DOCSLIB.ORG

Identification of Cysteine As the Reactive Group in Pyruvate Kinase Alkylated by 5-Chloro4.Oxopentanoic Acid by R

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Identification of Cysteine As the Reactive Group in Pyruvate Kinase Alkylated by 5-Chloro4.Oxopentanoic Acid by R Biochem. J. (1976) 159,213-219 213 Printed in Great Britain Identification of Cysteine as the Reactive Group in Pyruvate Kinase Alkylated by 5-Chloro4.oxopentanoic Acid By R. ALAN CHALKLEY and DAVID P. BLOXHAM Department ofPhysiology and Biochemistry, University of Southampton, Southampton S09 3TU, U.K. (Received 8 March 1976) 4-Hydroxypentanoic acid alanine thioether was synthesized and characterized by n.m.r. spectroscopy. This derivative corresponded to the modified amino acid obtained by allowing 5-chloro4oxo[3,5-3H]pentanoic acid to react with rabbit muscle pyruvate kinase. Performic acid oxidation of 4-oxo[3,5-3H]pentanoic acid alanine thioether in pyruvate kinase gave [3H]succinate (67%) and [3H]carboxymethylcysteine (33%) as expected. Evidence is presented to show that NaBH4 reduction followed by periodate oxidation and analysis of radioactive formaldehyde production may provide a con- venient method for distinguishing between thiol and amino alkylation by halogeno- methyl ketone compounds. Peptide 'mapping' confirms that the modification by 5-chloro- 4-oxopentanoic acid occurs primarily at one region of pyruvate kinase. In the preceding paper (Bloxham & Chalkley, (Bloxham & Chalkley, 1976). In all these experiments 1976), 5-chloro-4-oxopentanoic acid was shown to the reaction was terminated by adjusting the pH to specifically alkylate rabbit muscle pyruvate kinase at 7.0 with 1 M-acetic acid before 70% loss of activity to a group which might be located close to the 'phos- eliminate any problems due to protein aggregation. phoryl overlap' region of the active site (Reynard et For the experiments involving amino acid analysis or al., 1961). The next stage in the study of this reaction periodate oxidation the protein was reduced with was to identify the nature of the functional group at 5mg of NaBH4. All the 5-chloro-4-oxopentanoate- the active site. The report describes the synthesis of a labelled pyruvate kinase samples were exhaustively standard reference amino acid (4-hydroxypentanoic dialysed against water at 4°C and finally freeze-dried. acid alanine thioether, I) and the use of performic acid oxidation to analyse the labelled amino acid. Degradation by performic acid oxidation should be Chromatographic analysis ofmodified amino acids particularly useful in this system, since the proposed structure of the inhibitor amino acid adduct Labelled pyruvate kinase (25mg) was hydrolysed in at 0 lOml of6M-HCI 110°C for 18h. The hydrolysate 11 was flash-evaporated and then vacuum-dried twice ml water. was (X-CH2--C-CH2--CH2--CO2H) means that the from 5 of High-voltage electrophoresis compound should be split into two chemically performed with either a Gilson high-voltage electro- identifiable intermediates (see below for detailed phorator model D or Locarte electrophoresis explanation). Although performic acid oxidation has apparatus. The buffers used were pH 1.9 (acetic acid/ been used previously to produce carboxymethyl- formic acid/water; 27:25:888, by vol.), pH3.5 amino acids from more complex amino acids (Petra (pyridine/acetic acid/water; 1:10:289, byvol.), pH4.7 et al., 1965; Husain & Lowe, 1968), the structure of (pyridine/acetic acid/water; 1:1:48, by vol.), and the degraded derivative allowed only the carboxy- pH6.5 (pyridine/aceticacid/water; 25:1:475, byvol.). methyl-amino acid to be analysed, and this meant Amino acids were located as either ninhydrin- that complete information on the mechanism of this positive spots or by radioactivity. For initial location reaction for protein-bound intermediates was not of radioactive spots a Camlab radiochromatogram obtained. The present communication