of the Fe3O4 particles was found to be about (14  1) nm. FT-IR absorption spectra of PVP coated Fe3O4 nanoparticles and pure PVP were measured with a PerkinElmer Spectrum 100. FT-IR Spectrometer in the spectral range of 650– –1 4000 cm . A comparison of the spectra of the prepared Fe3O4/PVP nanoparticles and pure PVP reveals similar absorption bands in regions of 3600–2400 cm−1 and 1650–650 cm−1. The absorbent peak centered at 1289 cm–1 is due to C–N stretching vibration of PVP. The peak observed in pure PVP at at 1660 cm–1 belongs to C=O group. No shift was observed in the sample Fe3O4/PVP. It indicated that large excessive PVP remained on this sample, probably just remained free on the surface, despite the successive washing steps were done after the synthesis. The excessive free PVP molecules prevent the aggregation of the magnetic particles.

Fig. 1. XRD pattern of the sample Fe3O4

In summary, the present work reports on the properties of magnetite (Fe3O4) nanoparticles synthetized with poly(N-vinylpyrrolidone) (PVP) with different molar mass. The characterization and functionalization of Fe3O4 nanoparticles with PVP opens the possibility of formulating a new generation of magnetic materials.

References: 1. Margarethe Hofmann-Amtenbrink, Brigitte von Rechenberg, Heinrich Hofmann. Superparamagnetic nanoparticles for biomedical applications. Nanostructured Materials for Biomedical Applications. (2009), № 37, p. 119.

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ELECTROPHORETIC DEPOSITION OF CdSe/ZnS/PVP NANOCOMPOSITE

Mirzac Alexandra1, Gutul Tatiana2, Vera Zubareva1, Ion Bulhac1

1Institute of Chemistry, ASM Chisinau, Academiei str.3, Chisinau, MD-2028, 2 Institute of Electronic Engineering and Nanotechnology, Academiei str.3/3, Chisinau, MD-2028 [email protected]

Inorganic semiconductor nanocrystals posses superior light absorption, exceptional photoluminescence (PL) efficiency, high photostability, and a small exciton binding energy. High-quality semiconductor nanocrystals are usually synthesized by colloidal routes in coordinating solvents. The as-synthesized nanocrystals with hydrophobic groups on their surfaces are insoluble in strong polar solvents [1]. Ligand exchange process can transfer nanocrystals into polar solvents, it often generates surface defect sites that cause nonradiative exciton recombination. Polyvinylpyrrolidone (PVP) is usually served as a stabilizer of nanopartciles as the building blocks exhibit good compatibility with many inorganic, organic, and biological materials. The Electrophoretic Deposition (EPD) of quantum dot thin films is accomplished by applying a voltage between two conductive electrodes that are suspended in a colloidal quantum dot solution. The electric field established between the electrodes drives quantum dot deposition onto the electrodes. EPD allows parallel processing, as well, it enables deposition of films onto the electrodes of arbitrary geometry [2]. We synthesized CdSe/ZnS nanoparticles according to methods described in [3] and [4]. The amount of CdSe/ZnS nanoparticles was dissolved in hexane. In our research, we used a suspension of CdSe/ZnS nanoparticles, dissolved in a solvent: isopropanol, acetyl-acetone and PVP, dispersed in ultrasound bath. After, the suspension of core-shell nanoparticles was placed into an EPD cell, supplied with 2 metallic electrodes placed at 8 mm distance from each other. It was applied alternating current of 100 CdSe/ZnS CdSe/ZnS/PVP Hz frequency, 600 V – amplitude. We 0,9 571nm used a glass electrode covered with 0,8

596nm In2O3-SnO2 layer (ITO), also a platinum 0,7 electrode. 0,6

0,5 Photoluminiscence spectra of

0,4 CdSe/ZnS/PVP nanocomposite shows

, arb. un. arb. , Pl I 0,3 maximum at E = 2,15 eV (λ=571 nm), 0,2 measured at T = 300 K. Thus, the 0,1 experimental results prove that 0,0 CdSe/ZnS/PVP nanocomposite is 440 460 480 500 520 540 560 580 600 620 640 660 680 transparent and has luminiscent , nm properties. Fig. 1. Photoluminiscence spectra of nanoparticles CdSe/ZnS and nanocomposite CdSe/ZnS/PVP.

References: [1]. Hucheng Zhang, Dong Xu, Jianji Wang, Passivation-promoted photoluminescence efficiency of CdSe/PVP nanocrystals photoactivation. Materials Chemistry and Physics 133 (2012) 655 – 660. [2]. Katherine W.Song, Ronny Costi, Vladimir Bulovic, Electrophoretic Deposition of CdSe/ZnS Quantum Dots for Light-Emitting Devices, Adv. Mater. 2013, 25, 1420 – 1423. [3]. C. Murray et al., J. Am. Chem. Soc., 115, 8706 (1993). [4]. Peng et al., J. Am. Chem. Soc., 123, 183 (2001).

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THE SIZE EFFECT OF THE CORROSION RATE OF COPPER IN THE PYROPHOSPHATE ELECTROLYTE

V. Myrzakab, А.I. Dikusara

aInstitute of Applied Physics, Academy of Sciences of Moldova, str. Academiei 5,Chisinau, MD- 2028, Republic of Moldova, [email protected] bInstitute of chemistry, Academy of Sciences of Moldova, str. Academiei 3,Chisinau, MD-2028, Republic of Moldova

The deposition of copper from the pyrophosphate electrolyte is studied over the past decades [1-3] as an effective method of copper plating, but the problems of corrosion, and especially the size effects of corrosion, works devoted not so much. This paper deals with direct measurements of size effects of the corrosion rate of copper in pyrophosphate solution. Corrosion was investigated on the samples of the electrodeposited copper (electrode disk diameter 10, 25, 50 and 500 micron) obtained from pyrophosphate electrolyte with the following . . composition: 12.5 g/L of CuSO4 5H20 and 100 g/L of Na4P4O7 5H20, pH = 8 at room temperature. Corrosion was studied in the same electrolyte (without the addition of a copper ion) by measuring polarization curves from - 0.8 V to + 0.1 V at a scan rate 5mV/s. The corrosion rate was calculated with Program GPES. It is obtained that for microelectrodes with radius of 5 microns corrosion rate increases by 8 times compared with microelectrodes with radius of 25 microns. While for microelectrodes with radii in the range 25-250 microns measured corrosion rate was not changed. It is obtained that the investigated corrosion process - is corrosion with oxygen depolarization (in the range of 5-25 microns radii of microelectrodes reduction rate (dissolved oxygen) increases in 8 times). The results of measurements of the observed size effects are confirmed by calculations for the diffusion currents of microelectrodes, from which it follows that the size effect (increasing density of the diffusion current with decreasing size of the electrode surface) should be observed for surfaces with a radius of less than 20-30 microns. This research was funded by the ASM projects number 11.817.05.05.A "Electrochemical methods of obtaining and processing of new materials and coatings with improved functional properties" and №15.817.02.05.A "Physical-chemical methods and engineering aspects of the production of new materials and surfaces for multi-scale technologies", and also from the European project IRSES № 295202 (Oil & Sugar). 1. Dini J.W., Snyder D.D. Electrodeposition of Copper. In: Modern Electroplating, 50th Ed., John Wiley & Sons, Inc , USA, 2010, part 2, 33-78. 2. Török T. I., Orosz V., Fekete Z., Szirmai G. Direct cathodic deposition of copper on steel wires from pyrophosphate baths. Mater Sci Engin. 2012, 37/2, 99–110. 3. Cerisier M., Attenborough K., Fransaer J., Van Haesendonck C., Celis J-P. Growth mode of copper films electrodeposited on silicon from sulfate and pyrophosphate solutions. J Electrochem Soc. 1999, 146, 2156-2162.

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SYNTHESIS, STRUCTURE, AND BIOLOGICAL ACTIVITY OF COPPER COORDINATION COMPOUNDS OF SUBSTITUTED PYRIDINE-2-CARBALDEHYDE 4-(o-, m-, p-METHOXYPHENYL)THIOSEMICARBAZONES

A. Gulea1, N. Mitkevich1, V. Tsapkov1, O. Garbuz1, V. Prisacari2

1 Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Moldova 2Department of Microbiology, Virusology and Immunology Nicolae Testemitsanu State University of Medicine and Pharmacy, Chisinau, Republic of Moldova e-mail: [email protected]

It is known that many thiosemicarbazide derivatives possess biological activity and so are widely used in medical practice for the treatment of infections that are caused by various microorganism. Many of these substances are able to form coordination compounds with transition metals. Many of these coordination compounds are also biologically active. This property allows their use as a base for preparations that can be used in biochemistry and pharmacology. Therefore, synthesis and study of new biometal coordination compounds with thiosemicarbazide derivatives are of both scientific and practical interest. The aim of this work is the synthesis, determination of the composition, structure, physicochemical properties, and biological activity of copper coordination compounds of 2- formyl- (HL1-3), 2-acetyl- (HL4-6), and 2-benzoylpyridine (HL7-9) 4-(o-, m-, p- methoxyphenyl)thiosemicarbazones. Thiosemicarbazones HL1-9 were obtained by the reaction of condensation: 1 1 2 3 4 HL : R = OCH3, R = R = H, R = H; 2 1 3 2 4 1 2 HL : R = R = H, R = OCH3, R = H; 4 R R R HL3 : R1 = R2 = H, R3 = OCH , R4= H; 4 1 2 3 3 4 3 HL : R = OCH3, R = R = H, R = CH3; C N NH C NH R 5 1 3 2 4 HL : R = R = H, R = OCH3, R = CH3; N S 6 1 2 3 4 HL : R = R = H, R = OCH3, R = CH3; 7 1 2 3 4 HL1-9 HL : R = OCH3, R = R = H, R = C6H5; 8 1 3 2 4 HL : R = R = H, R = OCH3, R = C6H5; 9 1 2 3 4 HL : R = R = H, R = OCH3, R = C6H5.

This thiosemicarbazones react with copper(II) salts forming coordination compounds 1-9     [Cu(L )X]· nH2O (X  Cl , Br , NO3 , CH3COO ; n  13). Composition and structure of these compounds were determined on the basis of data from elemental analysis, magnetochemical research, and IR spectroscopy. The synthesized compounds selectively inhibit growth of human promyelocytic leukemia HL-60 cells, breast cancer MCF7 cells, prostate cancer LNCaP cells, and human melanoma MeW-164 cells in the concentration 10-5-10-7 mol/L. In addition some of the synthesized coordination compounds show selective bacteriostatic and bactericidal activity for some gram-positive, gram-negative microorganisms and fungi in the range of concentration 0.59-200 μg/mL. It was determined that synthesized compounds manifest the best activity towards Candida albicans и Staphylococcus aureus.

This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F.

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NaIO4/LiBr-SUPPORTED FUNCTIONALIZATION OF ENT-KAUR-16-EN-19-OIC ACID

Olga Morarescu, Marina Grinco, Maria Lunganu, Nicon Ungur

Institute of Chemistry, Academy of Science of Moldova, 3, Academiei str. Chisinau, Republic of Moldova e-mail: [email protected]

The scientific interest in diterpenic tetracyclic ent-kaur-16-en-19-oic acid (1) is explained by the fact that this compound possesses a broad spectrum of biological activities [1-3]. It was isolated from different vegetal sources, especially from sunflower Helianthus sp. [4]. Polyfunctionalized tetracyclic ent-kauranic terpenoids are also of a great interest, as a result of their pronounced biological activity. For the functionalization of ent-kaur-16-en-19-oic acid (1) the catalytic version of Prevost - Woodward reaction was used. We report herein the results of the transformation of ent-kaur-16-en-19-oic acid (1) catalyzed by LiBr and mediated by NaIO4, using the method described in the literature [5]. As a result, a mixture of diterpenic compounds was obtained, which was purified by column chromatography, resulting in the isolation of the functionalized ent-kauranic diterpenoids (2) – (6). Their structures were elucidated by NMR and IR spectroscopies. It should be mentioned, that diterpenoids (2), (3) and (5) containing a bromine atom at C-17 can potentially be endowed with interesting biological properties.

H H Br H H Br H 17 OAc H NaIO4/LiBr H H H H + + + AcOH OAc OH H H H H H CO2H CO2H CO2H CO2H CO2H 1 2 17E 4 (32%) 5 (17%) 6 (19%) + (10%) 3 17Z

Figure 1. Functionalization of ent-kaur-16-en-19-oic acid.

As a result of Prevost–Woodward transformation of ent-kaur-16-en-19-oic acid (1), new derivatives of ent-kaurenic acid, functionalized at C-15, C-16 and C-17 carbon atoms, have been obtained.

[1] Na, M.K.; Oh, W.K.; Kim, Y.H.; Cai, X.F.; Kim, S.H.; Kim, B.Y.; Ahn, J.S. Inhibition of protein tyrosine phosphatase 1B by diterpenoids isolated from Acanthopanax koreanum. Bioorg. Med. Chem. Lett., 2006, 16, pp. 3061–3064 [2] Dang, N.H.; Zhang, X.F.; Zheng, M.S.; Son, K.H.; Chang, N.W.; Kim, H.P.; Bae, K.H.; Kang, S.S. Inhibitory constituents against cyclooxygenases from Aralia cordata Thunb. Arch. Pharm. Res., 2005, 28, pp. 28–33. [3] Jung, H.A.; Lee, E.J.; Kim, J.S.; Kang, S.S.; Lee, J.-H.; Min, B.-S.; Choi, J.S. Cholinesterase and BACE1 inhibitory diterpenoids from Aralia cordata. Arch. Pharm. Res., 2009, 32, pp. 1399–1408. [4] Ungur, N.; Grinco, M.; Kulciţki, V.; Barba, A.; Bîzîcci, T.; Vlad, P.F. Isolation of ent-kaur-16-en-19-oic and ent-trachiloban-19-oic acids from the sunflower Helianthus Annuus L. dry waste. Chem. J. Mold., 2008, 3, pp. 105–108. [5] Emmanuvel, L.; Ali Shaikh, T.M.; Sudalai, A. NaIO4/LiBr-Mediated diastereoselective dihydroxylation of olefins: A catalytic approach to the Prevost—Woodward reaction. Org. Lett., 2005, 7, pp. 5071–5074.

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STATISTICAL CLASSIFIERS BASED ON NMR FINGERPRINTING OF URINE

Alina Nicolescu,1,2 Mihaela Balan,1 Natalia Uşurelu,3 Romana Vulturar,4 Bianca Andreica-Sandica,5 Andrei Miu,6 Calin Deleanu.1,2

1. “Petru Poni” Institute of Macromolecular Chemistry of the Romanian Academy, Iasi, Romania. 2. “Costin D. Nenitescu” Centre of Organic Chemistry of the Romanian Academy, Bucharest, Romania. 3. The Institute of Mother and Child, Chişinău, R. of Moldova 4. “I.Hatieganu” University of Medicine and Pharmacy, Department of Cell and Molecular Biology, Cluj-Napoca, Romania. 5. “Iuliu Hatieganu” University of Medicine and Pharmacy, Department of Pediatric Psychiatry, Cluj-Napoca, Romania. 6. “Babeş-Bolyai” University, Faculty of Psychology and Educational Sciences, Cluj- Napoca, Romania

Starting early 1980’s, proton nuclear magnetic resonance spectroscopy has proven to be a noninvasive, robust and reliable method in biofluids analysis. Since then, the use of 1H-NMR Spectroscopy in biomedical research has widely spread. Chemometric and pattern recognition methods are currently used for classification of NMR data obtained from biofluids. Different biological fluids have been analyzed, and among them urine seems to be the most popular one. This can be mainly due to its high metabolite content, accessibility and little sample preparation requirements. In this study an NMR-based metabonomic method was used to characterize the urinary metabolic profiling of several subjects with inborn errors of metabolism, depressive disorders and healthy controls.

The authors acknowledge the financial support of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PNII-ID-PCCE-2011-2-0045.

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A NEW METHOD OF SYNTHESIS AND SPECTROSCOPIC CHARACTERISTICS OF THE WATER–SOLUBLE DERIVATIVE OF BORON CLUSTER ANION 2– 1,2–[B12H10(OH)2]

A. Ogarkov, M. Biriukova, S. Shevtsov, A. Chernyavskii, S. Sakharov, and K. Solntsev

A. Baikov Institute of Metallurgy and Materials Science, Russian Academy of Sciences Leninskii prosp. 49, Moscow 119991, Russia

2– Derivatives of closo–[B12H12] anion show promise first as compounds used for the treatment of cancers by 10B-neutron capture therapy (BNCT) [1]. The BNCT is based on the selective accumulation of 10B isotope atoms in tumor cells and subsequent irradiation of them with slow neutron fluence. High energy particles resulting from the nuclear reaction 10B + 1n  [11B]  4He + 7Li + Q, which are characterized by shorter ranges as compared to cell dimensions, destruct tumor cells. The principal requirements for the boron containing drug are their selectivity and high content in 2– tumor. Derivatives of [B12H12] anion are the most adequate candidates for the application for BNCT since they exhibit high chemical and biological stability, are characterized by high boron content per molecule, and as a rule low toxicity. 2– 1,2–[B12H10(OH)2] hydroxy derivative can be synthesized by alkali hydrolysis of 1,2– 2– [C6H5CH2C(O)OB12H10OH] anion [2]. During heating at 80 С, a parent anion salt mixed with acetone and concentrated hydrochloric acid gives a mixture of 1,2– and 1,7–isomers of 2– [B12H10(OH)2] hydroxy derivatives [3]. We consider the interaction between bis(tetrabutilammonium) dodecagidro–closo– dodecaborate (2–), (TBA)2[B12H12] and benzene–1,2–dicarboxylic acid during holding at 190– 195 С in a dry argon atmosphere followed by alkaline hydrolysis of the formed intermediate. In the course of found reaction benzene–1,2–dicarboxylic acid is both reagent and solvent. –1 Product was identified by elemental analysis, IR spectroscopy (2 475 cm B–H; 3 653, –1 –1 11 3 645 cm O–H; 1 011 cm B–B), and B NMR spectroscopy (CD3CN) {3.72 (s; B1, B2); – 16.16 (d; B3, B6; 1J(11B,1H) = 121.3); –18.13 (d; B4, B5, B7, B11; 1J(11B,1H) = 126.8); –21.51 (d; B8, B10; 1J(11B,1H) = 129.1); –25.23 (d; B9, B12; 1J(11B,1H) = 129.1)}.

11B– and 11B{1H} NMR

Hydrolysis of the reaction product between bis(tetrabutilammonium) dodecagidro–closo– dodecaborate (2–) (TBA)2[B12H12] and benzene–1,2–dicarboxylic acid melt in an inert 2– atmosphere results in the formation of 1,2–[B12H10(OH)2] water soluble ortho–isomer.

1. Hawthorne M.F. Angew. Chem. Int. Ed. Engl., 1993, 32, 950. 2. Krause U., Preetz W. Z. Anorg. Chem., 1995, 621, 516. 3. Zhizhin K.Yu., Votinova N.A., Goeva L.V., Kuznetsov N.T. Russ. J. Coord. Chem., 2001, 27, 625.

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SURFACE PHOTOCHEMISTRY OF VINCLOSOLINE WITH ADDITION OF AMMONIUM FERRIC CITRATE.

Ivan Osipov

Institute of Chemistry, Academy of Sciences of Moldova, Academiei str., 3, Kishinev MD-2028, Republic of Moldova

Natural solid-gas interfaces, such as soil and vegetation, can accumulate globally relevant pollutants such as the Persistent Organic Pollutants (POPs) and chemicals coming from chemical spills or resulting from applications with a specific purpose. Surfaces are, in most cases, the first contaminated environmental compartment and from which the generalized spread of organic pollutants takes place. A particular case is that of pesticide applications. They are needed on the surfaces during a certain period of time, to actuate, but after this they are unwanted compounds and their residues should be removed. Photo-degradation is recognized to be one of the major dissipation pathways of pesticides on solid surfaces under natural conditions [1]. We studied the photo-transformation of vinclozoline on the model surfaces silica and cellulose in the presence of additive that can increase the photo-degradation pathway under sunlight irradiation- citrate ammoniacal iron (III). The main photoproducts were obtained (figure III 1) for vinclozoline with addition of [2C6H5O7Fe · C6H6O7(NH4)2 ·nH2O]. Vinclozoline give one major product in silica and cellulose – 3,5 dichlorphenyl isocyanat and this is main product in phototransformation with and without addition of citrate ammoniacal iron (III) . Main product can be easy transformed in 3,5- dichloroaniline under influence of water or UV irradiation. With III addition of [2C6H5O7Fe · C6H6O7(NH4)2 ·nH2O] we can observe essential acceleration (comparative to the model without additives) of degradation of vinclozoline on solid support . After carrying out investigation on liquid and solid state we can say that phototransformation pathway with addition of citrate ammoniacal iron (III) is equal to pathway in natural conditions (on silica and cellulose).

Figure 1 : GS-MS traces of vinclozolin on silica 30 min UV irradiated (254 nm) without (2) and with addition of ammonium ferric citrate (1)

[1] Da Silva, J.P.; Ferreira, L.F.V.; Osipov, I.; Machado, I.F, J. Hazard. Mater. 179 (2010) 187–191.

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P83

SYNTHESIS AND IN VITRO ANTILEUKEMIA ACTIVITY OF COPPER (II) NITRATE COMPLEX WITH 2-HYDROXY-3-METHOXYBENZALDEHYDE 4-MORPHOLINETHIOSEMICARBAZONE.

A. Paholnitcaia1, D. Poirier2, M. Perreault2, I. Tatarciuc1, P. Petrenco3, A. Gulea1

1 Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Moldova e-mail: [email protected] 2 Laboratory of Medicinal Chemistry, CHU de Québec-Research Center Université Laval, Québec City, Canada 3.Institute of Applied Physics of Academy of Sciences of Moldova, Chisinau, Moldova

Thiosemicarbazones represent an important class of ligands with nitrogen and sulfur donor atoms due to their interesting chemical, biological and medicinal properties. The coordination chemistry of ONS donor ligands has been of considerable interest due to their remarkable structural and biological properties. Interactions between aromatic rings are very important in proteins and protein–DNA systems for protein stabilization and various regulatory processes. In our research coordination compound was obtained by template synthesis. A solution of copper salt was added to an ethanol solution of 4-morpholinethiosemicarbazide with 2-hydroxy-3-methoxybenzaldehyde. The resultant solution was heated (50-550C) and mixed continuously with a magnetic stirrer. After cooling, small green crystals appeared. They were filtered from the reaction mixture, washed with ethanol, and dried in air. Yield: 80%. Magnetic measurement of the coordination compound showed that it is paramagnetic. The value of the effective magnetic moment indicates its monomeric structure. The X-ray analysis showed that the copper atom in the mononuclear complex is five-coordinated. Complex has a distorted square pyramidal geometry. The basal coordination positions are occupied by the phenolic oxygen, azomethine nitrogen, and sulfur atoms of the thiosemicarbazone, the fourth place is occupy by oxygen from the water molecule, the fifth place is occupied by oxygen atom from the ethanol.(Fig.) The in vitro cytotoxicity of the complex on human promyelocytic leukemia cells (HL-60) was determined by a MTS-based assay. The cell proliferation of the control (untreated cells) was fixed to 100%. The results are expressed as the percentage of cell growth inhibition at three concentrations. The complex show a important antiproliferative activity at all concentrations. Thus, complex inhibited 95% of cell growth at 10µM, 95% of cell growth at 1µM and 3% of cell growth at 0,1 µM.

Figure: Structure of copper (II) nitrate complex with 2-hydroxy-3-methoxybenzaldehyde 4-morpholinethiosemicarbazone.

Acknowledgements: This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F

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SYNTHESIS, STRUCTURE, AND BIOLOGICAL ACTIVITY OF COPPER, NICKEL, AND ZINC COMPLEXES WITH 2-BENZOYLPYRIDINE 4-MORPHOLINETHIOSEMICARBAZONE

A. Paholnitcaia1, M. Perreault2, O.Garbuz1, V.Gudumac3, A. Gulea1

1 Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Moldova e-mail: [email protected] 2 Laboratory of Medicinal Chemistry, CHU de Québec-Rerarch Center Université Laval, Québec City, Canada 3.State University of Medicine and Pharmacy “N. Testemitanu”, Chisinau, Moldova.

Thiosemicarbazones are of considerable interest because of their potentially beneficial biological activities, such as antitumor, antibacterial, antiviral, and antimalarial activities. Some of them are already used in medical practice. It is found that in many cases, their useful properties correspond well to their ability to form chelates with metal ions. Biological activities of the metal complexes differ from those of either the ligand or the metal ion itself. Increased and/or decreased biological activities are reported for various metal complexes as well as the well-studied copper(II), zinc(II), and iron(III). Therefore, the synthesis and study of the structural characteristics of copper, nickel and zinc coordination compounds with thiosemicarbazones are of both practical and scientific interest. In our research coordination compounds were obtained by template synthesis. A solution of copper, nickel or zinc salt was added to an ethanol solution of 4-morpholinethiosemicarbazide with 2-benzoylpyridine. The resultant solution was heated (50-550C) and mixed continuously with a magnetic stirrer.

After cooling, small crystals appeared. They were filtered from the reaction mixture, washed with ethanol, and dried in air. Yield: 80-85%. Magnetic measurements showed that copper complexes have polynuclear structures; zinc and nickel complexes have monomeric structures. The in vitro cytotoxicity of the synthesed complexes on human promyelocytic leukemia cells (HL-60) was determined by a MTS-based assay The synthesized complexes selectively inhibits the growth and proliferation of human promyelocytic leukemia HL-60 cells in the concentration range 10-5-10-7 mol/L. The copper complexes have high cytotoxic activity. The nickel complexes have the lowest activity. The synthesized compounds also manifest antioxidant activity. The IC50 for copper complex is 90 M and for nichel complex is 17 M. Acknowledgements: This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F

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SYNTHESIS, CHARACTERIZATION AND BIOLOGICAL ACTIVITY OF NOVEL CU(II), PD(II), PT(II) COMPLEXES WITH 2-HYDROXY-8-ETHYL- TRICYCLO[7.3.1.0.2,7]TRIDECANE-13-ONE THIOSEMICARBAZONE

Elena Pahonțua, Codruța Paraschivescub, Diana-Carolina Ilieșc, Donald Poirierd, Camelia Opreane, Aurelian Guleaf, Tudor Roșuc

aInorganic Chemistry Department, Faculty of Pharmacy, University of Medicine and Pharmacy “Carol Davila”, 6 Traian Vuia Street, 020956 Bucharest, Romania; E-mail adress: [email protected] bOrganic Chemistry Department, Faculty of Chemistry, University of Bucharest, 90-92 Panduri Street,050663 Bucharest, Romania. cInorganic Chemistry Department, Faculty of Chemistry, University of Bucharest, 23 Dumbrava Rosie Street, 020462 Bucharest, Romania. dOncology and Molecular Endocrinology Research Center CHUL, Research Center and Universite Laval, CHUQ-CHUL, 2705 Boulevard Laurier, Quebec City G1V4G2 Canada. ePharmaceutical Chemistry Department , Faculty of Pharmacy, University of Medicine and Pharmacy “Victor Babeş“, 2 Eftimie Murgu Square, 300041 Timişoara, Romania. fCoordination Chemistry Department, Moldova State University, 60 Mateevici Street, 2009 Chisinau, Republic of Moldova.

The chemistry of transition metal complexes of thiosemicarbazones have gained considerable attention due to their diverse applications in the pharmacological field as antimicrobial agents [1- 4] and found to have in vitro cytotoxic effects against cancer cells [5]. In this research, we have synthesized and characterized new Cu(II), Pd(II) and Pt(II) complexes: [Cu(L)(H2O)2(OAc)](1),[Cu(L)(H2O)2(SO4)](2),[Cu(L)(H2O)2(NO3)](3),[Cu(L)(H2O)2(ClO4)](4) , [Cu(L)2(H2O)2] (5), [Pd(L)(OAc)]H2O (6), [Pt(L)2] (7) were HL= 2-hydroxy-8-ethyl-tricyclo [7.3.1.0.2,7]tridecane-13-one-thiosemicarbazone. The ligand has been characterized by elemental analyses, IR, 1H NMR and 13C NMR spectroscopy, mass spectroscopy. All complexes have been characterized by IR, 1H NMR, 13C NMR, UV-Vis, FAB, EPR, mass spectroscopy, elemental and thermal analysis, magnetic susceptibility measurements and molar electric conductivity. The physico-chemical analyses confirmed the composition and the structure of the newly obtained complex combinations. All complexes with 2-hydroxy-8-R- tricyclo[7.3.1.0.2,7]tridecane-13-one thiosemicarbazone have been tested for their antimicrobial activity against Escherichia coli, Salmonella enteritidis, Staphylococcus aureus, Enterococcus, Candida albicans and cytotoxicity against SKBR-3 human breast, MCF-7 human breast, A375 human melanoma cancer cells and HL-60 human promyelocytic leukemia cells.

References

[1] J.G. Cory, A.H. Cory, G. Rappa, A. Lorico, M.C. Liu, T.-S. Lin, A.C. Sartorelli; Biochem. Pharmacol. 48 (1994) 335–344. [2] T.S. Lobana, S. Khanna, R.J. Butcher, Dalton Trans. 41 (2012) 4845–4851. [3] N. Gokhale, S. Jain, M. Yadav; Curr. Top. Med. Chem. 15 (2015) 37-42. [4] T. Roșu, E. Pahonțu, S. Păsculescu, R. Georgescu, N. Stănică, A. Curaj, A. Popescu, M. Leabu; Eur. J. Med. Chem. 45 (2010) 1627-1634. [5] E. Pahonțu, V. Fala, A. Gulea, D. Poirier, V. Tapcov, T. Roșu; Molecules 18(8) (2013) 8812-8836.

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SOME NEW Cu(II), Co(II) AND Ni(II) COMPLEXES CONTAINING AN ONS DONOR THIOSEMICARBAZONE: SYNTHESIS, CRYSTAL STRUCTURES AND BIOLOGICAL ACTIVITY.

Elena Pahonțua, Felicia Juleab, Yurii Chumacovc, Petru Petrencoc, Tudor Roșud, Aurelian Guleab aInorganic Chemistry Department, Faculty of Pharmacy, University of Medicine and Pharmacy “Carol Davila”, 6 Traian Vuia Street, 020956 Bucharest, Romania; E-mail adress: [email protected] bCoordination Chemistry Department, Moldova State University, 60 Mateevici Street, 2009 Chisinau, Republic of Moldova. cInstitute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Republic of Moldova. dInorganic Chemistry Department, Faculty of Chemistry, University of Bucharest, 23 Dumbrava Rosie Street, 020462 Bucharest, Romania.

The coordination chemistry of thiosemicarbazone complexes involving pyrazolone-ring has excited great interest among chemists in recent years due to their applications in catalysis and their relevance to bio-inorganic systems [1- 4]. Complex combinations of Cu(II), Co(II), and Ni(II) with thiosemicarbazone derivatives of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone 4- R-thiosemicarbazone (where R= CH3, C6H5, C5H5N) were synthesized. The new obtained compounds were characterized by 1H NMR, 13C NMR, IR, UV-Vis, EPR spectroscopy, elemental analysis, molar electric conductibility and, magnetic susceptibility. In addition, the structures of the ligands and six complexes has been determined by X-ray diffraction method.

Fig.1. Molecular structures for two complexes of Cu(II).

The ligands and the newly formed complexes were tested for the effects on HL-60 cell proliferation.

References [1] K. Shanker, R. Rohini, K. Shravankumar, P. Muralidhar Reddy, Y.P. Ho, V. Ravinder; Spectrochim. Acta 73A (2009) 205–211. [2] P. Krishnamoorthy, P. Sathyadevi, A.H. Cowley, R.R. Butorac, N. Dharmaraj; Eur. J. Med. Chem. 46 (2011) 3376–3387. [3] T. Rosu, E. Pahontu, D-C Ilies, R. Georgescu, M. Mocanu, M. Leabu, S. Shova, A. Gulea; Eur. J. Med. Chem. 53 (2012) 380-389. [4]. E. Pahonțu, F. Julea, T. Roșu, V.L. Purcărea, Y. Chumakov, P. Petrenco, A. Gulea; J. Cell. Mol. Med. 19(4) (2015) 865-878.

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SUPRAMOLECULAR ASSEMBLIES OF CU(II) SYSTEMS BASED ON THIOSEMICARBAZONE LIGAND

Tatiana Palamarciuc1, Elena Stratulat1, Sergiu Sova1,2, A. Pui3, and Oleg Palamarciuc1*

State University of Moldova, Mateevici 60, Chisinau, MD-2009 Republic of Moldova 2Petru Poni Institute of Macromolecular Chemistry, Iași, Romania; 3Alexandru Ioan Cuza University, Iași, Romania. *E-mail: [email protected]

In memoriam to Prof. Mihail Revenco

The Cu(II) complexes with organic ligand derived from thiosemicarbazide fragment are known as compounds with original analytical, biological and magnetic properties. Coordination compounds of Cu(II) with thiosemicarbazide derivatives ligands are related as mononuclear in [1-3] and binuclear structures in [4]. In this work we show a new type of coordination of the thiosemicarbazide fragment - using the N(2) atom as a linker to obtain supramolecular systems. Firstly this type of assembling was established using salicylaldehyde S-methylisothiosemicarbazone in alkaline medium. Cu(II) complex is coordinated tridentate via ONN donor atoms from thiosemicarbazone. The mononuclear units are assembled in polymer via N(2) atom from neighboring molecule. In the case of imidazol thiosemicarbazone derivatives the reaction was realised between copper(II) perchlorate and HL in ethanol. The crystalline product was separate after three days by filtration, washed with ethanol and dried in vacuum. The X Ray crystallographic analysis shows a polymer structure of the complex similar with previously reported case of salicylaldehyde S- methylisothiosemicarbazone (Figure 1).

Fig. 1. ORTEP representation of Cu(II) 1D compound

The Cu(II) complex have pyramidal geometry. In mononuclear unit Cu(II) is coordinate tridentate via NNS donor atoms from thiosemicarbazone, O from perchlorate ion and in the fifth position is the N(2) atom from neighboring molecule. The N(2) atoms plays a role of linker to assemblies supramolecular Cu(II) systems.

Reference [1] Bourosh P. N. et al. Russ. J. Coord. Chem., Vol. 19, 1993, p. 864 - 871. [2] Bourosh P. N. et al. Russ. J. Inorg. Chem., Vol. 32 Nr. 10, (1987), p. 2482. [3] Simonov Yu. A. et al. Dokl. Acad. Nauk SSSR, Vol. 275, 1984, p. 1419 - 1423. [4] Герасимов В. И. и др. Кристалография, 1976, Том. 21, № 2, с. 399 - 401.

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ADIPIC ACID - CARBON STEEL CORROSION INHIBITOR IN NATURAL WATER

V.I.Lozan*, V.V.Parshutin**, N.S.Sholtoyan**, A.V.Kovali**, N.V.Chernysheva**

*Institute of Chemistry of the Academy of Sciences of Moldova ** Institute of Applied Physics of the Academy of Sciences of Moldova [email protected]

It was studied the suppression process of corrosion of steel in Chisinau tap water, which by total content of chloride and sulfate ions (more than 150 mg/l) is a strong corrosive medium and by value of Langelie index (-0.08) is close to its equilibrium state. As inhibitor has been used a representative of a number of saturated dibasic acid - adipic acid:

with concentration of 0,025-0,75 g/l.

This acid is important in the preparation of polymer compounds. It is formed by the oxidation of fats. It is used in small quantities in the food industry to replace the citric and tartaric acids. This acid is also found in beet juice. It is shown that the greatest effect is achieved by inhibiting the corrosion of steel when is used in an amount of 0,025-0,75 g/l of adipic acid. Thus, when the inhibitor concentration is 0,05 g/l and at 8 and 24 hours of testing, the corrosion losses are reduced accordingly 7,8 and 6 times, providing a degree of protection Z equal to 87,2% and 85% respectively. At inhibitor concentration of 0,1 g/l at 24 hours of test, the corrosion rate is reduced by 5.5 times, and at a concentration of 0,25 g/l and 72 hours of tests, the braking coefficient is 5.5. The quantity of inhibitor introduced into the corrosive medium, play a crucial role. The lower limit of the concentration is equal to 0,025 g/l, because at lower levels of the administration of the inhibitor in the medium insignificantly reduces the corrosion losses. The upper limit of concentration of inhibitor is to be regarded as 0,75 g/l, as a further increase in the concentration the corrosive loss only slightly decrease, but is growing the costs of inhibitor.

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THE INHIBITION OF CORROSION OF STEEL IN WATER BY α-KETOGLUTARIC ACID

L.F.Chapurina*, V.I.Lozan*, V.V.Parshutin**, N.S.Sholtoyan**, A.V.Kovali**, N.V.Chernysheva** [email protected]

*Institute of Chemistry of the Academy of Sciences of Moldova ** Institute of Applied Physics of the Academy of Sciences of Moldova

Chisinau tap water by the chemical composition is medium or moderately hard. As the total content of chloride and sulfate ions (more 150 mg/l), it relates to a highly aggressive 2¯ medium. The SO4 ions caused a common, relatively uniform corrosion. However, on the inner surface of pipes can be formed the pitting due to the presence in the water of activating chlorine ions, which in some cases may be through, which leads to an emergency. Moreover, the ionized iron by passing into the water, are accumulates there to deteriorate its quality. It is known to use as a corrosion inhibitor carboxylic acids or their salts. By us, was used α-ketoglutaric acid HOOC-C(=O)CH2-CH2-COOH with a concentration of 0.05-0.75 g/l. In this case, the corrosion loss of metal is reduced by more than 7 times, providing a degree of protection Z = 87,8 % at a concentration of 0,25 g/l and a test duration of 72 hours. It should be noted, that is observed a slight difference in the values of the parameters of inhibiting of steels in the corrosion medium from the holding time that says about the stability of the inhibitor. In the process of corrosion, the pH of medium is slightly basified with increasing the time of tests of samples. Thus, the higher the concentration of the inhibitor, the more anodic potential shifts to the positive side, which indicates about the difficulty of the of ionization process of the metal. Addition of inhibitor in the corrosion medium shifts the stationary potential of the de- energized electrode in the negative side that says that the inhibitor is the inhibitor of cathodic action. Thus, was developed an environmentally safe and convenient to operate inhibitor of corrosion of steel in hydraulic structures, where the medium is natural water.