shows that scanner was used. Subsequently the paper was cut there is a high degree of preference in the cleavage into 1 cm strips, soaked in 1 ml of water for 1 h and reaction. Finally, it is suggested that periodate then counted for radioactivity. Amino acid analyses oxidation may be advantageous in the preliminary of hydrolysed samples were performed with a JEOL screening to identify the amino acid. JLC-6AH amino acid analyser. The column for acidic and neutral amino acids contained JEOL Materials and Methods LCR2 resin. For radioactive samples, a stream splitter was used before the ninhydrin-analysing Pyruvate kinase modification system and approx. 10% of the eluate from the The exact conditions for the bulk modification of column was collected in a fraction collector. The pyruvate kinase were described in the previous paper entire sample was counted for radioactivity. Vol. 159 214 R. A. CHALKLEY AND D. P. BLOXHAM Performic acid oxidation vacuo. After acid hydrolysis, the amino acid analyser Performic acid was prepared by the addition of showed the presence of glutamate, glycine and a new H202 (30%, v/v) to formic acid (firs, 1956). In a amino acid, which was presumably compound I typical experiment, 25mg of 5-chloro-4-oxo[3,5-3H]- (Fig. 1). To confirm this, we purified the amino acid pentanoate-labelled material was dissolved in 0.5ml and identified its structure by n.m.r. spectroscopy. of formic acid, cooled on ice for 30min, andthen 1 ml Fortunately, the mixture of amino acids was easily of performic acid solution was added. After 2.5h at purified by high-voltage electrophoresis at pH3.5. 0WC, the sample was diluted with 25ml of water and After performing this chromatographic purification freeze-dried. The sample was hydrolysed and ana- twice, the modified amino acid gave only a single lysed by electrophoresis. N.-3-Carboxymethylhisti- ninhydrin-positive and radioactive peak in the dine and e-carboxymethyl-lysine (Gundlach et al., amino acid analyser. The n.m.r. spectrum of this 1959) were synthesized by Dr. G. Rasool of this compound was recorded in 2H20 by using a Varian department. XL100-12 machine operated in the CW mode at 100MHz with a "IF lock and extemal trimethylsilyl reference, The hydrogen resonances observed were as Periodate oxidation follows; 3 1.8-2.8p.p.m., 4H, multiplet, -CH2 The NaBH4-reduced 5-chloro4-oxo[3,5-3H]pen- CH2-; a 2.85p.p.m., doublet, S-CH2C; tanoate-labelled samples were oxidized with 100mg 2H, of NaIO4 in lOml of satd. NaHCO3 containing 02H 10mg ofcarrier formaldehyde. After 16h the niixture 3 3.05p.p.m., 2H, triplet, C-CH2-S; a 4.6-4.9 was adjusted to pH6 with 50% (w/v) acetic acid, and I formaldehyde was isolated as the dimedone complex N2H2 (Zaman et al., 1973). p.p.m., 1H, multiplet, --H. This spectrum ac- 5.Amino.4hydroxy[5-3H2]pentanoic acid was I donated by Dr. P. M. Jordan of this department. N2H2 counted for all the expected resonances. The methyl- Results and Discussion ene group adjacent to the amino group Synthesis and characterization of4-hydroxy[3,5_3H]- H-CH2-S in compound I is not a simple pentanoic acidalanine thioether (I) The first task in identifying the amino acid in \N2H2 pyruvate kinase modified by 5-chloro-4-oxopentano- ate was to synthesize an authentic reference amino acid. For this purpose we chose 4-hydroxypentanoic 1.0o In acid alanine thioether (I), since thealkylation reaction 0 was easily monitored by 5,5'-dithiobis-(2-nitro- V 0.8 8 benzoate) titration (Ellman, 1959). Further, gluta- 0in v: thione presents a useful N-blocked cysteine deriva- o 0.6 6 *5 tive, since its adducts are readily precipitated as the ._ barium salt, which aids purification. U U .* 0.4 4 .... OH NH2 .0 . 