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P90

TETRAACETATE-DI-(1.2-CYCLOHEXANEDIONEDIOXIME)-DI-AQUA(µ2-4,4'- BIPYRIDYL)-DI-ZINC(II) – INHIBITOR OF STEEL CORROSION IN WATER

Parshutin V.V.*, Sholtoyan N.S.*, Covali A.V.*, Chernishova N.V.*, Coropceanu E.**, Croitor L.*, Fonari M.S.*

*Institute of Applied Physics, Academy of Sciences of Moldova **Institute of Chemistry, Aсademy of Sciences of Moldova [email protected]

The aqueduct water from Chisinau (chemical composition, taking into account the 2- - 2- - 2+ 2+ seasonal deviations, mg/L: СО3 - 6; НСО3 - 98.0; SO4 - 204.0; Cl - 57.0; Са - 72.5; Mg - 19.5; the total salt content of 457 mg/L, total hardness of 5.22 mmol/L, pH variation within the limits of 7.2-7.6) is generally hard or with moderate hardness. After Langelier index value (- 0.08) its condition is close to that of balance. According to the summary content of chloride and sulfate ions (more than 150 mg/L) it presents a very aggressive environment favorable for corrosive processes. The inclusion in the environment of the tetraacetate-di-(1,2-cyclohexandiondioxime)-di- aqua(µ2-4,4'-bipyridyl)-di-zinc(II), not modifying the character of the dependence of the corrosion speed on the experiment time, hurries the formation of the protective layers on the metal surface and leads to a faster setting of the dynamic balance and the considerable decrease of corrosion, especially with a bigger concentration of the complex. The adding of the inhibitor in the concentration of 0.1 g/L makes the environment a little more basic. The increase of the concentration up to 0.5 g/L the pH values decrease at all the experiment periods. At all the concentrations of the inhibitor the duration of the experiment influences on the environment pH, corrosive as well. At the duration of 8 hours there is a rapid alkalization of the electrolyte, then there can be observed the acidification up to 24 hours. The increase of the experiment duration up to 72 hours the environment gets alkalized again, but with the increasing time, the pH remains constant. After changing the values of the stationary potential of the disconnected electrode, depending on the substance concentration and the test periods (shift in the negative direction) there was stated that the proposed coordination compound is an inhibitor of the cathode action. It was established that while the introduction of the inhibitor into the environment, at the corrosive metal surface there are formed coating protective layers, in the composition of which along with iron oxide and hydroxide (maghemite γ-Fe2O3 and lepidocrocite γ-FeOOH), deposits of carbonates in form of calcite and small amounts of sulfates enter insoluble complexes - products of the interaction of the ionized iron with the coordination compounds or products of their decomposition. Thus, it was developed a corrosion inhibitor for the closed systems of steel aqueducts for natural water, which ensures the growth of γ braking coefficient to 9.4 times and the level of Z protection up to 84%. According to these indicators the proposed coordination compound is superior to the organic inhibitors used in practice, containing acetates and it is more convenient for use because other preparations are multicomponent and contain high concentrations of constituent substances, a fact which makes it difficult to follow the process of elaborating inhibitors and keeping them in the required limits.

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P91

THE CRYSTAL STRUCTURES OF IMIDAZOLE-[2-(2-HYDROXО-BENZYLIDENE)- N-(PROP-2-EN-1-YL)HYDRAZINCARBOTHIOAMIDE]-COPPER(II) AND (3,5- DIBROMOPYRIDINE)-[2-(2-HYDROXОBENZYLIDENE)-N-(PROP-2-EN-1- YL)HYDRAZINECARBOTHIOAMIDE]COPPER(II) NITRATES

P. Petrenko1, V. Graur2, Yu. Chumakov1, V. Smaglii2, V. Tsapkov2, V. Crudu3, S. Eftodii3, А. Gulea2

1Institute of Applied Physics of Academy of Sciences of Moldova, Chisinau, Republic of Moldova 2Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Republic of Moldova 3Phthisiopneumology Institute ”Chiril Draganiuc”, Republic of Moldova e-mail: [email protected]

Salicylidenethiosemicarbazide and its derivatives contain a wide range of donor atoms and form with transition metal ions coordination compounds with various composition, structure, and properties. Many of these coordination compounds possess antimicrobial, antifungal, and antitumor activities. Coordination compounds of copper(II) manifest these properties more often than any other 3d-metal complexes. It was determined that insertion of various amines into inner sphere in many cases results in enhancement of these properties. Therefore, the synthesis and study of new mixed-ligand copper coordination compounds, which contain thiosemicarbazones and amines, are of both scientific and practical interest. The aim of this work is the synthesis, determination of structural features of imidazole-[2- (2-hydroxоbenzylidene)-N-(prop-2-en-1-yl)hydrazinecarbothioamide]copper(II) nitrate (I) and (3,5-dibromopyridine)-[2-(2-hydroxоbenzylidene)-N-(prop-2-en-1-yl)hydrazinecarbothioamide]copper(II) nitrate (II)

Fig. 1. The molecular structure of I Fig. 2. The molecular structure of II

The coordination compunds I and II were synthesized by the reaction between ethanolic solutions of copper(II) nitrate, salicylaldehyde 4-allylthiosemicarbazone (H2L) and imidazole or 3,5-dibromopyridine in 1:1:1 molar ratio. The X-ray diffraction analysis of monocrystals of I and II showed that these complexes have dimeric structures. Phenolic oxygen atoms of H2L bridge two copper atoms. H2L acts as a tridentate monodeprotonated ligand. The amines are monodentate. Two nitrate-ions are in the outer sphere. The synthesized coordination compounds selectively inhibit growth of human promyelocytic leukemia HL-60 cells in the range of concentration 10-5 -10-7 mol/L. Moreover, the sinthisezed coordination compounds show bacteriostatic activity towards tuberculosis bacteria H37Rv in the range of concentration 10-20 μg/mL.

This work was fulfilled with the financial support of the Project 14.518.04.07A of the State Program.

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THE CRYSTAL STRUCTURE AND ANTIMICROBIAL ACTIVITY OF BIS[METHYL- N’-(2-HYDROXOBENZYLIDENE)-N-PROP-2-EN-1- YLCARBAMOHYDRAZONOTHIOATE]CHROMIUM(III) NITRATE

P. Petrenko1, V. Graur2, Yu. Chumakov1, I. Truhina2, V. Tsapkov2, V. Prisacari3, E. Zariciuc3, V. Rudic3, А. Gulea2

1Institute of Applied Physics of Academy of Sciences of Moldova, Chisinau, Moldova 2Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Moldova 3State University of Medicine and Pharmacy “N. Testemitsanu” e-mail: [email protected]

The aim of this work is the synthesis, study of structure and antimicrobial activity of bis[methyl-N’-(2-hydroxobenzylidene)-N-prop-2-en-1-ylcarbamohydrazonothioate]- chromium(III) nitrate. The coordination compound was synthesized by the reaction between ethanolic solutions of chromium(III) nitrate hexahydrate and salicylaldehyde 4-allyl-S-methylisothiosemicarbazone (HL) in 1:2 molar ratio. Two types of monocrystals with different colures (orange and brown) were obtained as a result of recrystallization from ethanol. Their crystal structures of both type of crystals were determined by X-ray analysis.

Form a Form b Fig. 1. The crystal structure of bis[methyl-N’-(2-hydroxobenzylidene)-N-prop-2-en-1-ylcarbamohydrazonothioate]-chromium(III) nitrate.(forms a and b)

It was determined that forms a and b of these complex are optical isomers. There are two molecules of isothiosemicarbazone HL in the inner sphere that act as tridentate monodeprotonated ligands and coordinate to the central atom of chromium by phenolic oxygen atoms, azomethinic and thiocarbamidic nitrogen atoms forming five- and six-membered metallacycles. The molecules of isothiosemicarbazone HL are almost planar and are in the mutually perpendicular planes. One nitrate-ion is in the outer sphere of each complex. The synthesized compound manifests selective bacteriostatic and bactericidal activity for a series of gram-positive (Staphylococcus aureus and Enterococcus) and gram-negative (Escherichia coli and Salmonella abony) microorganisms and Candida albicans in the range of concentration 0,5-2,0 mg/mL.

This work was fulfilled with the financial support of the Project 14.518.04.07A of the State Program.

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HYDROGEN ADSORPTION PROPERTIES OF MICROWAVE ACTIVATED CARBONS

Oleg Petuhov, Lupascu Tudor

Institute of Chemistry of Academy of Science of Moldova, 3, Academiei str., Chisinau MD2028, Republic of Moldova, e-mail: [email protected]; phone: (+373 22) 72 54 90; fax: (+373 22) 73 99 54

The storage of hydrogen in an accessible form for use in fuel elements is a global problem. Current research in this field is aimed at synthesis of materials that would meet the criteria proposed by National Department of Energy of USA. These criteria take into account a wide range of parameters: the temperature and pressure, at which the material can be used, the amount of hydrogen that can be stored, the number of cycles and speed of loading/ unloading the hydrogen, toxicity and safety of the material etc. The methods for storage of hydrogen are diverse: compressed, liquid, chemical, adsorption storage, but none, at this moment, does not meet all the applicability requirements [1]. Physical adsorption method has some obvious advantages: fully reversible process, fast cycle life and refilling time. At the same time, the introduction into practice of this method is limited by the necessity of maintaining the low temperature and high pressure. The active carbons are a broad class of adsorbents that are widely studied in the process of hydrogen storage [2]. The attractiveness of activated charcoal is explained by large surface area and volume of micropores, posibility of controlling their structure and low production price. The goals of this study were to obtain microporous activated carbons by microwave treatment and to investigate their hydrogen adsorption properties. A series of activated carbons were prepared by impregnating the nut shells with KOH in ratio of 1:1 to 1:4 by weight and subsequent microwave activation. The microwave activation was performed at 700W for 5 minutes. The active carbons were studied by gas adsorbtion method at 77K, by using nitrogen and hydrogen as adsorbates. All the active carbons are mostly microporous with a large adsorption surface. Mass of adsorbed at 77K hydrogen well correlates with surface area and volume of micropores. The activated carbon obtained by impregnation with KOH in 1:4 ratio by weight possesses the best adsorption features with a maximum capacity of retaining hydrogen of 3.82wt.% and 0.05 wt.% at 77K and 296K, respectively. The energy of hydrogen adsorption in this sample constitutes 6.75 kJ/mol (77K) and 2.21 kJ/mol (296K). Subsequent investigations are aimed at modification of the activated carbon’s surface to increase the adsorption energy, which is expected to lead to an increase of adsorption at room temperature. The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/ under REA grant agreement no. PIRSES-GA-2013-612484.

[1] S. Niaz, T. Manzoor, A.H. Pandith, Hydrogen storage: Materials, methods and perspectives, Renewable and Sustainable Energy Reviews 50 (2015) 457–469. [2] Y. Xia, Z. Yang, Y. Zhu, Porous carbon-based materials for hydrogen storage: Advancement and challenges, J. Mater. Chem. A 1 (2013) 9365–9381.

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P94

DESIGN, SYNTHESIS AND RELATIONSHIP OF STRUCTURE-PROPERTY OF 1- (DICHLOROBENZYLOXY)-2-(2,4-DICHLOROPHENYL)ETHYL)-AZOLES AND THEIR BIOLOGICAL ACTIVITY

Serghei Pogrebnoi

Institute of Chemistry, Academy of Sciences of Moldova, 3 Academiei st., MD-2028, Chisinau, Moldova

Fluconazole and itraconazole are triazole-derived class of known antifungal agents, potentially used against various fungal species. 1,2,4-Triazoles compounds also possess a variety of interesting biological activities such as antibacterial, antitumor, antitubercular, anticonvulsant, anticancer, analgesic, cytotoxic, antiproliferative and plant growth regulatory [1]. Keeping in view biological and medicinal properties of triazole and the potential chemistry of Cu(II) we have synthesized a new azoles according the scheme 1 as a biologically active candidates to obtain complexes with Cu(II). Scheme 1. Cl N N Cl N Cl Cl N Cl N Bu4NN N Cl 1) N N 3) O N 2) N Cl Cl N Cl CH R1 O O OH R1 1) MeCN, reflux 2) NaBH , i-PrOH 3) NaH, dioxane, reflux 2 4 R

Three new Cu(II) coordination compounds with antifungal agent isoconazole (L), namely mononuclear complexes [CuCl2(L)2] (1), and [Cu(O2CMe)2(L)2]·2H2O (2) and coordination polymer [Cu(pht)(L)2]n (where H2pht – o-phthalic acid) were synthesized and characterized by IR spectroscopy, thermogravimetric analysis and X-ray crystallography [2].

Fig.1. Molecular structures of 1 (a) and 2 (b)

Acknowledgements: The author thanks for financial support (institutional project 15.817.02.17A) and Prof. Macaev F. and Dr. Stîngaci E. for helpful discussions.

References: [1]. European Journal of Medicinal Chemistry 45 (2010) pp.2739-2747. [2]. Polyhedron 52 (2013) pp106–114.

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P95

HETEROMETALLIC Pr(III)-Bi(III) COORDINATION COMPOUNDS WITH 1,2-CYCLOHEXANEDIAMINTETETRAACETATE LIGAND AND CHLORINE- CONTAINING ANIONS

Nelea Popa

Department of Chemistry, Moldova State University, Chisinau, Moldova

Modern coordination chemistry increasingly turns to metal compounds with versatile ligands, special emphasis being recently paid to heterometallic complexes that exhibit a wider range of valuable properties compared to homometallic complexes. The preparation of multimetallic complexes enables their nanoscopic dimensions to be combined with cumulative action and can lead to novel or enhanced valuable properties. The basic task of the research was to get heterometallic complexes with higher 4f- luminescence quantum yield than in the corresponding homometallic complexes. It was reported that Bi(III) can be used as a sensitizer of luminescence of lanthanides in the visible and near- infrared (IR) spectral region [1, 2]. Heterometallic compounds can be also considered as molecular precursors for mixed- oxides upon adequate thermal treatment. We proposed to investigate the impact of the chlorine source and of the heating rate on the composition and morphology of the final residues. Considering these, five heterometallic compounds of general formula Pr{Bi(cdta)}3------4- yXy·zH2O (X = CH2ClCOO , CHCl2COO , CCl3COO , ClO4 , Cl ; y = 1 or 2; z = 9 - 14; cdta = 1,2-cyclohexanediamintetetraacetate) have been synthesized and analyzed. The composition of the complexes has been determined by means of elemental analysis, thermogravimetry, IR spectrometry and single crystal X-ray diffraction. The crystal structures of the compounds represent two-or three-dimensional networks, with Bi(III) having a coordination number of 8 while praseodymium coordination number is 8, 9 or 10. The ligands 1,2-cyclohexanediamintetetraacetate are coordinated to Bi(III) ions through the 2N+4O atom sets. The coordination is completed to eight by bridging oxygen atoms of cdta4- or Cl- ions. The coordination sphere of Pr(III) is formed of water molecules, bridging oxygen atoms of cdta4- ligands and dichloro- or trichloroacetate ions. Non-ionized and non-coordinated dichloro- or trichloroacetic acids are also present in two structures. Thermogravimetric analysis results confirmed that at 0.5oC·min-1 heating rate the residue masses are in good agreement with the calculated values for the corresponding precursors. Notably, some residues represent heterometallic oxychlorides, while others are mixes-oxides thought all the precursors have chlorine in the composition. Accordingly, the appearance of the thermolysis products differs from precursor to precursor depending on the chorine source. It was determined that the heating rate affects the morphology of the residues. So, the products resulted after thermal treatment of the precursors at 10 oC·min-1 heating rate are formed of smaller grains than those eventually obtained at 0.5 oC·min-1.

1. Q. Xu, B. Lin, Y. Mao. J. Lumin., 128, 1965 (2008). 2. G. Lakshminarayana, J. Ruan, J. Qiu. J. Alloys Compd., 476, 878 (2009).

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P96

NON-CALORIMETRIC METHOD FOR DETERMINATION OF ENTHALPIES OF COMPLEX FORMATION REACTIONS FROM TEMPERATURE COEFFICIENTS OF METAL ION ACTIVITIES OR EQUILIBRIUM CONCENTRATIONS

Povar Igor, Spinu Oxana

Institute of Chemistry, Academy of Sciences of Moldova, 3 Academiei str., Chisinau, MD 2028, Republic of Moldova, e-mail: [email protected]

In this paper, a non-calorimetric method for measurement of the enthalpies of complex formation reactions from temperature coefficients of the metal ion activities (or equilibrium concentrations) has been developed. The reactions of complex formation of an arbitrary composition MmLn in aqueous solutions can be represented by the following scheme:

T T mM  nL  MmLn , mn,Hmn (1)

Near the reaction equation the related thermodynamic characteristics are written, namely, the T T equilibrium constant mn and the enthalpy of the complex formation reaction H mn at the temperature T (below this index is omitted). Within the method the H mn calculation is performed according to the equation of reaction-isobar or Gibbs-Helmholtz equation: d ln  H  RT 2 mn (2) mn dT d(G /T) H  T 2 mn (3) mn dT Therefore, for the determination it is necessary to know the dependency on temperature of the equilibrium constant or Gibbs energy change. The equations for calculating the dependence of temperature coefficients of the degree of complex formation reactions α on the variation of enthalpies of complex formation reactions have been derived. The processing of experimental data can be practically carried out by numerical methods, if for the initial composition of reactant mixture there are not less than five experimental values ln  (or  ln[M]) for different temperatures. To determine at temperature T it is necessary to know the set of equilibrium constants at this temperature and the dln  /dT values, which are calculated using numerical methods from experimental data ln α = f(T) or ln[M] = f(T), where [M] is the equilibrium concentration of metal ion. Deduced equations allow the approximate estimation of the actual error of the determination. Thus, the error in the  0.5 kJ/mol in the range of 300 K and the temperature variation interval of 10 degree corresponds to the ln[M] or value variation of 0.007 log units. Computation of enthalpies of the series of complex formation reactions from temperature coefficients of the degree of complexation has been performed. Comparison of the measured exp calc H mn values by the calorimetric method with the H mn values obtained by the developed method gives a quite satisfactory agreement.

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P97

INFLUENCE OF THE LOCAL BIOACTIVE COMPOUNDS ON GLUTATHIONE SYSTEM IN PHYSIOLOGICAL CONDITIONS AND ASTHMA

1 2 Procopisin Larisa , Mihalciuc Olga

1Institut of Phtisiopneumology "Chiril Draganiuc", Chisinau, Republic of Moldova 2State University of Medicine and Pharmacy "Nicolae Testemitanu", Chisinau, Republic of Moldova

Background. GSH metabolism dysorders are widely recognized as central pathogenetic link feature of many inflammatory lung diseases such as idiopathic pulmonary fibrosis, acute respiratory distress syndrome, cystic fibrosis and asthma. Identification, research and testing of new remedies for correction of the glutathione system disorders in asthma are of particular interest due to the increased incidence and severity of this pathological process, which leads to the disability of working age people. In this regard, local bioactive compounds (BC)  Schiff base, their combination with 3d metals that exhibit strong antioxidant, antiproliferative and cytotoxic effects are of special interest [Gulea A. et al., 2009, 2013]. However, their influence on the level of GSH and glutathione metabolism enzyme’s activity in physiological conditions and patients with asthma had not been studied. The aim of this research was to study in vitro the peculiarities of the local BC action on glutathione system in physiological conditions and in persistent asthma. Methods. The research was done on peripheral blood samples collected from 42 patients with mild, moderate and severe forms of persistent asthma, who have been treated at the Pneumology Department of the "Chiril Draganiuc" Institute of Phtiziopneumology. Local BC  CMD-4, CMD-8, CMJ-23 and CMJ-33, were synthesized at the Inorganic Chemistry Department of Moldova State University [Gulea A., 2009]. The blood was collected in the morning after fasting from the cubital vein and then, under sterile conditions, was placed in a vial containing 8 ml of Dulbecco's modified Eagle medium (DMEM), heparin (2.5 un/ml) gentamicin (100 mg/ml) and L-glutamine (0.6 mg/ml). For the study of the influence on glutathione system of the local BC 1.0 ml of this mixture was pipetted into 6 sterile tubes. 0.1 ml 0.9% NaCl were added into the first tube for the assay of the initial level of the studied indices. The tested BC, diluted in 0.1 ml 0.9% NaCl to a final concentration 50 nM/ml, were added into rest test-tubes. After 24 hours incubation at 37°C, the tubes were centrifuged for 5 minutes at 1500 rev/min. The glutation reductase (GR), thioredoxin reductase (TR) glutation peroxidase (GPO) and glutathione-S-transferase (GST) activity were evaluated in supernatants by spectrophotometric micromethod adapted to the Hybrid Multi-mode Microplate Rider Synergy H1, "BioTek" (USA). Results. It was established that in healthy people the compounds CMD-4, CMD-8, CMJ-33 and CMJ-23 does not change the GR and GST activity; the CMD-4 decreases, and the CMD-8 and CMJ-23 increase the activity of TR. The activity of GPO decrease after CMD-4, CMD-8 and CMJ-33 administration compared to baseline. In the mild form of asthma all studied BC exercise potent modulatory effects on glutathione metabolic enzymes, as confirmed by the increase of the TR, GST and GPO activity compared with healthy individuals. In moderate forms of asthma the studied BC increase the GR, TR, GST, and GPO values, and in the severe forms of asthma the BC mainly reduce the GR, TR and GST activity. Conclusions: The study established the effectiveness of local bioactive compounds  CMD-4, CMD-8, CMJ-33 and CMJ -23, confirmed by their ability to improve the functional state of glutathione system in different forms of persistent asthma and to maintain the thiol- disulfide cell balance, which would allow the development of new treatment strategies of asthma.

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P98

“LIQUID TRIANGLES”: IRON CONTAINING TASK-SPECIFIC IONIC LIQUIDS

D. Prodiusa,b, A. K. Powella,c

a Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstr. 15, 76128 Karlsruhe, Germany. e-mail: [email protected] b Institute of Chemistry ASM, Academiei str. 3, MD-2028 Chisinau, Moldova c Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

Metal-ion-containing ionic liquids (ILs) represent a promising subclass of ILs since they may have interesting magnetic, luminescence or catalytic properties. Apart from a few examples of ILs based on rare earth metal ions, most investigations on metal-based ILs have been limited to Z+ 3+ (n-z)− − transition metals (M ) or Al in [MXn] anions containing compounds (where X = halide , − − − − 5-/6- SCN , Tf2N , (OC(CF3)3) , (F6-acac) ) or as inorganic ILs with POM anions [MTiW11O39] . The examples of ILs containing transition metal-based cations are limited to derivatives of N- alkylimidazoles, R1-NH-R2 or metallocenium-based ligands. Herein we discuss about the synthesis, structural characterization and catalytic properties of a new class of ILs which contain III 7+ septuply positively charged antiferromagnetically coupled {Fe 3O(RCOO)6L3} cationic triangles [1]. A survey of the Cambridge Crystallographic Database (CSD) up to Dec. 2012 reveals that more than 1100 crystal structures of metal carboxylates containing μ3-oxo bridged metal triangle motifs have been deposited. However, so far the use of this motif in ILs is unprecedented.

ACKNOWLEDGEMENTS We thank the DFG CFN and Alexander von Humboldt Foundation (D.P) for financial support and co-authors for their contributions.

[1] D. Prodius, F. Macaev, E. Stingaci, V. Pogrebnoi, V. Mereacre, G. Novitchi, G. E. Kostakis, C. E. Anson, A. K. Powell, “Catalytic “Triangles”: Binding of Iron in Task-Specific Ionic Liquids”, Chem. Commun., 2013, 49, 1915-1917.

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P99

II III HETEROMETALLIC HEXANUCLEAR {Co 2Co 2Dy2} PIVALATE CLUSTER

I. Radu,a V. Ch. Kravtsov,a S. G. Baca,a K. Krämer,b S. Decurtins,b S.-X. Liu,b O. S. Reu,a S. M. Ostrovsky,a A. V. Palii,a S. I. Klokishner a

aInstitute of Applied Physics, Academy of Sciences of Moldova, Academiei str. 5, MD2028 Chişinau, R. Moldova b Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012-Bern, Switzerland

II III A new heterometallic hexanuclear {Co 2Co 2Dy2} compound with composition [Co4Dy2(OH)2(O2CCMe3)8(HO2CCMe3)2(teaH)2(N3)2] · 2(EtOH) (1) has been prepared from the reaction of dinuclear cobalt(II) pivalate with dysprosium(III) nitrate hexahydrate, trietanolamine (teaH3) ligand and sodium azide and characterized by elemental analysis, IR spectroscopy, and thermogravimetric studies. A single-crystal X-ray diffraction analysis showed that compound 1 crystallizes in the tetragonal space group I41/a and comprises neutral centrosymmetric clusters and crystallization ethanol molecules. The cluster is composed of two CoII, two diamagnetic III III  Co , and two Dy ions bridged by two 3-hydroxy groups, two azide N3 anions, six bridging pivalate residues and additionally linked by two doubly deprotonated teaH2 ligands (Fig. 1). The neutral monodentate pivalic acid and chelating pivalate ion additionally cupped each of the DyIII II III centers. All cobalt atoms have an octahedral surrounding: NO5 for Co and N2O4 for Co centers. The Dy atoms have a square-antiprismatic O8 geometry. A model for description of the magnetic properties of the obtained cluster has been developed. The model takes into account the crystal fields acting on the DyIII ions and the exchange interaction in the pairs CoIIDyIII and II II 6 III Co Co . The Stark structure of the ground H15/2 multiplet of the Dy ions is calculated in the exchange charge model of the crystal field with allowance for covalence effects. The magnetic susceptibility and magnetization are well reproduced in the low temperature range T < 100 K (Fig. 2), projecting the exchange interaction between the CoII and DyIII ions onto the basis representing the direct product of the Kramers doublet ground state for the CoII ions and all Stark III levels of the Dy ions. 35

30 16 -1 25

12 A

20 N

B 

K mol K 8 3

15 M/ 4

10 T, cm T,

 0 5 0 1 2 3 4 5 Magnetic Field / Tesla 0 0 50 100 150 200 250 300 T,K II III Fig. 1. Structure of the {Co 2Co 2Dy2} Fig. 2. χT vs. T and magnetization vs. external magnetic II III cluster. field (T=1.9 K) for the {Co 2Co 2Dy2} cluster: experiment  circles, theory  solid lines. At higher temperatures the magnetic susceptibility is not affected by the exchange interaction in the CoII-DyIII and CoII-CoII pairs due to its smallness as compared with kT, and good agree-ment between the calculated and experimental χT data is achieved taking into account the population of the Stark levels of the DyIII ions and all spin-orbital multiplets for the CoII ions.

Acknowledgement. The authors thank SCOPES IZ73Z0_152404/1 for financial support.

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P100

SYNTHESIS OF SILVER NANOPARTICLES IN BIOMASS FRACTIONS OF PHOTOSYNTHETIC MICROORGANISMS

Rudic Va., Cepoi La., Chiriac Ta., Zinicovscaia Ib,c., Rudi L.,a Codreanu S.,a Miscu V.,a Dumbrăveanu Va.

aInstitute of Microbiology and Biotechnology, Academy of Sciences of Moldova, 1, Academiei str., 2028, Chisinau, R. Moldova bInstitute of Chemistry, Academy of Sciences of Moldova, 3, Academiei str., 2028, Chisinau, R. Moldova cJoint Institute for Nuclear Research, 6 Joliot-Curie str., 1419890, Dubna, Russia

Production and application of nanoparticles in biology is an important and constantly changing field of nanotechnology. Many of physical and chemical methods for the synthesis of silver nanoparticles are at the testing stages and often their implementation is linked to numerous problems related to stability, crystal growth and aggregation of nanoparticles. Biosynthesis of silver nanoparticles is conducted under usual conditions of temperature, pH and pressure; also it does not require aggressive growth, reducing or stabilising agents. The most widely used for this purpose are bacteria and fungi. However, in this context, too little attention is paid to photosynthetic microorganisms, despite, the technologies involving them being much chipper, due to the fact, that they do not require organic media. These organisms are equipped with antioxidant protection mechanisms that may be included in the processes of metal reduction and synthesis of silver nanoparticles. The marine microalgae Porphyridium cruentum CNMN -AR-01 biomass’s protein fraction was used to establish the possibility of obtaining silver nanoparticles in biomass fractions of photosynthetic microorganisms. Silver nitrate solution has been used as a source of silver.

a b

(a) Silver nanoparticles synthesized in protein matrix of Porphyridium cruentum biomass 6 hours after contact. (b) EDAX spectrum of protein fractions from Porphyridium cruentum biomass

The 15-24 nm spherical shaped monosphers silver nanoparticles are synthesised in the first 6 hours of contact of the protein fraction of Porphyridium cruentum biomass with the silver nitrate solution. The research was conducted within the project "Cost Effective Technologies for obtaining silver nanoparticles, using cyanobacteria and microalgae" and the State Program "Chemicals design and materials architecture shaping for various applications".

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P101

USING OF NEW HYBRID COMPOUNDS WITH TERPENOID AND AZAHETEROCICLIC SKELETON TO INCREASE ANTIOXIDANT ACTIVITY OF THE NOSTOC LINCKIA

Rudic Va., Arîcu Ab., Cucicova Cb., Cepoi La., Rudi La., Codreanu Sa., Secara Eb., Valuța Aa., Barbă A.,b Miscu Va., Vlad P.,b Chiriac Ta.

The application of potentially toxic compounds in very low quantities can cause a moderate stress, leading to the intense accumulation in biomass of antioxidant compounds, without cellular components damage. This paper describes the test results of two new chemical compounds with terpenoid and azaheterociclic hybrid skeleton as inductor to provide high antioxidant activity of Nostoc linckia biomass. Below are presented the schemes of the synthesis process. 19 20

12 18 21 O CO2H COCl CO 11 17 22 16 HN N N O 1 3 13 23 (COCl)2 NH2 10 8 28 C H 0 5 7 6 6 CH2Cl2, 20 C, 10 h; 3 27 24 , 5 h 26 25 1 2 15 14 4 (60%) 5 Scheme for the preparation of N-(8,13-biciclohomofarneseno-ilamino)carbazole. O 17 12 N(4) CO2H COCl CO N 11 N(1) O NH2 3 N 18 1 13 (2) (COCl)2 N NH 10 8 NH2 C H 0 3 5 6 6 CH2Cl2, 20 C, 3 h 6

1 2 15 14 4 (58%) 5 Scheme for the preparation of 1-(8,13-bicyclohomofarnesenoil)-3-amino-1,2,4-triazole. The compounds were added to the nutrient medium of cyanobacteria N. linckia, in the amounts indicated in the table. The antiradical activity of the ethanolic extract obtained from cell biomass was determined using DPPH assay. The results are shown in the table.

The antioxidant activity of 70% (1 mg/ml) ethanolic extract of Nostoc linckia biomass resulting from the chemical stimulation

Chemical compound Compound concentration g/L Antioxidant activity, % Inhibition of DPPH Control sample - 28,03±0,72 1-(8,13-Bicyclohomofarnesenoil)- 0,050 60,14±1,09 3-amino-1,2,4-triazole 0,060 67,44±1,15 0,100 59,16±2,04 N-(8,13- 0,050 64,35±0,98 biciclohomofarnesenoilamino) 0,060 76,41±1,69 carbazole 0,100 71,24±1,48

The results show increased antioxidant activity of the ethanolic extract from 2.11 to 2.73 times compared to the control. With increasing antioxidant activity of then ethanol extract grows the value of Nostoc biomass as an antioxidant producer.

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P102

SYNTHESIS AND ANTITUMOR PROPERTIES OF DERIVATIVES 4-SUBSTITUTED-5-(PIRIDIN-4-YL)-4H-1,2,4-TRIAZOLE-3-THIOL R. Rusnac 1, A. Zatîc1, A. Paholnitcaia1, N. Barbă1, M. Perreault2, A. Gulea1

1 Laboratory of Advanced Materials in Biopharmacy and Technics, State University of Moldova, 60, str. Mateevici, Chisinau, MD 2009, e-mail: [email protected] 2Laboratory of Medicinal Chemistry, CHU de Québec-Research Center University Laval, Québec City, Canada

In recent years, the chemistry of triazoles and their fused heterocyclic derivatives has received considerable attention owing to their synthetic and effective biological importance [1]. Literature survey reveals that 1,2,4-triazole derivatives exhibit a wide range of biological activities including Antibacterial, Antifungal, Antitumour, Anti-inflammatory, Antitubercular, Hypoglycemic, Antidepressant, Anticonvulsant, Anticancer, Antimalarial, Antiviral, Antiproliferative, Analgesic and Antimigraine [1,2]. The derivatives of 4-substituted-5(piridin-4- yl)-4H-1,2,4-triazole-3-thiol were synthesized according to scheme:

O R= b) 2-CH3-C6H4 -, c) 4-NaO3S-C6H4 -, d) C6H5 -, e) 4-C2H5O-C6H4 –

Table. The antiproliferative activity of 4-substituted-5-(piridin-4-yl)-4H-1,2,4-triazole-3-thiol on human on leukemia (HL-60) cells. Inhibition of cells proliferation (%) Compound 0.1µM 1 µM 10 µM a 0 0 0 b 3.26 11.08 10.20 c 7.24 9.46 11.15

The obtained data demonstate that the synthesized compounds show moderate (3-11%) antiproliferative activity. Compounds e and d were tested on melanoma (MeW-164) and on human leukemia (HL-60) cells, in the range of (0,1-10 µM) concentrations. The results proved thait they have a higher (16-23%) antiproliferative activity. Acknowledgements: This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F Bibliography [1] Vandana Sharma, Birendra Shrivastava, Rakesh Bhatia, Mukesh Bachwani, Rakhi Khandelwal, Jyoti Ameta. Pharmacologyonline 1: 1192-1222 (2011) [2] Mukhtyar S. Sainiand Jaya Dwivedi. Saini and Dwivedi, IJPSR, 2013; Vol. 4(8): 2866-2879

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P103

- 2- DETERMINATION OF NITRATE IN WATER IN THE PRESENCE OF NO2 , SiO3 , + NH4 , UREA AND SURFACE ACTIVE SUBSTANCES

Maria Sandua*, Tudor Lupascub, Anatol Taritaa, Tatiana Goreacioca, Sergiu Turcana, Elena Mosanua

aInstitute of Ecology and Geography, A.S.M., 1, Academiei str., Chisinau MD-2028, Republic of Moldova bInstitute of Chemistry, A.S.M., 3, Academiei str., Chisinau MD-2028, Republic of Moldova *e-mail: [email protected]

The problem of nitrate monitoring in waters intended for human consumption (drinking water, water for foods preparation, etc.) is in attention of specialized institutions [3]. Nitrification in natural waters has mandatory stage the appearance of nitrite content of which in surface waters in Moldova ranges from 0-0.4 mg/dm3 to tens of mg/dm3 in small rivers water downstream of sewage discharges, insufficiently treated in biopurification plants. This study relates to determination of nitrate in presence of compounds that are present in - 2- + surface and underground waters: NO2 , SiO3 , NH4 ions, urea and cationic and anionic surface active substances (SAS Ct and SAS An) in the base of developed method for determining nitrate in presence of nitrite in water including the removal of nitrite with sulphaminic acid, the nitrate ion reduction to nitrite using a reducing mixture that contains Na2SO4 and zinc dust in ratio of 100:5 and determining the nitrite with the Griess reagent [2]. - In the study it was established that 0,1-10 mg/dm3 of NO3 in the presence of 20 - 3 3 mg/dm3 NO2 can be determined in the presence of 1,5 mg/dm SAS An and 18 mg/dm 2- 3 SiO3 (fig. 1). Cationic active substance doesn’t influence process of about 150 mg/dm ; + 3 urea and NH4 ions – more than 1000 mg/dm .

SAS An SAS Ct 0,25 1,4 0,2 1,2 1 0,15 0,8 0,1 0,6

Abs., 520 nm Abs., 0,05 0,4 Abs., 520 nm Abs., 0 0,2 0 0 1,5 7,5 15 22,5 30 150 0 2 6 10 14 18 22 60 mg/dm3 SAS mg/dm3 SiO32-

3 - Figure 1. The absorbance of the solutions containing 20 mg/dm of NO2 , 3 mg of - 2- 3 - sulphaminic acid, SAS An and Ct (2 mg/dm3 NO3 ), SiO3 ions (1 mg/dm NO3 ) in the - conditions of NO3 ions determination.

Bibliography: [1] Government Decision of Republic of Moldova, 15.08.2007/934, on automated information system establishment, State Register of natural mineral waters, drinking water and bottled soft drinks. Official Monitor no. 131-135, Art. No. 970 (Published: 24.08.2007) (in Romanian). [2] SANDU, M.; LUPAŞCU, T.; TĂRÎŢĂ, A.; GOREACIOC, T.; ŢURCAN, S.; MOŞANU, E. Method for nitrate determination in water in the presence of nitrite. Chemistry Journal of Moldova. 2014, 9(2), 8-13. ISSN 1857- 1727.

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INFLUENCE OF LOCAL BIOACTIVE COMPOUNDS ON SPLEEN CARBOHYDRATE METABOLISM IN ETHYLENE GLYCOL INTOXICATION

Sardari Veronica1, Rudic Valeriu2, Tagadiuc Olga,1 Mihalciuc Olga1, Shvets Inna1

1State University of Medicine and Pharmacy "Nicolae Testemitanu" 2Institute of Microbiology and Biotechnology of Academy of Science of Moldova Chisinau, Republic of Moldova

Background. Metabolic disorders, including those of the carbohydrate metabolism, are important elements of the pathogenesis of numerous diseases. More interest in the usage of different biologic active compounds, which could exert significant influence on metabolic processes, aroused currently. Local bioactive compounds (BC)  Schiff bases, their combination with 3d metals, manifest important biologic activity [1, 2], but their influence on carbohydrate metabolism in spleen in ethylene glycol (EG) intoxication was not studied. The aim of the study was to elucidate the peculiarities of spleen carbohydrate metabolism in ethylene glycol intoxication and after its remediation with local BC. Methods. Carbohydrate metabolism was studied in spleen in EG intoxication by measuring the activities of lactate dehydrogenase isoforms  LDH-L (catalyzes the conversion of lactate into pyruvate) and the LD-P (catalyses the conversion of pyruvate to lactate), as well as the functionality of the glucose-6-phosphate dehydrogenase (G6P DH) – the source of reducing equivalent NADPH+H+, and anabolic NADP-dependent malate dehydrogenase (MDH-NADPd) by spectrophotometric micromethod adapted to the Hybrid Multi-mode Microplate Rider Synergy H1, "BioTek" (USA). Treatment of ethylene glycol poisoning was carried out with local BC: Schiff bases, their combination with 3d metals  CMD-4, CMD-8, CMJ-23, and cyanobacterial remedy  BioR-Ge, with enhanced content of organically bound Ge. Results. Experimental EG intoxication induced the decrease of LDH-P and G6P DH activities, while the functional level of NADP-MDH increased slightly compared with reference values. CMD-4 had led to the normalization of the activity of both LDH isoforms, while BioR- Ge reduced it. CMD-8 and CMJ-23 kept low LDH-P. Medication with CMD-8 and BioR-Ge returned to normal values, while CMJ-23 induced statistically conclusive the functional level of G-6-P DH activity. CMD-4, CMD-8, CMJ-23 and BioR-Ge increased MDH-NADPd activity in the spleen of animals with EG intoxication. Conclusions. Studied local BC exhibit the capacity to normalize the activity of the majority of carbohydrate metabolism enzymes in spleen. The selective action of the tested compounds, which probably depends on their degree of engagement at different stages of metabolism, is obvious. Studied BC can be used as pathogenic remedies for the correction of metabolic disorders, which are specific for the ethylene glycol induced toxic lesions of the spleen. Research conducted in this area would allow to develop new methods of efficient and harmless treatment of various immune system disorders that would ensure a high therapeutic effect and preventive action in respect to severe complications.