04 I ..r- 0.2 2 ,,x CO2H-[CH2]2-CH-CH2-S-CH2--CH-CO2H z o" (I) 120 140 160 180 200 220 240 260 Glutathione (0.3mmol) was allowed to react with Retention time (min) 5-chloro4oxo[3,5-3Hlpentanoate (0.42mmol; 2.5 x Fig. 1. Chromatography of 4-hydroxy(3,5-3-H]pentanoic 103d.p,m./nmol) in water, pH8 (maintained with acidalanine by using the amino acidanalyser IM-NaOH) for 2h at room temperature (20°3). About 80 % ofthereactionwascompletewithin 0min This Figure shows the chromatography of 4-hydroxy- as judged by both 5,5'-dithiobis-(2-nitrobenzoate) [3,5-3H]pentanoic acid alanine thioether, which was titration and alkali uptake. The carbonyl group in the produced either synthetically from glutathione or by alkylation of pyruvate kinase. The trace shows the elution adduct was then reduced with NaBH4 and after profile from only the acidic and neutral column of the 30min an excess of barium acetate (4m1, 1M) was amino acid analyser. o, Ninhydrin-positive trace whlen added. The barium salt was precipitated with 4vol. 5- chloro-4-oxo[3,5-3H]pentanoate-labelled glutathione of ice-cold ethanol and collected by centrifugation, was analysed. *, Distribution of radioactivity when After washing three times with ice-cold ethanol and 5-cWoro-4'oxo[3,5_3H]pentanoate-labelled pyruvate kin- twice with diethyl ether the product was dried in ase was analysed. 1976 ALKYLATION OF CYSTEINE BY 5-CHLORO-4-OXOPENTANOIC ACID 215 doublet, but is more complex. This may be due to the derived from position 3 of5-chloro-4-oxopentanoate) fact that it is adjacent to an asymmetric centre which and [3H]formaldehyde. This route gives no informa- was derived from the L-cysteine in glutathione. This tion on the nature of the amino acid modified. In may be contrasted with the methylene group adjacent contrast, route (b) leads to the formation of the [3H]- to the hydroxyl group (S-CH2-CH- which is a carboxymethyl-amino acid (eH derived from position 5 of 5-chloro-4-oxopentanoate), which can be k 02H1 identified by comparison with standards. [3H]- simple doublet, reflecting that the NaBH4 reduction Hydroxypropionate formed by route (b) will be of the carbonyl produces a racemic mixture. volatile and not analysed.
Load more

Recommended publications
  • Acta Sci. Pol., Technol. Aliment. 12(4) 2013, 385-393 IMPEDIMETRIC
    M PO RU LO IA N T O N R E U Acta Sci. Pol., Technol. Aliment. 12(4) 2013, 385-393 I M C S ACTA pISSN 1644-0730 eISSN 1889-9594 www.food.actapol.net/ IMPEDIMETRIC TEST FOR RAPID DETERMINATION OF PERFORMIC ACID (PFA) BIOCIDAL ACTIVITY TOWARD ECHERICHIA COLI Małgorzata Lasik1, Renata Dobrucka2, Piotr Konieczny1 1Faculty of Food Sciences and Nutrition, Poznań University of Life Sciences Wojska Polskiego 28, 60-637 Poznań, Poland 2Department of Industrial Products Quality and Ecology, Poznań University of Economics Niepodległości 10, 61-875 Poznań, Poland ABSTRACT Background. Performic acid has recently become available on a commercial scale for potential use in waste- water disinfection and can become an innovative biocide for various purposes in food processing. The aim of our study was: 1) to investigate the antimicrobial resistance of performic acid as high active and non toxic chemical disinfectant against Escherichi coli (hygiene indicator test microorganism used in industrial micro- biology) and 2) to evaluate the electrical impedance measurement method usefulness for fast and high precise test of antibacterial activity. Material and methods. Four types of antimicrobial disinfectants (commercial 35% hydrogen peroxide, 1% performic acid, 35% hydrogen peroxide and 15% formic acid) were tested against Escherichia coli as hy- giene indicator test microorganism. By evaluating the biocidal activity of selected disinfectants two methods were compared: electrical impedance measurement and classical serial dilution method with turbidity effect. Results. It was stated that the performic acid expressed the highest antibacterial activity in comparison to other tested peroxide disinfectants: commercial 35% hydrogen peroxide solution and components required for performic acid production: 35% hydrogen peroxide solution with stabilizers and 15% formic acid solution with stabilizers).