Bibliography. 1. Roşu T., Gulea A., Nicolae A., Georgescu R. Complexes of 3dn Metal Ions with Thiosemicarbazones: Synthesis and Antimicrobial Activity // Molecules 2007, 12, p.782-796. 2. Gulea A., et al. In vitro antileukemia, antibacterial and antifungal activities of some 3d metal complexes: Chemical synthesis and structure – activity relationships // Journal of Enzyme Inhibition and Medicinal Chemistry, 2008; V. 23. Nr.6, pp.806- 818.

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ONE DIMENTIONAL SYSTEM WITH HELICAL STRUCTURE Mihail Secua, Oleg Palamarciuca, Rodolphe Cléracb aMoldova State University; bCNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP),Laboratory for "Molecular Materials and Magnetism", 115 avenue du Dr. Albert Schweitzer, Pessac, F-33600, France In memoriam to Prof. Mihail Revenco Cyanide is an efficient and versatile mediator for magnetic coupling. The cyanido- bridged bimetallic assemblies have been widely studied because of their rich magnetic behavior, including high-Tc magnetism, photo- and electromagnetism, and single-molecule or single-chain magnetism [1]. Miyasaka et al. have prepared a series of cyanido-bridged complexes derived from the reaction of manganese(III) Schiff base complexes and hexacyanidometallic anions [2]. To develop new magnets, we focused our attention on bimetallic systems with cyanidometallic anion and manganese(III) Schiff base complex. In this context, the thiosemicarbazide type ligands possess interesting chelating and coordinating properties for metal ions and in particular manganese at different oxidation states. Herein, we report the synthesis of a new cyanido-bridged heterobimetallic one dimensional system obtained from anisotropic building-block based on manganese(III) N1,N4-bis(salicylidene)S- methylisothiosemicarbazide (MnL+) and ferricyanide anion. Single-crystal X-ray diffraction studies revealed helical one dimensional system with the formula III [Mn(L)(CH3OH)2][{Mn(L)}2{Fe (CN)6}CH3CN]·CH3CN (Figure 1).

(a) (b)

III - Figure 1. (a) Representation of one dimensional system [{Mn(L)}2{Fe (CN)6}CH3CN] and III (b) Packing of the [Mn(L)(CH3OH)2][{Mn(L)}2{Fe (CN)6}CH3CN]·CH3CN

[1] M. N. Leuenberger, D. Loss, Nature, 410, 2001, 789. [2] H. Miyasaka, R. Clérac, W. Wernsdorfer, L. Lecren, C. Bonhomme, K.-i. Sugiura, and M. Yamashita, Angew.Chem. Int. Ed., 2004, 43, 2801;R.Clérac, H. Miyasaka, M. Yamashita and C. Coulon, J. Am. Chem. Soc., 2002, 124, 12837; H. Miyasaka, A. Saitoh, M. Yamashita and R. Clérac Dalton Trans.2008, 2422.

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SPECTROPHOTOMETRICAL STUDY OF EXTRACTS FROM THE HERB ST. JOHN'S WORT (Hypericum perforatum)

D. Shepel, E. Vieru

Institute of Chemistry, Academy of Sciences of Moldova, 3 Academiei str., Chisinau, Republic of Moldova, MD-2028 [email protected]

A photometric method based on measurement of optical density (A) at the absorption maximum of the flavonoid complex with AlCl3 in the region 400-430 nm are widely used for determination of the total content of flavonoids (FL) in plants. The amount of FL is expressed in units of rutin. However, in various literature sources conditions of extraction and complex formation with AlCl3 differ significantly. Our studies were carried out on the example of a very well-known and widely used medicinal plant Hypericum perforatum or the herb St. John's wort. The best extractant for FL extraction was 70% ethanol. But in this case nonpolar compounds, chlorophylls, hyperforins, anthracene derivatives were extracted from the herb St. John's wort simultaneously with FL which may also interact with AlCl3 and distort results of the analysis. Special noise could make chlorophylls, which intense Soret bands were observed in the spectrum in the region of analytical bands of FL (300 - 450 nm). Quercetin (aglycone) and rutin (glycoside of quercetin) were used as model flavonoid compounds. Solubility of FL was evaluated by the values of A in the maxima for quercetin (374 - 380 nm) and rutin (363 nm) of saturated solutions in various solvents. On the basis of the obtained data it was shown a scheme of a consecutive fractional extraction of substances that prevent the determination of FL (see on the scheme, LPh - liquid phase, SPh - solid phase). The spectra in the region of 200 - 700 nm of extracts from petals of flowers and leaves of the herb St. John's Wort obtained by consecutive extraction with hexane, chloroform, and an aqueous solution of 0.1 M AlCl3, ethanol and ethanol total extract were studied. Spectra were recorded on a Lambda 25 spectrophotometer (PerkinElmer, USA, 2005). The resulting spectral data showed that the proposed scheme for determination of the total content of flavonoids in the aqueous extract 0.1 M AlCl3 simplifies the analysis and specified the results. Chlorophylls and anthracene derivatives were extracted from Hypericum perforatum by ethanol along with the FL, and interacted with AlCl3, which led to changes in the spectrum of the initial extracts. Thus, we proposed the scheme of a consecutive fractional extraction of the FL from plant material for determination of the FL total content and it is recommended for analytical practice.

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INVESTIGATION OF THE STRUCTURE OF COAL OBTAINED FROM NUTSHELL BY IR SPECTROSCOPY

D. Shepel, M. Rusu, T. Lupascu

Institute of Chemistry, Academy of Sciences of Moldova, 3 Academiei str., Chisinau, Republic of Moldova, MD-2028 [email protected]

Various physicochemical methods, including infrared spectroscopy are applied for studying the structure and composition of activated carbons. The aim of the work was investigation of structure activated carbons obtained from nutshell after various heat treatment with use of IR spectroscopy method in KBr pellets. IR spectra were recorded on a FTIR Spectrometer Spectrum 100, PerkimElmer (2007) in the range of 4000-400 cm-1, and they are represented on the figure below.

It was found that the substantial changes occurred in the carbons with temperature rising from 250 to 600С. With temperature raising a broad band with a maximum at 2077 cm-1 was appeared in the IR spectrum, that related to (CС) alkyne and v(C=C) allene structures. A typical intense band at 1620 cm-1, corresponding to v(C=C) of the benzene rings and graphite was observed [1]. A group of strongly intersecting bands was revealed in the region 1600-1200 cm-1 in the spectra of the activated carbons where the v(C=C) frequencies of the benzene rings are situated. An area of v(C-C) skeletal vibrations was presented the intensive intersecting bands forming the complex contour in the range of 1230-1080 cm-1. Contours of the spectra before and after heat treatment were different. It follows that at higher temperatures there are structural changes in activated carbons from nutshell.

[1] Bellamy, L.J. The Infrared Spectra of Complex Molecules. Foreign Literature Publishing House: Moscow, 1963, 592 p. (in Russian).

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STRUCTURE OF TETRACHLOROMETALLATES Со (II), Zn (II) WITH COMPLEX CATIONS OF GERMANIUM (IV) ON BASE IR, PMR, X-RAY ABSORPTION SPECTROSCOPY EXAFS DATA

N.V. Shmatkovaa, I.I. Seifullinaa, N. V. Khitricha, V.G. Vlasenkob, A.N. Morozovc, L.D. Popovc, S.I. Levchenkovd

aI.I. Mechnikov Odessa National University, Dvoryanskaya St., 2, 65082, Ukraine [email protected] bInstitute of Physics of Southern Federal University, Stachki pr., 194, Rostov-on-Don, 344090 cSouthern Federal University, B. Sadovaya St., 105, Rostov-on-Don, 344104, Russia dSouthern Scientific Center of Russian Academy of Sciences, Chekhova St., 41, Rostov-on-Don, 344006, Russia

By the way of reagents interaction the complexes of general formulas [Ge(-, - Ls·H)2][MCl4]·СН3ОН, where М = Со:  – (I),  – (II), М = Zn:  – (III); [Ge(-, - Lnf·H)2][MCl4], where М = Со:  - (IV),  - (V); М = Zn:  – (VI) were obtained from the systems «GeCl4 – 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde nycotinoyl-, isonycotinoylhydrazones (-, - H2Ls and -, - H2Lnf, respectively) – МCl2 (М = Со (II), Zn (II)) – СН3ОН». The electrolytic dissociation type and thermolysis mechanism were determined. By the methods of IR spectroscopy (I-VI), PMR (for Ge-Zn complexes III, VI) and X-ray absorption spectroscopy EXAFS (for Ge-Co complexes I, II, IV, V) it was determined that complexes I-VI have octahedral polyhedron {GeO4N2} due to O(C-O)-N(CH=N)-O(Ph-O) coordination of two hydrazone molecules which have two protonated exochelate nitrogen atoms Npy. In the IR spectra of I-VI are absent (OH), (NH), (C = O) and  (NH) compared to hydrazones, are present vibrations frequency the fragment C = NN = C (1600-1607 cm-1) and -N=CO- (1547-1545 cm-1), ν(Ge-O) ~ 680 cm-1 and ν(Ge←N) ~ 615 cm-1. Frequencies δ(Npy) rings increased by ~15 cm-1 compared to hydrazones (610, 900 cm-1), which confirms their protonation in the complexes. In PMR spectrums of Ge-Zn complexes (III, VI) the signals of NH-, Ar-OH groups protons are absent, НС=N shifted to 9,622 - 9,365 ppm and НN+py observes at 5.05 – 5.5 ppm. The formed 2- germanium complex cation neutralize the charge [MCl4] . 10 2- Given the coordination number of zinc and 3d configuration of zinc (II), [ZnCl4] has a 4 4 4 4 tetrahedron structure. The electronic transitions ( А2g T1g(F) and А2g T1g(P)) observed in the diffuse reflection spectrums and эфф (4.01-4.38 BM, Т = 295К) values for Ge-Co complexes (I, II, IV, V) specify on the tetrahedron structure of the cobalt polyhedron. The local arrangements, bonds lengths and the germanium (IV) and cobalt (II) polyhedrons geometry were determined by EXAFS spectroscopy. MFT EXAFS GeK-edge for I-VI consist of base peak with r = 1.45 - 1.48 Å, corresponding scattering of photoelectronic wave on the six nearest atoms of nitrogen and oxygen ligands that make up the first coordination sphere, and peaks with smaller amplitude at large r. MFT EXAFS CoK-edge consist only of base peak with r = 1.79 - 1.83 Å approximately equal amplitude, which is well satisfies model of local atomic environment of the cobalt ion with four chlorine atoms. Bond lengths Со–Сl 2.25 - 2.26 Å.

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X-RAY EXAFS, MÖSSBAUER AND IR ABSORPTION SPECTROSCOPY STUDY

STRUCTURE OF THE COMPLEXES [Ge(L∙HCl)(L∙H)][FeCl4] ∙ CH3OH, H2L –2-OH- ARYLALDEHYDES NYCOTINOYL-, ISONYCOTINOYLHYDRAZONES

N.V. Shmatkovaa, I.I. Seifullinaa, V.G. Vlasenkob, A.L. Trigubc, V.V. Kitaev b, S.I. Levchenkovd

aI.I. Mechnikov Odessa National University, Dvoryanskaya St., 2, 65082, Ukraine [email protected] bInstitute of Physics of Southern Federal University, Stachki pr., 194, Rostov-on-Don, 344090 c NRC "Kurchatov Institute", sq. Academica Kurchatova, 1, Moscow, 123098, Russia dSouthern Scientific Center of Russian Academy of Sciences, Chekhova St., 41, Rostov-on-Don, 344006, Russia

Previously, it was shown that by reacting GeCl4 with 2- hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde nycotinoyl-, isonycotinoylhydrazones (-, - H2Ls and - , - H2Lnf, respectively) in methanol complexes [Ge(Ls∙HCl)2] and [Ge(Inf∙HCl)2] are formed. O, N, O- coordination of protonated by Npy enol form of the ligand (Fig. 1) with compensation charge of chloride ion is realized in them.

In this study established that the introduction of FeCl3 in systems «H2Ls (H2Lnf) – GeCl4 – CH3OH» complexes [Ge(Ls∙HCl)(Ls∙H)][FeCl4] ∙ CH3OH, -(I), - (II), 2+ [Ge(Lnf∙HCl)(Lnf∙H)][FeCl4] ∙ CH3OH, - (III), - (IV) Fig. 1. Structure [Ge(-Lnf∙H)2] in are formed. composition of [Ge(-Lnf∙HСl)2] Form Ge K-edge XANES region of X-ray absorption spectra, which determined by 1s4p dipole electronic transition, corresponds to a maximum of C and indicates a highly-octahedral configuration of germanium ions in the I-IV (Fig. 2). The main peak (r = 1.46-1.48 Å) in MTF EXAFS GeK-edges for the I-IV corresponds to the scattering of waves on the six nearest atoms N and O ligands coordination unit {GeO4N2}. Mossbauer spectrum IV (Fig. 3) – doublet with parameters (Qs = 0.336 ± 0.006 mm/s and Is = 0.325 ± Fig. 2. XANES GeK-edge for I-IV - 0.003 mm/s) is typical for [FeCl4] and corresponds to the realization in the anion charge Fe3+ with S = 5/2 and coordination number (Fe) = 4. The quantities eff (5.87 - 5.89 BM) for the I-IV at 25 ◦C confirm high-spin 3d5 configuration with a tetrahedral coordination enviropment of Fe (III). Taking into account the data of - IR spectra in the I-IV ion [FeCl4] compensates for the protonated form of only one of ligand in the composition of cations Ge (IV), the second ligand linked with germanium in hydrochloride form; the coordinating unit Fig. 3. Mossbauer spectrum of IV at {GeO4N2} (Fig. 1) is retained. T = 13 K.

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CRYSTAL STRUCTURE, AIM AND HIRSHFELD SURFACE ANALYSIS OF Sn(IV) COMPLEX WITH SALICYLIC ALDEHYDE BENZOYLHYDRAZONE

Alexander Korlyukov a, b, Nаtalia Shmatkovac, Inna Seifullinac, Anna Vologzhaninaa

aNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St., 28, Moscow, GSP-1, 117813, Russian Federation [email protected] bPirogov Russian National Research Medical University, Ostrovitianov Str., 1, Moscow, 117997, Russian Federation cI.I. Mechnikov Odessa National University, Dvoryanskaya St., 2, 65082, Ukraine [email protected]

The molecular and crystal structures of complex [SnCl3(HBs)] (I) (Fig.), where H2Bs – salicylic aldehyde benzoylhydrazone, are determined by X-ray crystallography [1]. Tin(IV) adopts distorted octahedral coordination and the H2Bs is coordinated in a O(C=O)–N(N=CH)–O(Ph) tridentate-chelate mode. Fig. Molecular structure I Equatorial Sn(1)–Cl(1) distance is shorter than axial ones both for isolated molecule and for crystal structure (donation of electron density to the Cl(1) atom from the opposite N(2) atom). Theoretical results of periodic PW-DFT calculations for I obtained with VASP satisfactorily reproduced the experimental crystal structure. To mimic the isolated molecule of I, we used MP2/6-311G(d,p) method/basis set combination. In contrast to PW-DFT, all Sn–Cl and the Sn(1)–O(2) bond lengths in isolated molecule are in very good agreement with experimental ones. To obtain detailed information on the chemical bonding pattern in I, the topological analysis in terms of the Bader’s “Atoms in Molecules” (AIM) theory of experimental, PW-DFT and MP2/6-311G(d,p) calculated electron density distribution functions was carried out. In accordance with AIM, the crystal structure of I is formed by the C–H···Cl and C–H···O bonds, specific Cl···Cl and Cl···N interactions and weak C(π)···C(π) and H···H contacts. Analysis of AIM charges has revealed that amount of charge transferred from ligand to SnCl3 moiety is equal to ≈0.3 e that leads to significant redistribution of bond lengths. Comparison of geometry and characteristics of electron density distribution indicates the weakening of coordination Sn–O and Sn–N bonds in isolated molecule in comparison with crystal up to 10 kcal/mol. This effect was explained by the intermolecular H···Cl bonding. According to the Hirshfeld surface analysis, these interactions have the most pronounced contribution to the crystal packing energy. The significance of this communication lies in both the detailed inspection of the crystal packing effect on the coordination bonds of the tin(IV) atom and intermolecular interactions governing the supramolecular self-assembly of hydrogen-bonded chains by means of specific interactions and π···π stacking. The usage of the topological analysis for study of chemical bonding in complexes of tin(IV) allowed estimation of such important bond characteristics as the nature of Sn–Cl, Sn–O and Sn–N bonds and their energies. Both experimental and theoretical values are in qualitative agreement.

[1]. N. V. Shmatkova;I. I. Seifullina;A. A. Korlyukov. Complexation of SnCl4 with salicylic aldehyde benzoylhydrazone (H2Bs) and isonicotinoylhydrazone (H2Is): Molecular and crystal structures of [SnCl3(HBs] and [SnCl3(Is H] 2CH3CN // Rus. J. Inorg. Chem. – 2015 – Vol. 60, N. 7. –p. 879–885.

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THE INTERACTION OF COBALT(II), NICKEL(II) AND COPPER(II) WITH 5- (METHYLENETRIMETYLAMONIUM)SALICYLALDEHYDE THIOSEMICARBAZONE

Angela Sîrbu, Mihail Secu, Mihail Revenco

Moldova State University

The difficulties associated with low solubility of thiosemicarbazones based reagents were overcome by changing the molecular structure through the introduction of easily ionizable groups. The thiosemicarbazones coordinative compounds with different metals have been investigated via various aspects, including also solution investigation from analytical point of view. This work presents the results of spectrophotometric study of metal complexation with 5- (methylenetrimethylamonium)salicylaldehyde thiosemicarbazone ([H2L]Cl). Investigated thiosemicarbazone has an ionic structure, is water soluble, forming stable solutions over time. In acidic water solution are colorless and are spectral characterized by maximum absorption at wavelength of 300 and 327 nm. In alkaline medium the color of solution turns yellow with an absorption maximum at 370 nm. The color change of the pH variation can be attributed to the reagent dissociation. The addition of metal salt solutions to the thiosemicarbazone provokes the color change in the pH ˂ 7 ranges. Visible changes was observed in the presence of copper(II) and nickel(II) ions. The new complex solution has an yellow-green color compared to colorless solution of the reagent at the same condition. The solutions become yellow in the presence of cobalt(II) salts. The electronic absorption spectrum shows a maximum at 375 nm, 373 nm, 390 nm, for copper, nickel and cobalt respectively. All of this concludes that under the indicated conditions could occur formation of coordination compounds with these metals. The composition of the obtained complexes was determined by the method of continuous variations and molar ratios. Molar absorptivity and stability constants were calculated using the Komari method. The table 1 shows the values of the main parameters of coordination compounds. Table 1. The characteristics of formed coordination compounds with copper(II), nickel(II), cobalt(II) The parameter Cu(II) Ni(II) Co(II) Maximum of electronic spectrum (nm) 375 373 390 Molar ratio metal:ligand 1:1 1:1 1:2 The optimal formation domain (pH) 4,7-5,9 6,0-6,6 5,0-6,1 Molar absorptivity (Ԑ, mol-1∙l∙cm-1) 10050 11040 12260 Stability (lgK) 7,69 5,66 12,27 The analysis results show that [H2L]Cl is not selective. The maxima in the electronic spectra differ slightly being located in the same area. The molar ratio metal:ligand is 1:1 for copper(II) and nickel(II), and 1:2 for cobalt(II). This different behavior can be explained by structure of the complex generators, as well as the coordinating capacity of the reagent. The nature of chemical bonds in the reagent and topology of coordination centers profess that the studied thiosemicarbazone can be a planar tridentate ligand. Copper and nickel ions tend to form compounds with the square-planar geometry allowing the coordination of only one tridentate ligand to the metal. Cobalt ions have an octahedral geometry with the ligands and combining ratio 1:2 seems to be real. The optimal formation domain of coordination compounds is practically the same for all studied ions, which indicates that the complexation occurs with one of the deprotonated forms. The value of complexes stability is higher for copper and cobalt. These metal complexes have a high molar absorptivity, which allows us to try reagent [H2L]Cl for spectrophotometry determination of these metals.