    [Show full text]
  • Kinetics of the Epoxide Ring Opening Reactions
    processes Article Soybean Oil Epoxidation: Kinetics of the Epoxide Ring Opening Reactions Elio Santacesaria 1,* , Rosa Turco 2 , Vincenzo Russo 2 , Riccardo Tesser 2 and Martino Di Serio 2 1 CEO of Eurochem Engineering Ltd., 20139 Milano, Italy 2 NICL—Department of Chemical Science, University of Naples Federico II, 80126 Naples, Italy; [email protected] (R.T.); [email protected] (V.R.); [email protected] (R.T.); [email protected] (M.D.S.) * Correspondence: [email protected] Received: 7 July 2020; Accepted: 9 September 2020; Published: 11 September 2020 Abstract: The epoxide ring opening reaction (ROR) can be considered as the most important side reaction occurring in the epoxidation of soybean oil reaction network. This reaction consistently reduces the selectivity to epoxidized soybean oil (ESBO). The reaction is also important for producing polyols and lubricants. In this work, the reaction was studied in different operative conditions to evaluate the effect on ROR rate respectively: (i) The Bronsted acidity of the mineral acid (H2SO4 or H3PO4), used as catalyst for promoting the oxidation with hydrogen peroxide of formic to performic acid, that is, the reactant in the epoxide formation; (ii) the concentration of the nucleophilic agents, normally present during the ESBO synthesis like HCOOH, HCOOOH, H2O, H2O2; (iii) the stirring rate that changes the oil–water interface area and affects the mass transfer rate; (iv) the adopted temperature. Many different kinetic runs were made in different operative conditions, starting from an already epoxidized soybean oil. On the basis of these runs two different reaction mechanisms were hypothesized, one promoted by the Bronsted acidity mainly occurring at the oil–water interface and one promoted by the nucleophilic agents, in particular by formic acid.
    [Show full text]
  • 2 3 0 Material Safety Data Sheet
    He a lt h 2 2 Fire 2 3 0 Re a c t iv it y 0 Pe rs o n a l Pro t e c t io n H Material Safety Data Sheet Aniline MSDS Section 1: Chemical Product and Company Identification Product Name: Aniline Contact Information: Catalog Codes: SLA1735 Sciencelab.com, Inc. 14025 Smith Rd. CAS#: 62-53-3 Houston, Texas 77396 RTECS: BW6650000 US Sales: 1-800-901-7247 International Sales: 1-281-441-4400 TSCA: TSCA 8(b) inventory: Aniline Order Online: ScienceLab.com CI#: Not applicable. CHEMTREC (24HR Emergency Telephone), call: Synonym: Aminobenzene; Benzenamine; Aminophen 1-800-424-9300 Chemical Name: Aniline International CHEMTREC, call: 1-703-527-3887 Chemical Formula: C6H5NH2 For non-emergency assistance, call: 1-281-441-4400 Section 2: Composition and Information on Ingredients Composition: Name CAS # % by Weight Aniline 62-53-3 100 Toxicological Data on Ingredients: Aniline: ORAL (LD50): Acute: 250 mg/kg [Rat.]. 464 mg/kg [Mouse]. DERMAL (LD50): Acute: 820 mg/kg [Rabbit.]. 1400 mg/kg [Rat]. Section 3: Hazards Identification Potential Acute Health Effects: Hazardous in case of skin contact (irritant, permeator), of eye contact (irritant), of ingestion, of inhalation. Severe over- exposure can result in death. Potential Chronic Health Effects: Slightly hazardous in case of skin contact (sensitizer). CARCINOGENIC EFFECTS: Classified A3 (Proven for animal.) by ACGIH. 3 (Not classifiable for human.) by IARC. MUTAGENIC EFFECTS: Mutagenic for mammalian somatic cells. Mutagenic for bacteria and/or yeast. TERATOGENIC EFFECTS: Not available. DEVELOPMENTAL TOXICITY: Not available. The substance may be toxic to blood, kidneys, liver, bladder, spleen, cardiovascular system, central nervous system (CNS).
    [Show full text]
  • Epoxidation of Fatty Acid Methyl Esters Derived from Algae Biomass to Develop Sustainable Bio-Based Epoxy Resins
    polymers Article Epoxidation of Fatty Acid Methyl Esters Derived from Algae Biomass to Develop Sustainable Bio-Based Epoxy Resins Pamela Hidalgo 1,*, Simona Álvarez 1, Renato Hunter 2 and Alejandra Sánchez 1 1 Department of Industrial Processes, Faculty of Engineering, Universidad Católica de Temuco, Temuco 4780000, Chile; [email protected] (S.Á.); [email protected] (A.S.) 2 Department of Mechanical Engineering, Universidad de La Frontera, Casilla 54-D, Temuco 4811230, Chile; [email protected] * Correspondence: [email protected]; Tel.: +56-45-222-5672 Received: 15 June 2020; Accepted: 7 September 2020; Published: 10 October 2020 Abstract: The objective of this research was to investigate the development of epoxides from Chlorella vulgaris lipids to obtain a novel bio-based resin. The process involved the production of fatty acid methyl esters (FAMEs) by in situ transesterification of microalgal biomass, followed by epoxidation of the FAMEs to obtain bioresin. During the FAME production process, an assessment was made of the main factors affecting the production of unsaturated fatty acid methyl esters (UFAMEs), such as catalyst dosage and methanol:hexane volume ratio. For step epoxidation, an evaluation of the catalyst concentration, temperature and formic acid:hydrogen peroxide ratio was made. From the results obtained, UFAME production was maximized using 20 wt% of catalyst dosage and a volume ratio of 1:2 (v/v, methanol:hexane). Then, in the epoxidation stage, a higher yield was obtained using 1 wt% of catalyst with a volume ratio of 1:1 and maintaining a temperature of 70 ◦C. The bioresin was blended with neat epoxy resin (DGEBA) and cured with tetraethylenepentamine (TEPA).
    [Show full text]
  • Bactericidal Effect of Performic Acid on Salivary Bacteria
    J Osaka Dent Univ 2018 (April) ; 52 (1) :11−15. Bactericidal effect of performic acid on salivary bacteria Hiroki Morioka1, Takayuki Nambu2 and Kazuya Takahashi3 1Department of Geriatric Dentistry, Graduate School of Dentistry, 2Department of Bacteriology, and 3Department of Geriatric Dentistry, Osaka Dental University, 8-1 Kuzuhahanazono-cho, Hirakata-shi, Osaka 573-1121, Japan Although heat­sensitive semi­critical medical devices (e.g., transnasal endoscopes) should undergo high­level disinfection between patients, these devices are often harmful to humans and the environment due to their residual toxicity caused by disinfectants. We analyzed the bactericidal activity against salivary bacteria of performic acid (PFA) which has strong antibacterial activity and has shown a consistent absence of genotoxic and mutagenic effects on human cells. Collected saliva samples were mixed with various concentrations of PFA. After incubation, bactericidal activity was assessed with colony­ forming assays and quantification of ATP produced by metabolically active cells. Even for a 1­minute exposure, PFA showed a strong bactericidal effect against salivary bacte­ ria, in which more than 99.9% and 67.1% of bacterial colonies were suppressed at 8×10−4 % (w/v) and 8×10−6% (w/v) PFA, respectively. This effect was enhanced by prolonged in­ cubation. Bacterial viability assay based on ATP measurement also showed concentration­dependent bactericidal effects of PFA. PFA showed comparatively strong antibacterial activity against salivary bacteria, even with
    [Show full text]
  • UNIVERSITY of CALIFORNIA, SAN DIEGO an Experimental And
    UNIVERSITY OF CALIFORNIA, SAN DIEGO An Experimental and Theoretical Investigation of Atmospheric Hydrogen Bonded Systems in the Gas Phase A Thesis submitted in partial satisfaction of the requirements for the degree Master of Science in Chemistry by Matthew Kenneth Louie Committee in charge: Professor Amitabha Sinha, Chair Professor Judy Kim Professor Joseph O’Connor 2014 The Thesis of Matthew Kenneth Louie is approved and it is accepted in quality and form for publication on microfilm and electronically: _______________________________________________________________________ _______________________________________________________________________ _______________________________________________________________________ Chair University of California, San Diego 2014 iii DEDICATION To my parents Edward and Louisa, and my older sisters, Lisa, Melissa, and Erica, for always giving me their love and support iv TABLE OF CONTENTS Signature Page ................................................................................................................... iii Dedication .......................................................................................................................... iv Table of Contents .................................................................................................................v List of Figures .................................................................................................................. viii List of Tables ....................................................................................................................