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DESYMMETRIZING THE FERROCENE MOLECULE Dumitru Sirbua, Constantin Turtaa†, Andrew C. Bennistonb

aInstitute of Chemistry of ASM, 3, Academiei str., Chisinau, Republic of Moldova, MD-2028; bMolecular Photonics Laboratory, School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU The first reports in 1951 by Kealy and Pauson, and later in 1952 by Miller et al., on a new organo-iron compound with the chemical formula, FeC10H10, opened up a new area of chemistry. Later in 1973 the Nobel Prize in Chemistry was awarded jointly to Fischer and Wilkinson "for their pioneering work, performed independently, on the chemistry of the organometallic, so called sandwich compounds." The so called compound ferrocene was born. Ferrocene undergoes typical aromatic reactions, such as Friedel-Crafts acetylation, alkylation, formylation, sulfonation and metalation with butyllithium, thus opening access to a wide variety of derivatives. Notably, 1,1′- and 1,2-unsymmetrical ferrocene ligands are widely studied as catalysts for organometallic cross-coupling, hydrogenations, allylic substitutions, hydroformylations, Au-, Ag-catalysed aldol reactions etc. Selective reactions on a single Cp ring to introduce two disparate functional groups (e.g., PPh2, dihydrooxazole) are possible giving planar chiral ligands. For each ring to incorporate a different functional group can be more difficult, requiring a long reaction time and a convoluted purification method. A very mild, fast and chromatography-free method to achieve a similar outcome would appear to be appealing, provided the two functional groups are useful for further reactions. The new method for desymmetrization of ferrocene molecule consists of simple oxidation with potassium permanganate of 1,1′-ferrocenedicarboxaldehyde (1), to give the desymmetrized compounds 1'-formyl-ferrocenecarboxylic acid (2) and 1'-((E)-3-oxo-but-1-enyl)- ferrocenecarboxylic acid (3). These proved to be useful starting materials employed in various reactions like Michael addition and Kröhnke reactions, and as result five new compounds were obtained. The composition and structure of products was confirmed by IR, NMR, mass spectroscopies, elemental analysis and X-ray crystallography, while Mössbauer and UV-Vis absorption spectroscopies were used to study their physico-chemical properties.

Fig. 2.1. Reagents and conditions: (i) KMnO4, CH3CN/H2O, 0 °C; (ii) KMnO4, acetone/H2O, 0 °C.

Acknowledgements: We thank the Engineering and Physical Sciences (EPSRC)-sponsored mass spectrometry service at Swansea for collection of mass spectra, the FP7-PEOPLE-2009-IRSES- 246902 grant for the exchange of researchers, EPSRC for a crystallography equipment grant, and Diamond Light Source for access to synchrotron facilities.

†Deceased 23 March 2015.

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COORDINATION COMPOUND OF PALLADIUM (II) AS MODELS OF ACTIVE CENTERS OF HYDROGENASES

Tatiana STRAISTARI a,b, Constantin TURTA a, Marius REGLIERb

aInstitute of Chemistry, Academy of Sciences of Moldova, 3, Academiei str., Chisinau, Republic of Moldova, MD2028; bISM2/BiosCiences, Aix Marseille Université, Campus Scientifique de Saint Jérôme, avenue Escadrille Normandie-Niemen 13397 MARSEILLE CEDEX 20, France

Climate change and rising global energy demands have prompted an urgent search for new renewable energy solutions. Molecular fuels offer an attractive option for resolving this issue owing to the high energy density that can be concentrated within chemical bonds. In order to expand the nature of metal in complexes modelling the active centres of Hydrogenase, a Pd(II) complex with ligand containing nitrogen and sulphur donor atoms was synthesized (Fig.1). The compound shows electrocatalytic proton reduction in the cyclic voltammetry experiment (Fig.2). The analogical investigation was realised in the presence of trifluoroacetic acid (TFA) (Fig.3). Linear dependence of ic/ip – f([TFA)] permits to determine the value of turnover frequency (TOF ≥ 1800 s-1).

Figure 1. View of the molecule of PdL.

Figure 2. Cyclic voltammograms of [PdL] (1 Figure 3. a) Voltammograms of [PdL], (1 mM) at a mM) at a stationary glassy carbon electrode in stationary glassy carbon electrode in DMF in the DMF, at different scan rates. increasing concentrations of TFA (equiv) b) Plots of ic/ip versus acid concentration for a 1 mM solution of [PdL], in DMF.

Acknowledgements: Present work was supported by the Institutional Project (15.817 02.01F) and bilateral project Moldova France (13.820.08.01/FrF), Dr. Michel Giorgi, Spectropole-RX, Aix-Marseille Université, France References: 1. Anne Volbeda, Marie-Helene Charon, Claudine Piras, Nature 373, 580 - 587 16 1995;

2. B. Loll, J. Kern, W. Saenger, A. Zouni and J. Biesiadka, Nature, 2005, 438, 1040.

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SYNTHESIS OF ZINC AND RUTHENIUM DIMERS WITH (4 - (P-METOXIFENIL)-THIOSEMICARBAZONE) - 2, 3-BUTANE LIGAND

Tatiana STRAISTARI a,b, Constantin TURTA a, Marius REGLIERb, Sergiu SHOVAa

The compounds [Zn2L2](DMF)3 (1) and [Ru2(LH)2Cl2](DMF)x (2) have been obtained from the reaction mixtures Zn(CH3COO)2 4H2O – H2L (methanol - DMF) and Ru(DMSO)2Cl2 4H2O – H2L (methanol - DMF) where H2L (4 - (p-metoxifenil)-thiosemicarbazone) - 2, 3- butane).

Figure 1. View of the molecule of [Zn2L2] (1) Figure 2. View of the molecule of [Ru2(LH)2Cl2] (2) The experimental data of X -ray diffraction pattern for zinc complex is a dimer with 3 molecules of DMF, each zinc atom has a distorted square pyramidal geometry. The bottom positions of the pyramid are occupied by sulfur and nitrogen atoms of the bis (4 - (p- methoxyphenyl)-thiosemicarbazon) -2,4-butane) ligand with bond lengths: Zn(1) – S(1) 2.3175(5) Å, Zn(1) – S(2) 2.4245(6) Å, Zn(1) – N(3) 2.106(2) Å, Zn(1) – N(4) 2.097(2) Å, Zn(2) – S(3) 2.4505(6) Å, Zn(2) – S(4) 2.3127(6) Å, Zn(2) – N(9) 2.095(2) Å, Zn(2) – N(10) 2.092(2) Å. The positions of the top of the pyramids are occupied by sulfur atoms, which plays the role of a bridge between two zinc atoms: Zn(1) - S (3) 2.5132 (7) Å, Zn (2) - S (2) 2.4798 (7) Å. The ruthenium complex is a dimer, where each ruthenium atom has an octahedral geometry. The coordination in the equatorial plane are realized by sulfur and nitrogen atoms of the bis (4 - (p-methoxyphenyl)-thiosemicarbazon) -2,4-butane) ligand with bond lengths for the Ru(01) are Ru(01) – S(033) 2.311(4) Å, Ru(01) – S(108) 2.380(5) Å, Ru(01) – N(018) 1.98(2) Å, Ru(01) – N(74) 1.96(1) Å, and for Ru(02): Ru(02) – S(03) 2.277(5) Å, Ru(02) – S(008) 2.375(6) Å, Ru(02) – N(134) 2.04(2) Å, Ru(02) – N(030) 2.02() Å. In the axial plane for ruthenium complex one position is occupied by the chloride anion, and the other by a sulfur atom bridging between two atoms of ruthenium Ru(01) – S(03) 2.269(6) Å, Ru(01) – Cl(015) 2.408(6) Å, Ru(02) – S(033) 2.290(6) Å, Ru(02) – Cl(014) 2.402(6) Å.

Acknowledgements: Present work was supported by the Institutional Project (15.817 02.01F), Dr. Michel Giorgi, Spectropole-RX, Aix-Marseille Université, France.

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SYNTHESIS, STRUCTURE AND BIOLOGICAL PROPERTIES OF COPPER(II) COORDINATION COMPOUNDS WITH QUINOLINE 4-SUBSTITUTED THIOSEMICARBAZONE

E. Stratulat1, P.Bourosh2, I. Corja1, A. Pui3, A. Dizdari4, V. Prisacari4, O.Palamarciuc1

1Moldova1State University, Chișinău, Republic of Moldova 2Institute of Applied Physics, Chișinău, Republic of Moldova 3Alexandru Ioan Cuza University, Iași, Romania 4State University of Medicine and Pharmacy ″N. Testemitanu″, Chișinău, Republic of Moldova

Thiosemicarbazones are currently well established as an important class of sulphur donor ligands particularly for transition metal ions. Thiosemicarbazones and their metal complexes have received considerable attention because of their antifungal, antibacterial, anti-inflammatory, antiviral and antitumor activities [1, 2]. Interest cooper(II) complexes with 8-formylquinoline thiosemicarbazone derivatives has been stimulated because that their biological activities are often enhanced on complexation [3]. Two compounds with the general formula Cu(HL)(NO3)2·nH2O obtained in reaction of 1 Cu(NO3)2·3H2O with corresponding organic ligands (HL - 4-[2,3- dimethylphenyl]thiosemicarbazone 8-formylquinoline (1) and HL2-4-[2,4- dimethylphenyl]thiosemicarbazone 8-formylquinoline (2)) were separated and structurally characterized. Single crystals suitable for X-ray diffraction studies were obtained by slow evaporation of the solvent from an aqueous solution of the product at room temperature. X-ray analisys shows a mononuclear structure of the products. The copper(II) metal ions are coordinated hexadentate - NNS from organic ligands, two water molecues and one oxygen from nitro anion.

Fig. 1. Crystal structure of the compound 1 (left) and 2 (right).

The antimicrobial activities of the complexes were evaluated. The antimicrobial activity are superior with reference furaciline - compound.

1. Ainscough E., W., Brodie A. M., Denny W. A., Finlay G. J. and Ranford J. D., J. Inorg.Biochem., 1998, 70(3-4), 175–185. 2. Kovala-Demertzi D., Miller J. R., Kourkoumelis N., Hadjikakou S. K. and Demertzis M. A., Polyhedron, 1999, 18, 1005–1013. 3. M. D. Revenko, V. I. Prisacari, A. V. Dizdari, E. F. Stratulat, I. D. Corja, L. M. Proca. Pharmaceutical Chemistry Journal 09/2011; 45(6) p.351-354.

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SUPRAMOLECULAR ARCHITECTURES GENERATED BY HYDROGEN BONDING AND π-π STACKING INTERACTIONS IN THE MONONUCLEAR Cr(III) COMPLEXES

Elena Melnic,a Ecaterina Tocana,b Anatolii V. Siminel,a Lilia Croitora

a Institute of Applied Physics Academy of Sciences of R. Moldova, Academy str., 5 MD2028, Chisinau, Moldova; Tel.: + 373 22 738154; fax:+ 373 22 725887, [email protected]; b Tiraspol State University, Iablocikin str. 5 MD2069, Chisinau, Moldova.

The design of innovative metallo-supramolecular assemblies based on the non-covalent interactions such as π–π stacking and hydrogen bonding may adjust the dimensionality and lead to new topologies with desired functions [1]. It is known that the introduction of polycyclic aromatic chelating ligands containing N-donors, like 2,2'-bipyridine (bipy) and 1,10- phenanthroline (phen) into the metal-acetylacetonato systems prevent the formation of higher dimensional coordination networks and may provide supramolecular recognition sites for π–π, C–H–π stacking and C–H···O hydrogen bonding to form supramolecular structures [1d, 2]. Herein, we report three supramolecular systems constructed by combining two or three organizing forces: metal-coordination, hydrogen bonds and π–π stacking interactions, [Cr(acac)2(bipy)]NO3·2H2O (1), [Cr(acac)2(phen)]NO3·2H2O (2) and [Cr(acac)2(phen)]ClO4·0.25H2O (3), Hacac = acetylacetone. Compound 1 crystallizes in the monoclinic centrosymmetric P2/c (No 13) space group + - and the crystal structure consists of the mononuclear [Cr(acac)2(bipy)] cation, NO3 anion and two crystallization water molecules. Compounds 2 and 3 were obtained similarly and crystallize in the monoclinic centrosymmetric P2/c (No 13) (2) and P21/c (No 14) (3) space groups. Compounds 1 and 2 are isomorphous with consequential increase of unit cell volume in 2 (V=2388.04(15) Å) against 1 (V=2295.5(3) Å). The crystal structures of 2 and 3 contain the + similar mononuclear [Cr(acac)2(phen)] cation and nitrate anion and two solvated water molecules in 2 and perchlorate ion and solvated water molecule in 3 refined with 0.25 occupancy. Each chromium(III) ion displays a distorted octahedral coordination involving two N atoms of the chelating bipy/phen group and four O atoms from two bidentate chelating acac ligands. In the crystal structure of 1 the chelate bipy ligands are stacked by the π–π interactions along the crystallographic b axis, giving supramolecular polymer. In the crystal structures of 2 and 3 π–π stacking interactions are noted between neighboring hydrophobic phen molecules of mononuclear cations, yielding 1D supramolecular zipper-like chains along the b direction in 2 similar to 1 and a direction in 3. Crystal packings in 1 and 2 reveal that the hydrophilic outer - sphere groups (NO3 and H2O) are interconnected through the hydrogen bonds generated a - tetrameric water cluster, that are further organized in a 1D chain with NO3 anions via hydrogen - bond interactions. The disordered ClO4 anions and H2O molecules in crystal packing of 3 are accumulated in the interchain space, held there by the electrostatic and van der Waals forces. Compounds 1-3 show ligand-based luminescent properties.

Acknowledgement. Financial support was provided by the Grant for Young Scientists (15.819.02.03F).

1. (a) C. Janiak, Dalton Trans, 2003, p.2781; (b) B. Moulton, M. J. Zaworotko, Chem. Rev. 101, 2001, p.1629; (c) G. Marinescu, M. Andruh, F. Lloret, M. Julve, Coord. Chem. Rev. 255, 2011, 161; (d) L. Androš, M. Jurić, K. Molčanov, P. Planinić, Dalton Trans., 41, 2012, 14611. 2. (a) P. Mahata, S. Natarajan, Eur. J. Inorg. Chem. 2005, 2156; (b) X. L. Wang, C. Qin, E. B. Wang, L. Xu, Z. M. Su, C. W. Hu, Angew. Chem., Int. Ed. 43, 2004, 5036; (c) B. H. Ye, M. L. Tong, X. M. Chen, Coord. Chem. Rev. 249, 2005, 545. 145

P117

THE CRYSTAL STRUCTURE AND ANTITUMOR ACTIVITY OF 1,6-DINITRATO-BIS[2-(5-METHYLSULFANYL)-4-(PROP-2-EN-1-YL)-4- -(1,2,4-TRIAZOL-3-YL)PYRIDINE]COPPER

P. Petrenko1, V. Graur2, Yu. Chumakov1, I. Truhina2, V. Tsapkov2, D. Poirier3, А. Gulea2

1Institute of Applied Physics of Academy of Sciences of Moldova, Chisinau, Moldova 2Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Moldova 3Centre hospitalier universitaire de Quebec (CHUQ), Sainte-Foy (Quebec), Canada e-mail: [email protected]

The aim of this work is the determination of structural features and biological properties of the coordination compound obtained by the reaction between copper(II) nitrate and 2- formylpyridine 4-allyl-S-methylisothiosemicarbazone. The experiment showed that mentioned above substances react in ethanolic solutions regardless of the combined molar ratios forming fine-crystalline dark green coordination compound with composition С22H24N10O6S2Cu (I). The X-ray diffraction analysis of obtained monocrystals of the complex I showed that there is not any molecule of initial isothiosemicarbazone. The coordination compound I is a square-bipyramidal copper(II) complex which contains two ligands of 2-(5-methylsulfanyl)-4-(prop-2-en-1-yl)-4-(1,2,4-triazol-3- yl)pyridine (L). This ligand has formed in the reaction mixture as a result of oxidative cyclization of 2-formylpyridine 4-allyl-S-methylisothiosemicarbazone. These molecules L are in the inner sphere of the coordination compound in the equatorial plane. They behave like bidentate ligands coordinating to the central atom of copper by pyridinic and azomethinic nitrogen atoms forming five-membered metallacycles. Such case of template cyclization of thiosemicarbazone ligand has been previously described in the literature source [1]. The apical positions are occupied by two monodentate nitrate ions. It is known that coordination compounds with such ligands in many cases manifest biological activity. Therefore, it was studied antitumor activity of this coordination compound. It was determined that thee synthesized complex selectively inhibits the growth

Fig. 1. The crystal structure of I and proliferation of human promyelocytic leukemia HL-60 cells at the concentration 10-5mol/L for 98%. At the concentration 10-6 mol/L and 10-7 mol/L it inhibits 6 and 3% of these cells, respectively. This work showed that the study of new biometal coordination compounds with ligands obtained from heterocyclic aldehyde, ketones and thiosemicarbazones has prospects. References: 1. V.V. Bon, S.I. Orysyk, V.I. Pekhnyo. Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 2, pp. 149– 152.

This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F.

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SYNTHESIS AND BIOLOGICAL ACTIVITY OF COPPER, NICKEL, AND COBALT COORDINATION COMPOUNDS OF CONDENSATION PRODUCTS OF SOME CHALCONES WITH 4-PHENYLTHIOSEMICARBAZIDE

V. Tsapkov1, M. Boeva1, M. Botnaru1, O. Garbuz1, V.Gudumac2, A. Gulea1

1 Laboratory of Advanced Materials in Biopharmaceutics, Moldova State University, 60 Mateevici St., Chisinau, MD 2009, Moldova, 2Department of Microbiology, Virusology and Immunology Nicolae Testemitsanu State University of Medicine and Pharmacy, Chisinau, Republic of Moldova e-mail: [email protected]

The aim of this work is the synthesis, determination of the composition, structure, antioxidant properties of copper, nickel, and cobalt coordination compounds of condensation products of 3-(3,4-dimethoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one, 3-(4- (dimethylamino)phenyl)-1-(pyridin-2-yl)prop-2-en-1-one, and 3-(4-methoxyphenyl)-1-(pyridin- 2-yl)prop-2-en-1-one with 4-phenylthiosemicarbazide. Coordination compounds were synthesized by template reactions between chalcones and 4-phenylthiosemicarbazide in presence of copper, nickel, cobalt chlorides and nitates. The composition of these compounds was determined using elemental analysis: [Cu(L1- 3 . )X] nH2O - - ( X = Cl , NO3 , n = 0 - 2); 1 1 2 1-3 . - - L : R = OCH3; R = H; [ Ni(L )2] nH2O ( X = Cl , NO3 , 2 1 2 1-3 . L : R = N(CH3)2; R = H; n = 0 - 2); [ Co(L ) 2]X nH2O 3 1 2 - - L : R = R = OCH3. ( X = Cl , NO3 , n = 0 - 2). The magnetochemical research showed that synthesized coordination compounds of copper have polynuclear structure. The nickel and cobalt complexes have octahedral structures. The study of biological properties showed that complex CuL1Cl inhibits growth and reproduction of melanoma MeW-164 cells in the range of concentration 10-5 -10-7mol/L. At the concentration 10-5 mol/L it inhibits 90%, at the 10-6 mol/L - 60% and at 10-7 mol / L - 6% of tumor cells. The calculated IC50 value is 0,4 μmol/L. At the same time this compound doesn’t have so much influence on the healthy cells. The IC50 value for Aw-4 fibroblasts is 4,9 μmol/L. On this basis it is presupposed that this substance has lower cytotoxic effect on healthy cells of human organism. It was determined that initial chalcones doesn’t manifest antioxidant activity except 3-(4-(dimethylamino)phenyl)-1-(pyridin-2-yl)prop-2-en-1-one. On the other hand, all synthesized coordination compounds manifest antioxidant activity at the concentration 10-6mol/L. Antioxidant activity depends on the nature of the anion that is part of the complex. Coordination compounds that were obtained from copper chloride possess generally more pronounced antioxidant activity than complexes obtained from copper nitrate. antioxidant activity also depends on the nature of substituents in the phenylic ring of the chalcones. Introduction of the second methoxy group and substitution of the methoxy group by a dimethylamino group lead to an enhancement of the antioxidant activity. This work was fulfilled with the financial support of the Institutional Project 15.817.02.24F.

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SYNTHESIS AND STRUCTURE OF TWO NEW COORDINATION POLYMERS OF COBALT(II) AND NICKEL(II) WITH 1,2,3-BENZENETRICARBOXYLIC ACID AND 4,4'-BIS(1H-IMIDAZOL-1-YL)BIPHENYL

Irina Voda1, Vadim Druta1, Vasile Lozan1, Constantin Turta1 Gamall Makhloufi2, Christoph Janiak2

1Institute of Chemistry, Academy of Sciences of Moldova, 3, Academiei str., MD-2028 Chisinau, Moldova; 2Institute of Inorganic and Structural Chemistry, Heinrich-Heine-University, Düsseldorf 40225, Germany.

Metal-organic frameworks (MOFs) are a class of materials representing coordination polymers based on two main components: the organic linkers and the metal centres or clusters that are connected to each other by coordination bonds, together with other intermolecular interactions generating 2D or 3D extended structures [1]. Here we report the synthesis of two new 1D and 2D MOFs of cobalt(II) and nickel(II) using 4,4'-bis(1H-imidazol-1-yl)biphenyl (BIBP) and 1,2,3-benzenetricarboxylic acid (H3BDC) as ligands. The change of metal ion caused differences in compounds’ structures. The reaction with nickel(II) ions results in a 1D polymer of the general formula {[Ni3(BIBP)3(BTC)2(H2O)4]∙2H2O}n. Each metal center is six-coordinated and has a distorted octahedral geometry. Every 2 carboxylic groups of the acid displays monodentate binding mode through a μ2-oxo bridge. Polymer chain extension is blocked by the 2 water molecules that complete the octahedral surrounding of the 2 marginal nickel(II) ions. This fact is not seen in cobalt compound which is a 2D polymer with general formula [Co3(BIBP)2(BTC)2(H2O)2]n. The 3 cobalt(II) ions of coordinative node have different environment: the central ion is six- coordinated with octahedral arrangement, the other 2 ions are five-coordinated with a distorted trigonal bipyramidal surrounding. Two monodentate carboxylic groups connect 2 cobalt(II) ions of neighboring structural units, while the third carboxylic group acts as a chelate-bridge for marginal cobalt(II) ions. BIBP units serve as pillars to join the chain building a two-dimensional layer (Fig. 1).

Fig. 1. The coordinating nodes and architecture of the polymers {[Ni3(BIBP)3(BTC)2(H2O)4]∙2H2O}n (left) and [Co3(BIBP)2(BTC)2(H2O)2]n (right).

Sorption and thermal properties of the compounds have been investigated.

Acknowledgements Present work was supported by the Moldova State Project Nr. 14.518.02.05A and bilateral Moldovan-German Project Nr. 13.820.08.03/GF.

Reference [1] S. Qiu, G. Zhu. Coord. Chem. Rev. 253(23-24) (2009) 2891.

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A NEW 1D COBALT(II) COORDINATION POLYMER WITH 1,3,5-TRIS(4- CARBOXYPHENYL)BENZENE AND 4,4'-BIS(1H-IMIDAZOL-1-YL)BIPHENYL. STRUCTURE AND INVESTIGATIONS

Irina Voda1, Vadim Druta1, Constantin Indricean1, Vasile Lozan1, Gamall Makhloufi2, Christoph Janiak2

Coordination polymers recently known as metal-organic frameworks (MOFs) have become a forefront in scientific research and public interest, due to the potential for neutral guest bonding including gas storage studies such as hydrogen storage and gas separations [1]. The supramolecular coordination chemistry orientates around various deprotonated anions states of benzenepolycarboxylate ligands and their subsequent coordination to transition metals. {[Co(BIBP)1.5(HBTB)]∙2H2O}n was synthesized using hydrothermal techniques, where BIBP = 4,4'-bis(1H-imidazol-1-yl)biphenyl and HBTB = monoprotonated form of 1,3,5-tris(4- carboxyphenyl)benzene. The compound structure was determined by X-ray analysis showing a new one-dimensional polymer chain. The coordination number of the metal center is 5 with a distorted trigonal bipyramidal surrounding. The three carboxylic groups have a different role: one coordinates cobalt(II) ion in a monodentate way, while the second has a bidentate chelating effect upon a vicinal metal ion. The third group remains protonated, thereby hindering the process of polymer "growth" (Fig. 1).

Fig. 1. The 1D chain of [Co(BIBP)1.5(HBTB)]n, water molecules within pores are omitted.

Sorption properties have been tested through N2 adsorption, unfortunately surface area 2 (SBET = 12.24 m /g) is small comparing with values known from literature. On the other hand, an important feature of the polymer is thermal stability - after water molecules removal from pores the polymer is thermally stable until 340 °C, and then decomposes in 3 steps.

Acknowledgements Present work was supported by the Moldova State Project Nr. 14.518.02.05A and bilateral Moldovan-German Project Nr. 13.820.08.03/GF.

Reference [1] L. Xu, E. Choi, Y. Kwon. Inorg. Chem. 47 (2007) 10670.

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SYNTHESIS, CRYSTAL STRUCTURE AND STUDY OF TWO NEW ZINC(II) AND COBALT(II) COORDINATION POLYMERS BASED ON 2,6- PYRIDINEDICARBOXYLIC ACID AND 1,4-BIS((1H-IMIDAZOYL-1- YL)METHYL)BENZENE

Irina Voda1, Vadim Druta1, Constantin Turta 1, Andrew C. Benniston2

1Institute of Chemistry, Academy of Sciences of Moldova, 3, Academiei str., MD-2028 Chisinau, Moldova; 2Molecular Photonics Laboratory, School of Chemistry, Newcastle University, NE1 7RU Newcastle upon Tyne, United Kingdom.

The latest MOFs investigations are dictated by a large area of applications since they display interesting properties in catalysis, gas adsorption and separation, sensing, magnetism, luminescence, etc. [1] Our own research effort has focussed on using 1,4-bis((1H-imidazoyl-1- yl)methyl)benzene (BIB) to create pore-like structures. As an extension to this work the ligand with zinc(II) and cobalt(II) in the presence of the tridentate 2,6-pyridinedicarboxylic acid (H2PDC) were reacted to produce coordination polymers (see the scheme) with general formulae {[Zn2(BIB)2(PDC)2]·9.5H2O}n (ZnP) and {[Co(BIB)1.5PDC]·4H2O}n (CoP). X-ray crystallography method together with elemental and IR analyses showed that molecular structure of zinc complex comprises of four zinc(II) ions, each with a coordination BIB PDC PDC geometry consisting of {(N )2 N (O )2} node. The five coordinate geometry at each zinc(II) ion is slightly different but resembles a distorted trigonal bipyramid. Two different strands of the coordination polymer interweave with each other in a snake-like manner. In the cobalt(II) complex metal ions are six coordinated with a distorted octahedral geometry, BIB PDC PDC coordination node consists of {(N )3 N (O )2}.

Thermal stability of complexes is quite high, after the removal of water molecules from the structures they remain stable up to 200-230 °C. Unfortunately, sorption measurements have shown small values of BET surface areas (1.63 for ZnP and 9.09 m2/g for CoP). Further investigations are needed to elucidate the field of their implementation.

Acknowledgements Present work was supported by PCAP FP7-PEOPLE-2009-IRSES, Nr. 246902. Authors are grateful to Crystallography Laboratory, School of Chemistry, Newcastle University.

References [1] C. Janiak, J. K. Vieth. New J. Chem. 34 (2010) 2366.

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DETERMINATION OF COPPER (II) AND LEAD (II) IONS BY SODIUM SALT OF 4-PHENYLSEMICARBAZONE 1,2-NAPHTHOQUINONE-4-SULFONIC ACID

Oxana Zagurskaya-Sharaevskaya1, Igor Povar2 (1) Department of Chemistry and Chemical Technology, State University of Moldova, Chisinau, Moldova, e-mail: [email protected]. (2) Department of Physicochemical Methods of Analysis and Research, Institute of Chemistry of the Academy of Sciences of Moldova, Chisinau, Moldova, e-mail: [email protected]

For spectrophotometric determination of copper (II) and lead (II) ions a new reagent, sodium salt of 4-phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic acid has been proposed, which allows to measure the micro-amounts of copper in the tap water, copper alloys and lead ions in alloys in the presence of interfering ions (bismuth (III), mercury (II)). This method is relatively simple in the synthesis of reagent, which is easily re-crystallized from water-ethanol solution and is stable in the crystalline state. It is also characterized by low cost and high sensitivity. Copper (II) and lead (II) ions in acetate buffer, pH 5.74 - 6.51 (for copper ions) and pH of 6.1 - 7.0 (for lead ion) form colored complexes of red-pink color with absorption maxima at 520 nm and 550 nm, respectively, while the individual reagent under these conditions absorbs at 440 nm. The following optimal conditions of complexation have been established: the acidity of the medium, the concentration of copper (II) and lead (II) ions, compliance to the key law of light absorption (Beer–Lambert–Bouguer), the complex composition (1:1 for copper and 1:2 for lead). The calculated value of the complex stability constant for copper ions (II) is logβ = 4.53, the molar absorption coefficient is 3•104 L•mol-1•cm-1, the Beer–Lambert–Bouguer law obeys within the concentration range of 0.3 • 10-6 up 4.0 • 10-5 mol/L. For lead (II) ions the complex stability constant is logβ = 9.18, the measured molar absorption coefficient is 1.5•104 L•mol- 1•cm-1, the Beer–Lambert–Bouguer law is accomplished between the concentration range 2.0 • 10-6 and 1.0 • 10-5 mol/L. The methods of determining copper (II) ions in tap water, superconducting ceramics and copper alloys, as well as lead (II) ions in alloys, have been developed. For their determination the following ions do not interfere: iron (II), iron (III), manganese (II), magnesium, calcium, sodium, potassium (at concentrations not exceeding 1.0 • 10-2 mol/L). The interfering effect exerts bismuth (III) and mercury (II) ions at concentrations of 1.0 • 10-5 mol/L and higher).

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X-RAY STUDY AND CHARACTERISATION OF A NEW PALLADIUM COMPLEX WITH 2-(2H-BENZOTRIAZOL-2-YL)-4,6-DITERT-PENTYLPHENOL LIGAND

Olesea CUZAN1,3, Sergiu SHOVA1,2, Michel MAFFEI3, Marius REGLIER3, Andrew C. BENNISTON4, Constantin TURTA

1Institute of Chemistry of the Academy of Sciences of Moldova, Academiei str. 3, MD-2028 Chishinau, Moldova 2Institute of Macromolecular Chemistry "Petru Poni" 41A Grigore Ghica Voda Alley, Iasi- 700487, Romania 3Aix Marseille Université, ISM2, UMR CNRS 7313, Av. Escadrille Normandie Niemen, 13397 Marseille, cedex 20, France 4Molecular Photonics Laboratory, School of Chemistry, Newcastle University, Newcastle upon Tyne NE1 7RU, UK

This work reflects the synthesis and characterization of the new bis[2-(2H-benzotriazol-2-yl)- 4,6-ditert-pentylphenolato]palladium(II) complex as potential catalyst in the reaction of water splitting. Monocrystals of title compound were obtained upon recrystallization from THF solution. The compound crystallizes in monoclinic P21/n space group, a = 15.7047(8), b = 29.5155(19), c = 20.0274(11) Å, β = 102.241(6) °.

Single crystal X-ray diffraction study of the complex reveals two similar but symmetry independent centrosymmetric mononuclear complexes, in which two molecules of bidentate ligand coordinate to the palladium central atom via Nitrogen and two Oxygen atoms resulting in a distorted square plan coordination of the metal.

Figure 1. Molecular structure of Bis[2-(2H-benzotriazol-2-yl)-4,6-ditert- pentylphenolato]palladium(II) complex.

Elemental analysis and spectroscopic methods (IR, 1H NMR and 13C NMR) are in concordance with the X-ray structure.

Aknoledgements: This research was supported by the National Scholarship of World Federation of Scientists and the 14.518.02.05A project.

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SYNTHESIS AND CRYSTAL STRUCTURE OF DINUCLEAR DIOXOVANADIUM(V) COMPLEXES

Natalia Talmaci1, Diana Dragancea1, Sergiu Shova2

1 Institute of Chemistry of the Academy of Sciences of Moldova, Academiei str. 3, MD-2028, Chisinau, Republic of Moldova, e-mail:[email protected]; 2”Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, 700487, Iasi, Romania

The coordination chemistry of vanadium with its variety of oxidation states has been the subject of extensive research mainly due to two type of activity: biological and catalytic. Recently, a number of vanadium(V) complexes with bis-hydrazone ligands exhibited high catalytic activity in alkane oxidation reactions [1-2]. As a part of the study of coordination behavior of carbohydrazone based ligands, we are extending our research on the synthesis of vanadium complexes. This work describes the preparation and structural characterization of 1-2 dinuclear dioxovanadium(V) complexes (NH4)[(VO2)(H2L )]·CH3OH (1-2), which involve the 1 symmetrical Schiff base ligands 1,5-bis(salicylaldehyde)carbohydrazone (H2L ) and 1,5-bis(5- 2 methyl-salicylaldehyde)carbohydrazone (H2L ). Vanadium complexes were prepared by treating methanolic solution of the corresponding ligand with two equivalents of NH4VO3. Single-crystal X-ray diffraction analyses reveal that complexes 1−2 are isostructural. As 1 shown in Fig. 1 the ligand H2L acts as a triply-deprotonated base in the enolic form anti bonding to two cis-VO2 moieties through two tridentate units ONO and ONN, respectively. Each vanadium(V) ion is five-coordinate in a tetragonal pyramidal environment, with the doubly bonded oxygen O(1)and O(2) and O(6) and O(7) in the apex.

Fig. 1. Molecular structure of complex 1

References 1. S. Gupta, M. V. Kirillova, M. F. C. Guedes da Silva, A. J. L. Pombeiro, A. M. Kirillov. Inorg. Chem., 2013, 52, 8601−8611. 2. S. Gupta, M. V. Kirillova, M. F. C. Guedes da Silva, A. J. L. Pombeiro. Appl. Catal. A, General, 460–461, 2013, 82–89. 3. M. Sutradhar, N. V. Shvydkiy, M. F. C. Guedes da Silva, M. V. Kirillova, Yu N. Kozlov, A. J. L. Pombeiro, G. B. Shul’pin. Dalton Trans., 2013, 42, 11791–11803.

153

P125

MODIFICATION OF TiO2 PARTICLES NANOSTRUCTURE FOR PHOTOCATALYTIC APPLICATIONS

*Covaliova Olga, **Covaliov Victor, *Duca Gheorghe

*Institute of Chemistry, Academy of Sciences of Moldova, Chișinău, MD 2028, Str.Academiei 3 **State University of Moldova, Research Center of Applied and Ecological Chemistry, Republic of Moldova. Chișinău, MD 2009, Str.Mateevici 60 e-mail: [email protected]

Water treatment technologies based on the heterogeneous catalysis, specifically applied for waters containing the organic pollutants, receive special attention of the researchers in different countries. Using of the fine metal oxide particles, such as TiO2 with nanotubular structure, is one of the most promising approaches. Photocatalytic activity of TiO2 may be explained with that the light quanta under the UV-irradiation with the wavelength l<385 nm, excite the electrons, moving them from the valency zone to conductivity zone with the formation of electron-hole - + pairs, i.e. TiO2 + hν → TiO2(е +h ). This promotes the formation of high reactive oxygen- - containing radicals such as 'OH, 'О2 , 'НО2, 'О2- etc. in water environment [1]. Photocatalytical treatment of waters containing the persistent organic pollutants, may result in their mineralization due to the development of the reduction-oxidation processes with the involvement of active radicals. This leads to the formation of simple non-toxic compounds • following the general type reaction: ОН + О2 + СnOmH(2n-2m+2) → nCO2 + (n-m+1)H2O. The improved methods of electrochemical synthesis of nanostructured TiO2 were proposed. The resulted products were in the form of deposits strongly attached to Ti base, and separate particles formed in water environment [2]. The mechanism of nano-tubular TiO2 structure formation was discussed from the point of view of the structural-geometric theory. The role of the barrier layer as well as the other factors is discussed, which determine the character of tubular structure of the anodic layers on Ti. It was shown that, independently on the anodic treatment regime, the ratio of elementary cell and applied voltage is maintained: W = 2SE + D = 2L + D, where W – cell dimension (diameter); E – oxide forming voltage; D – pore diameter; S – relative thickness of cell wall, characterizing the thickness share per each V of forming voltage; L – cell wall thickness. Dependence of barrier layer (Т) and elementary cell wall thickness is expressed by the formula: T = 1,2 L. The correlation between the pores diameter, cell diameter and thickness of barrier layer is: D = W – 1,67 T. The specific amount of nanotubes’ elementary cells, calculated on the base of cell dimensions, makes (3-5)∙108 in 1 сm2 and is changing in inverse proportion to voltage. A new principle of flow-through photocatalytic reactor on the base of nano-tubular TiO2 was developed [3]. The composite compounds production and applications was tested [4]. The developed reactor makes it possible to obtain the nano-tubes surface covered with copper layer by chemical-catalytic reduction. The TiO2 nanotubes covered with Cu may be perspective for using in the reactors that can help to radically increase the rate of CO2 conversion, in mixture with water vapour, in natural gas under the solar irradiation. This can help to resolve the greenhouse gases emissions problem in future.

References: 1. O.Covaliova. Titanium dioxide production of photocatalytic processes. Studia Universitatis, Nat. Sci.Ser., 6 (26) (2009), p.187-194. 2. Patent Nr. 227Y MD. Method of nanodisperse titanium oxide preparation. O.Covaliova, M.Enachi. BOPI, 6 (2010) 3. Patent Nr. 186Y MD. Photocatalytic reactor for water treatment. О.Covaliova, М.Enachi. BOPI, 4 (2010). 4. Patent Nr. 4294 MD. Method of TiO2 nanotubes production and equipment for its realization. V.Covaliov, O.Covaliova, Gh.Duca, M. Enachi. BOPI, 7 (2014).