    [Show full text]
  • 2-Aminobenzaldehydes from Quinolinium Salts and Alkaline Hydrogen Peroxide
    Issue in Honor of Prof. Charles Rees ARKIVOC 2002 (vi) 4-14 2-Aminobenzaldehydes from quinolinium salts and alkaline hydrogen peroxide Ian Allan Apple and Otto Meth-Cohn* # Chemistry Department, University of Sunderland, Sunderland, SR1 3SD, UK. E-mail: [email protected] Dedicated to Professor Charles Rees on the occasion of his 75th birthday (received 09 May 02; accepted 02 Jul 02; published on the web 10 Jul 02) Abstract 2-Formylanilines are very handy. For building various heterocyclic rings. But making them is not so very dandy. Low yields and multi-step ‘mongst other things. N-Alkylquinoliniums cleave with great ease. With hydrogen peroxide / aqueous base. (The mechanism’s clear to such as Charles Rees). To give these anilines – good yields, good pace. Keywords: 2-Aminobenzaldehydes, quinolinium salts, alkaline hydrogen peroxide Introduction 2-Aminobenzaldehyde and its derivatives are key intermediates in heterocyclic synthesis. Thus the Friedländer synthesis of quinolines1 (base-catalysed condensation of 2- aminobenzaldehyde with aliphatic aldehydes and ketones) is a widely used method. Both 2- and 4-quinolones2 as well as acridines and acridones3 are easily made from these versatile precursors as are indoles,4 while dimerisation of N-methyl-2-aminobenzaldehyde yields oxa-analogues of Tröger’s base.5 Various other macrocyclic applications have been described.6 Numerous quinazolines have been made efficiently7 while Michael additions of 2-aminobenzaldehydes to alkenes and alkynes present a versatile route to quinolines and fused quinolines.8 Most syntheses of 2-aminobenzaldehydes involve more than one step and at best are moderate in yield. For example, the synthesis of 2-aminobenzaldehyde itself has been reported from easily derived precursors such as 2-nitroaniline (by way of the Beech reaction, employing formaldoxime coupling with the derived diazonium salt in 33% yield9) or from 2-nitrotoluene (oxidation with CrO3/Ac2O followed by hydrolysis of the derived aldehyde diacetate in 24% yield10) (Scheme 1).
    [Show full text]
  • Formalin 37-7 HM - US
    Safety data sheet Issue Date 21-Mar-2018 Revision Date 21-Mar-2018 Version 2 1. IDENTIFICATION Product identifier Product Name Formalin 37-7 HM - US Other means of identification Synonyms Formaldehyde solution Pure substance/mixture Substance Recommended use of the chemical and restrictions on use Application Chemical intermediate Uses advised against Consumer use. Details of the supplier of the safety data sheet Manufacturer Address Perstorp Polyols, Inc. 600 Matzinger Road Toledo, Ohio 43612 Phone: 419-729-5448 800-537-0280 Fax: 419-729-3291 www.perstorp.com E-mail address [email protected] Emergency telephone number USA (+)1 866 519 4752 (contract no: 334101) 2. HAZARDS IDENTIFICATION Classification of the substance or mixture This chemical is considered hazardous by the 2012 OSHA Hazard Communication Standard (29 CFR 1910.1200): Acute toxicity - Oral - Category 3 Acute toxicity - Dermal - Category 3 Acute toxicity - Inhalation (Vapors) - Category 2 Skin corrosion/irritation - Category 1 Sub-category B Serious eye damage/eye irritation - Category 1 Skin sensitization - Category 1A Germ cell mutagenicity - Category 2 Carcinogenicity - Category 1A Specific target organ toxicity (single exposure) Category 1; optic nerve, - central nervous system Specific target organ toxicity (single exposure) - Category 3 Flammable liquids - Category 4 Label elements Symbols/Pictograms ___________________________________________________________________________________________ Page 1 / 12 AGHS - EN Formalin 37-7 HM - US Revision Date 21-Mar-2018
    [Show full text]