154

P126

A NEW METHOD OF CYANCOBALAMIN (VITAMIN B12) PRODUCTION AND ITS PRACTICAL USES

*Covaliova Olga, **Covaliov Victor, *Duca Gheorghe, **Nenno Vladimir, **Bobeica Valentin

*Institute of Chemistry, Academy of Sciences of Moldova, Chișinău,MD 2028, Str.Academiei 3 **State University of Moldova, Research Center of Applied and Ecological Chemistry, Republic of Moldova. Chișinău, MD 2009, Str.Mateevici 60 e-mail: [email protected]

Cyanocobalamin is widely used in medicine as a therapeutic drug, as well as a cattle and poultry feed additive as an important preparation against many diseases. This is a complex protein Co compound of porphyrin series with general formula С63Н90О14N14PCo and molecular weight 1357,39, being the largest metal-organic molecule which structure was determined by Nobel Prize Winner Dorothy Hodgkin in 1956 [1]. СN group in the B12 molecule can be substituted with ОН, ОNО, SO3, SCN, Cl, Br and other groups, forming the appropriate cobalamins derivatives, many of them possessing the biological activity. In spite of the long-term efforts of the researchers, among them Woodwarth and Eshengover [2, 3], chemical synthesis of cobalamin still remained to be extremely complicated and low-productive process. Therefore, the industrial synthesis of cyanocobalamin is performed exclusively with the methanogenic bacteria during their living activity. The typical production technology is based on the anaerobic digestion processes of mainly the distillery or winery vinasse, which sludge contained the raw protein (34,2-37,2 % dry substance mass), aminoacids, fat-like substances (10-14,7%) and other valuable components. However, the product yield is low and the process is energy-consuming. Due to its solubility in water, cobalamin is extracted from water fraction by the long-term (about one-month) evaporation. Our studies made it possible to proposed the improved technology for vitamin B12 production, which involves the anaerobic microbiological synthesis of B12 under the meso- or thermophylic digestion regime, along with the biomethane formation. The intergater reactor for this process realization was developed. To intensify the anaerobic digestion process, types new phytocatalysts related to the natural biologically active compounds, were proposed. In this way, a higher target product and methane yield was reached. As a cobalt-containing additives, being the precursors of anaerobic synthesis of vitamin B12, suppliers of Co and cyanide, the inorganic substances attainable for methanogenic microorganisms were selected: Co complexes – cytrate-mmonia complex [2C6H5O7Со(III)· C6H6O7(NH4)2 ·nH2O] and tartrate-ammonia one [2 С4Н3О6Со(III)· C4H4O6(NH4)2 ·nH2O], as well as potassium ferrocyanide. To extract cobalamin from the liquid fraction, instead of evaporation, use of the natural diatomite was proposed. The resulted product, enriched with vitamin B12, is an important component of the mixed cattle forage, stimulating the animals growth. This work is based on the series of Moldovan patents: Nr. 322, 3716, 4129, 4156, 4176, 4192 (Pat.MD). Currently, the pilot equipment for the production of forage additive containing vitamin B12 is on the stage of manufacturing.

References: 1. Hodgkin, D. Crowfoot; Kamper, J.; Mackay, M.; Pickworth, J.; Trueblood, K.N.; White, J. G. (1956). "Structure of Vitamin B12". Nature 178 (4524): 64–66. 2. Woodward, R. B. (1973). "The total synthesis of vitamin B12". Pure Appl. Chem. 33 (1): 145–178. 3. Eschenmoser, A.; Wintner, C. E. (1977). "Natural Product Synthesis and Vitamin B12". Science (Washington, DC, U. S.) 196 (4297): 1410–1420.

155

P127

SUPRAMOLECULAR ENSEMBLE CONTAINING DINUCLEAR AMINE-THIOLATE COMPLEXES AND ORGANIC COMPONENTS

Vasile Lozan

Institute of Chemistry, Academy of Sciences of Moldova, 3, Academiei str., MD-2028 Chisinau, Moldova The chemistry of container molecules has developed extensively over the past two decades. Many container molecules such as calixarenes, resorcarenes, cyclodextrins, carcerands and glycourils have been invaluable in studying the fundamental principles of inclusion phenomena and consequently their use in separation science or drug delivery, as two examples of application. Importantly, the area has attracted interest in the field of supramolecular chemistry because the properties of such host–guest compounds are often different from those of their constituent components. By adjusting the size and form of the binding cavity it is often possible to complex co-ligands in unusual coordination modes, to activateand transform small molecules, or to stabilize reactive intermediates [1, 2]. One subclass are the metallated container molecules, in which metal ions and clusters are used as both a point of recognition and to give the container a well-defined structure. Such compounds also allow for an interplay of molecular recognition and transition-metal catalysis, and for the construction of more effective enzyme mimics. Of interest to the present work is the ability of metallocavitands to recognize and encapsulate difunctionalised molecules towards stabilising or enhancing the optical and electronic properties of redox- and photo-active compounds within a confined environment set up by two hemispheres.

II 2+ 1 [(LNi 2)2(acetylenedicarboxylate)] II 2+ 2. [(LNi 2)2(terephtalate)] II 2+ 3. [(LNi 2)2(isophtalate)] II 2 2+ 4. [(LNi 2) (ferrocendicarboxylate)] II 2 2+ 5. [(LNi 2) (naphthalene diimide dicarboxylate)]

The complexes 1-5 were readily prepared from the reaction of the dinuclear complex II + [LNi 2(μ-Cl)] (L=24-membered macrocyclic hexaaza-dithiophenolate ligand) and the corresponding triethylammonium dicarboxylate, prepared in situ from the acid and triethylamine in methanol in a 1:2 molar ratio, and isolated in high yield as the perchlorate or tetraphenylbora-te salts.The complexes, have been synthesized and characterised by UV/Vis-, IR-spectrosco-py, Cyclovoltamperometry, and X-ray crystallography. Each dicarboxylate dianion acts as a quadri- dentate bridging ligand linking two bioctahedral LM2 units via μ1,3-bridging carboxy-late functions to generate discrete dications with a central LM2(O2CR-CO2)M2L core. Magnetic susceptibility measurements on the complexes over the range 2.0 -295K reveal the presence of II weak ferromagnetic exchange interactions between the Ni ions within the dinuclear subunits.

Reference [1] Lozan V. Chem. J. Mold. 2013, 8(1), 58-77. [2] Lozan V., Loose C., Kortus, J., Kersting B. Coord. Chem. Rev., 2009, 253, 2261-2285.

156

P128

SYNTHESIS AND STUDY OF A NEW Co(II) MOF USING RIGIDE LIGANDS

Vadim Druta1, Irina Voda1, Polina Bourosh2, Victor Kravtsov2, Vasile Lozan1

1Institute of Chemistry, Academy of Sciences of Moldova, Chisinau, Moldova 2Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Moldova

The aim of this work was the synthesis, determination of the composition, structure, and sorption properties of Co(II) MOFs using rigide ligands. There we report a method of solvothermal synthesis of Co(II) complex using 1,3,5-tris(4- carboxyphenyl)benzene acid (CFB) and bis-imidazolyl-bis-phenylene (BIBPh) as starting ligands. The synthesized product represents a tridimensional polymeric compound of formula

{Co3O(OH)(1,3,5-CFB)2(DMF)2(H2O)3}∞. The composition and structure of complex was demonstrated by various methods of analyses (EA, IR, thermogravimetry, single crystal X-ray). Thermogravimetric study has demonstrated, that heating of polymeric sample up to 250 °C leads solely to elimination of solvent molecules from micropores. The degassed compound is stable up to 360 °C, then a process of irreversible destruction of molecular carcass is occuring. Single crystal X-ray structure investigation of coordination compound {Co O(OH)(1,3,5-CFB) (DMF) (H O) } has demonstrated, that in the crystalline phase an 3 2 2 2 3 n unusual polymeric structure was obtained, where trinuclear groups {µ -O-Co3(II)OH} are 3 interconnected by bridging molecules of hexadentate ligand 1,3,5-CFB. In polymer are present two types of large cavities where solvent molecules of H O and DMF are adsorbed. 2

Fig. 1. Crystal structure (left) and molecular packing (right) of the polymeric compound {Co3O(OH)(1,3,5-CFB)2(DMF)2(H2O)3}∞.

0 Sorption properties have been tested through N2 adsorption at 273 K and shown a 3 2 maximum sorptio value ~110 cm /g. The surface area (SBET = ~330 m /g) is relatively moderate comparing with known highest values.

Present work was supported by the ASM-BMBF joint research project Nr. 13.820.08.03/GF.

157

Index of authors

Ailiesei G. P2 Cariati Elena, P39 Aldoshin S.M. L3 Cazac T. P17 Amarandi R.-M. P3 Cazacu M. O8, O13, P1, P49 Anachii A. P24 Ando Y. O6 Cepoi L. P100, P101 Andreica-Sandica B. P80 Andronache L. P4 Chapurina L.F. P89 Andronati S. A. P59 Chernyavskii A. P81 Andruh M. L6 Chernysheva N.V. P14, P46, P88, Anghel L. P5 P89, P90 Aricu A. P6, P7, P21, P64, Chiriac T. P100, P101 P101 Chisca D. P18, P19 Arsene I. P8, P23, P42, P44 Choquesillo-Lazarte D. P60 Chumakov Yu. P9, P26, P86, Azarov S.M. P55 P91, P92, P117 Azarova T.A. P54, P55 Ciobanu M. P2 Baca S. G. P15, P16, P19, Ciocarlan A. P2, P21, P64 P30, P38, P70, Clapco S. P20 P99 Clérac R. L13, O5, O7, P37, Bairac N. P9 P105 Balan C. P22 Cocu M. P22 Balan M. O13, P2, P80 Codreanu S. P100 P101 Barba A. P6, P7, P34, P56, Corja I. P17, P115 P40 P47, P101 Cornei N. O3 Coropceanu E. P18, P19, P23, P28, P39, P90 Barbă N. P102 Cotovaia A. P11, P12, P24, Bartha E. P10 P25 Bartolomé F. O1 Covali A.V. P46, P90 Bartolomé J. L12, O1 Covaliov V. P13 Baumer V. N. P58 Covaliova O. P13 Benniston A. C. L8, P112, P121, Crisan L. P27 P123 Crisan M. P26 Bernic V. P74 Croitor L. P18, P19, P28, Birca M., P11, P12 P30, P39, P90, Biriukova M. P81 P116 Bivol C. M., P20 Crudu V. P12, P91 Bobeică V. P13 Cuba Lidia P63 Boeva M. P118 Cucicova C. P101 Bologa О. А. P14, P20, P23 Cuzan O. P123 Botezat O.I. P15 D’Ambrosio M. P21 Botnaru M. P118 Danac R. P29 Bourosh P. P16, P17, P23, Darii M. P30 P26, P115, P128 Dascalu M. O13 Branitskiy G.A. P55 Dănilă D. P2 Brazzolotto D. O7 Dechambenoit P. L13 Bulhac I. P14, P20, P22 Decurtins S. P16, P19, P99 P23, P63, P76 Dehghan A. P31 Deleanu C. O9, P2, P65, P80 Bulimestru I. O3 Bulmaga P. P17 Deleanu M. P10 Cadot E. L14 Deleanu M. P32 158

Deseatnic- Ciloci A. P20 P91, P92, P102, Dikusar А.I. P77 P117, P118 Diru M. P33 Gutsanu V. O12 Dizdari A. P115 Gutsu Ia. P25 Dorif A. P34 Gutsul T. P75, P76 Dorogoncean C. P50 Guțu T. P47 Dragalin I.P P6, P7, P35 Halimova E. I. P59 Dragancea D. P36, P124 Halip L. P26 Druta V. P119, P120, Hamagawa M. O6 P121, P128 Handa M. O6 Duboc C. O7 Handa M. P57 Duca G. L1, O2, P5, P41 Hanganu A. P10 Duldner M. P10 Hauser J. P16 Dumbrăveanu V. P100 Hori S. O6 Dvornina E.G P20 Hosoya S. P48 Eftodii S. P12, P91 Iacob M. P49 Ellern A. P66, P67 Iancu S. P10 Ennan A. A. P58 Ilieș D.-C. P85 Erhan R. V. P5 Ilkhani A. R. O10, O11, P31 Ferbinteanu M. P62 Indricean C. P45, P120 Filippova I.G. P38 Ionescu S. P10 Floquet S. L14 Isac-Gutul T. P50, P51 Fonari M.S. P18, P19, P28, Ivancic A. P13, P52 P39, P59, P90 Ivanets A.I. P53, P54, P55 Forni A. P39 Jalbă S. P56 Fruth V. P61 Janiak Ch. L5, P119, P120 Fujimori R. O6 Jeon I.-R. L13 Garbuz O. P4, P11, P24, Julea F. P86 P25, P74 P78, Kabanova T. A. P59 P84, P118 Karlshøj S. P3 Gdaniec M. P68, P69 Kawauchi S. P57 Gelmboldt V. O. P58 Khitrich N. V. P108 Gennari M. O7 Khoma R. E. P58 Georgescu E. P65 Kitaev V.V. P109 Georgescu F. P65 Klokishner S. I. P99 Geru I. I. L16, P34, P42 Kögerler P. P15 Gherciu I. P52 Koksharova T. V. P58 Gîrbu V. P40 Korlyukov A. P110 Gonţa M. P41 Koumousi E. S. L13 Gorbachev M. Yu. P42, P43, P44 Kovali А.V. P14, P88, P89 Goreacioc T. P103 Krämer K. P19, P99 Gorinchioy N. O10, P8, P42, Kravtsov V. Ch. O2 P43, P44 Kravtsov V. Ch. P15, P16, P30, Gorinchoy V. P45, P46 P59, P70, P99, Gorincioi E. P6, P7, P40 P128 Gorincioi N. P23 Kuchkova K.I., P6 P7 Graur V. P25, P91, P92, Kuriyama T. O6 P117 Kuznetsova T.F. P53, P54 Grinco M. P40, P79 Kӧgerler P. P66, P67 Gudumac V. P4, P11, P24, Labliuc S.V. P20 P25, P84, P118 Lazarescu A. P60, P61, P62 Gulea A. L4, O3, P4, P9, Levchenkov S.I. P108, P109 P11, P12, P24, Lipkowski J. L10, P59 P25, P56, P73, Liu S.-X. P16, P19, P99 P74, P78, P83, Lozan V. P45, P46, P88, P84, P85, P86, P60, P89, P119, 159

P120, P127, P128 Paraschivescu C. P85 Lunganu M. P79 Parshutin V.V. P14, P46, P89, Lungu L. P21, P64 P88, P90 Lupascu T. P93, P103, P107 Pavlovsky V. I. P59 Macsim A.-M. P2, P65 Pécaut J. O7 Maffei M. P123 Perreault M. P83, P84, P102 Makhloufi G. P119, P120 Petcenco I. P11 Malaestean Iu. P66, P67 Petrenko P. P9, P75, P83, Malic E. P11, P12 P86, P91, P92, Malik S. O4 P117 Mangalagiu I. I. L11, P29, P64 Petuhov O. P93 Mathonière C. L13 Pogrebnoi S. P94 Mazepa A.V. P58 Poirier D. L9, P83, P85, Melnic E. P70, P71, P116 P117 Melnic S. P68, P69 Popa N. O3, P95 Mentre O. O3 Popov L.D. P108 Mereacre V. P72 Popovici L. P29 Mezey R.-Ș. P73 Povar I. P96, P122 Mihalciuc O. P74, P97, P104 Powell A. K. L15, P72, P98 Mikuriya M. O6, P48, P57 Preda S. P61 Mironic T. P75 Prisacari V. P78, P92, P115 Mirzac A. P63, P76 Prisacaru V. P47 Miscu V. P100, P101 Procopisin L. P97 Mitcov D. L13 Prodius D. P98 Mitina T. P63 Prozorovich V.G. P53 Mitkevich N. P78 Pui A. P3, P87, P115 Mitsuhashi R. O6, P48, P57 Pushcashu B. P45 Miu A. P80 Racles C. O13 Modrea V. M. P73 Radkevich A.V. P53 Morarescu O. P35, P79 Radu I. P16, P99 Morari P. P33 Réglier M. L7, P113, P114, Morozov A.N. P108 P123 Mosanu E. P103 Reu O. S. P99 Munteanu C. P61 Revenco M. P111 Myrzak V. P77 Righetto S. P39 Nedelko N. P62 Robu Ş. P52 Nenno V. P13 Rosca R. M. P35 Nica S. P10 Rosenkilde M. M. P3 Nicolenco A. P25 Roșu T. P73, P85, P86 Nicolescu A. O9, P2, P65, P80 Rouzières M. O7 Nicorici A. P61, P75 Rudi L. P100, P101 Ogarkov A. P81 Rudic V. P92, P100, P101, Ono K. P57 P104 Oprean C. P85 Rusnac R. P102 Orio M. O7 Rusu M. P107 Osipov I. P43, P82 Sakharov S. P81 Ostrovsky S. M. P99 Sanda G. M. P32 Pacureanu L. P27 Sandu M. P103 Paholinitcaia A. P50, P51, P83, Sanina N.A. L3 P84, P102 Sardari V. P104 Pahonțu E. P85, P86 Sârbu C. P45 Palamarciuc O. O5, P37, P115, Secara E. P101 P87, P105 Secu M. O5, P33, P105, Palamarciuc T. O5, P87 P111 Palii A. V. L3, P99 Sedcenco M. P35 Pantea V. P4, P74 Seifullina I.I. P108, P109, P110 160

Shepel D. P106, P107 Ungur N. P6, P7, P40, P79 Shevtsov S. P81 Ushakov I. Yu. P59 Shmatkova N.V. P108, P109, P110 Uşurelu N. O9, P80 Sholtoyan N.S. P14, P46, P88, Valuța A. P101 P89, P90 van Leusen J. P15 Shova S. O13, P1, P64, Vieru E. P106 P68, P69, P114, Vitiu A., P23 P123, P124 Vlad A. P1 Shvets I. P104 Vlad P. P6, P7, P101 Silion M. P2 Vlasenko V.G. P108, P109 Sima A. V. P32 Voda I. P119, P120, Siminel A. V. P116 P121, P128 Simionescu B. C. L2 Vologzhanina A. P110 Sirbu D. P49, P112 Vornicu N. P21, P64 Siretanu D. L13 Voronets E.A. P54 Sîrbu A. P17, P111 Vulturar R. O9, P80 Ślawska-Waniewska A. P62 Yamamoto H. O6 Smagli V. P91 Yoshioka D. O6, P57 Solntsev K. P81 Yu S. O7 Soroceanu A. O8 Zagurskaya- P122 Sova S. O3, O5, P37, P87 Sharaevskaya O. Spinu O. P96 Zaltariov M.-F. O8, P1 Stavarache C. P2, P65 Zariciuc E. P92 Stiubianu G. P49 Zarubo A.M. P53 Straistari T. P113, P114 Zatîc A. P102 Stratulat E. O5 Zbancioc G. P64 Stratulat E. P37, P87, P115 Zinicovscaia I. P100 Stroncea M. P21 Zubareva V. P76 Suzuki T. P48 Şavga C. P41 Ştefanache C. P2 Tagadiuc O. P4, P104 Talmaci N. P124 Tancret N. O3 Tarita A. P103 Tatarciuc I. P83 Terenti N. P60 Tiurin J.P. P20 Tocana E. P116 Tomioka N. O6 Triboi C. P51 Trigub A.L. P109 Truhina I. P92, P117 Tsapkov V. P11, P12, P25, P24, P78, P91, P92, P117, P118

Tugui C. P49 Turcan S. P103

Turta C. L12, P68, P69, P112, P113, P114, P119, P121, P123 Tutovan E. P50, P51 Uehara N. O6

161