  • Development, Characterization and Commercial Application of Palm Based Dihydroxystearic Acid and Its Derivatives: an Overview Gregory F
    Journal of Oleo Science Copyright ©2011 by Japan Oil Chemists’ Society J. Oleo Sci. 60, (5) 237-265 (2011) REVIEW Development, Characterization and Commercial Application of Palm Based Dihydroxystearic Acid and Its Derivatives: an Overview Gregory F. L. Koay1, 2, Teong-Guan Chuah1, 3＊ , Sumaiya Zainal-Abidin2, 4, Salmiah Ahmad2, 5 and Thomas S. Y. Choong1 1 Department of Chemical and Environmental Engineering, Universiti Putra Malaysia (43400 UPM Serdang, Selangor Darul Ehsan, MALAYSIA) 2 Advanced Oleochemical Technology Division, Malaysian Palm Oil Board (43650 Bandar Baru Bangi, Selangor Darul Ehsan, MALAYSIA) 3 Institute of Tropical Forest and Forestry Products, Universiti Putra Malaysia (43400 UPM Serdang, Selangor Darul Ehsan, MALAYSIA) 4 Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang (25000 Kuantan, Pahang Darul Makmur, MALAYSIA) 5 Director General’s Offi ce, Malaysian Rubber Board (50450 Kuala Lumpur, MALAYSIA) Abstract: Hydroxyl fatty acids and their derivatives are of high value due to their wide range of industrial application, including cosmetic, food, personal care and pharmaceutical products. Realizing the importance of hydroxyl fatty acids, and yet due to the absence of the conventional starting raw materials, Malaysia has developed 9,10-dihydroxystearic acid (9,10-DHSA) and its derivatives from locally abundant palm based oils. The aim of this article is to provide a general description of the works that have thus far being done on palm based 9,10-DHSA: starting from its conception and production from commercial grade palm based crude oleic acid via epoxidation and hydrolysis, purification through solvent crystallization and characterization through wet and analytical chemistry, moving on to developmental works done on producing its derivatives through blending, esterifi cation, amidation and polymerization, and completing with applications of 9,10-DHSA and its derivatives, e.g.
    [Show full text]
  • FORMALDEHYDE 1. Exposure Data
    039-104.qxp 13/12/2006 11:27 Page 39 FORMALDEHYDE This substance was considered by previous working groups in October 1981 (IARC, 1982), March 1987 (IARC, 1987a) and October 1994 (IARC, 1995). Since that time, new data have become available, and these have been incorporated in the monograph and taken into consideration in the evaluation. 1. Exposure Data 1.1 Chemical and physical data 1.1.1 Nomenclature Chem. Abstr. Serv. Reg. No.: 50-00-0 Deleted CAS Reg. Nos.: 8005-38-7; 8006-07-3; 8013-13-6; 112068-71-0 Chem. Abstr. Name: Formaldehyde IUPAC Systematic Name: Methanal Synonyms: Formaldehyde, gas; formic aldehyde; methaldehyde; methyl aldehyde; methylene oxide; oxomethane; oxymethylene 1.1.2 Structural and molecular formulae and relative molecular mass H C O H CH2O Relative molecular mass: 30.03 1.1.3 Chemical and physical properties of the pure substance From Lide (2003), unless otherwise specified (a) Description: Colourless gas with a pungent odour (Reuss et al., 2003) (b) Boiling-point: –19.1 °C (c) Melting-point: –92 °C (d) Density: 0.815 at –20 °C –39– 039-104.qxp 13/12/2006 11:13 Page 40 40 IARC MONOGRAPHS VOLUME 88 (e) Spectroscopy data: Infrared [prism, 2538], ultraviolet [3.1] and mass spectral data have been reported (Weast & Astle, 1985; Sadtler Research Laboratories, 1991). ( f ) Solubility: Soluble in water, ethanol and chloroform; miscible with acetone, benzene and diethyl ether (g) Stability: Commercial formaldehyde–alcohol solutions are stable; the gas is stable in the absence of water; incompatible with oxidizers, alkalis, acids, phenols and urea (IARC, 1995; Reuss et al., 2003; Gerberich & Seaman, 2004).
    [Show full text]
  • Process for Concurrently Producing Aryl Formate and Aromatic Carboxylic Acid
    Europaisches Patentamt 19 European Patent Office Office europeen des brevets © Publication number : 0 520 762 A2 12) EUROPEAN PATENT APPLICATION @ Application number : 92305792.1 © int. ci.5: C07C 63/04, C07C 51/235, C07C 409/30 (22) Date of filing : 24.06.92 @ Priority: 26.06.91 JP 181982/91 (72) Inventor : Tanaka, Tom, c/o Mizushima Works of Mitsubishi Gas Chem. Comp., Inc., 3-10 Kaigandori, @ Date of publication of application : Mizushima 30.12.92 Bulletin 92/53 Kurashiki-shi, Okayama-ken (JP) Inventor : Tanaka, Kazuo, c/o Mizushima Works of Mitsubishi @ Designated Contracting States : Gas Chem. Comp., Inc., 3-10 Kaigandori, BE CH DE FR GB IT LI NL Mizushima Kurashiki-shi, Okayama-ken (JP) Inventor : Aratake, Teruo, c/o Mizushima @ Applicant : MITSUBISHI GAS CHEMICAL Works of Mitsubishi COMPANY, INC. Gas Chem. Comp., Inc., 3-10 Kaigandori, No. 5-2, Marunouchi 2-chome Mizushima Chiyoda-ku, Tokyo (JP) Kurashiki-shi, Okayama-ken (JP) (74) Representative : Myerscough, Philip Boyd et al J.A. Kemp & Co. 14 South Square, Gray's Inn London WC1R 5LX (GB) (54) Process for concurrently producing aryl formate and aromatic carboxylic acid. (57) A process for efficiently producing aryl formate and aromatic carboxylic acid from aldehyde, which comprises oxidizing an aromatic aldehyde with an oxygen-containing gas in the presence of a volatile solvent up to a reaction ratio of 40 to 70 mol% to convert the aromatic aldehyde to a peracid, adding a stabilizer, and allowing the remaining aromatic aldehyde and the aromatic peracid to react while the volatile solvent is distilled off. CM < CM CO h- o CM If) LU Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 520 762 A2 The present invention relates to a process for producing aryl formate and aromatic carboxylic acid from aromatic aldehyde.
    [Show full text]
  • United States Patent Office
    Patented Jan. 23, 1951 2,539,178 UNITED STATES PATENT OFFICE 2,539,178 METALLIZED AZO DYESTUFF AND PROCESS OF PRODUCING THE SAME Heinrich Hugo Bestehorn, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application November 6, 1947, Serial No. 784,507 2 Claims. (C. 260-148) 1 2 The present invention relates to new metallized contemplated herein, are obtained by coupling a azo dyestuffs and to a method for their pro diazotized amine of the benzene or naphthalene duction. Series free from Substituents ortho to the azo It is rather standard procedure in the dyestuff group with a hydroxy bearing coupling compo art to increase the fastness properties of a ZO nent capable of coupling under alkaline con dyestuffs by subjecting these dyestuffs to metal ditions in ortho position to said hydroxyl group. lization, either in Substance or on the fiber. It xamples of suitable primary amines for use has always been the impression of the art that in the preparation of the involved dyestuffs are: in order to effect this result, the azo dyes treated should have in o-position to and on Opposite n-Nitroaniline sides of the azo bridge, groupS Such as hydroxyi, p-Nitroaniline amino, carboxy, and the like, capable of cooperat N-acetyl-p-phenylenediamine ing with the metallizing agents employed to effect N-amino-o-cresol ethyl ether the desired chelation. Inasmuch as the number p-Amino phenol of azo dyes having the desired groups on opposite 5 Sulfanilic acid sides of the azo bridge and in o-position thereto Aniline are comparatively few in number, the very ad p-Toluidine vantageous metallizing process for increasing the m-Chloroaniline fastness of the dyes has been fairly limited.
    [Show full text]