Lipase catalyzed polytransesterification in an organic solvent

Summary Lipase-catalyzed polytransesterification ofbis(2,2,2-trifluoroethyl) dodecanedioate with aliphatic diols (from 1,2-ethanediol to 1,6-hexanediol) was studied with 4 enzymes and a number of solvents. The effects of experimental parameters were investigated with the purpose of obtaining a polyester of as high as possible average molar mass. The highest mass average molar mass (M _w) of 34,750 g mol^-1 (DP = 122) was obtained under vacuum with 1,4-butanediol,Mucor miehei lipase, and diphenyl ether as solvent.     

Side Chain Hydroxylation of Aromatic Compounds by Fungi. Part 6. Biotransformation of Olefins by Mortierella Isabellina

The fungus Mortierella isabellina ATCC 42613 converts phenyl-substituted olefins to vicinal diols. The substrate selectivity and product stereochemistry of this biotransformation can be rationalized by application of the model developed for benzylic hydroxylation of aromatic hydrocarbons by M isabellina.     

Construction of chiral polyesters from polycondensation of multifunctional monomer containing both flexible amino acid and rigid pendant groups with aromatic diols

A number of chiral wholly aromatic polyesters (PEs) with phthalimido and flexible chiral unit in the backbone were prepared from a chiral synthesized diacid monomer, 5-(3-methyl-2-phthalimidylpentanoylamino)isophthalic acid (1), and various aromatic diols via the polyesterification reaction. The tosyl chloride/pyridine/N,N-dimethylformamide (DMF) system was used as a condensing agent. All of the these polymers having bulky phthalimido and amino acid functionalities in the side chain showed excellent solubility and readily dissolved in various solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide and DMF. Since, these chiral polymers have natural amino acids in the polymer architecture, they are expected to be biodegradable and therefore may be classified under eco-friendly polymers. They had useful levels of thermal stability associated with excellent solubility. Thermogravimetric analysis (TGA) showed that the obtained PEs are rather thermally stable, 10% weight loss temperatures in excess of 317°C, and char yields at 700°C in the nitrogen atmosphere higher than 24%. The resulting polymers were obtained in good yields with inherent viscosities ranging between 0.22 and 0.56 dL/g and were characterized with FT-IR, ¹H-NMR, elemental and TGA techniques.     

Application of (S)‐TBMB carboxylic acid‐based on‐line HPLC‐exciton CD analysis to acyclic vicinal alcohols and amino alcohols

Applications of the on‐line HPLC‐exciton CD analysis using (S)‐2‐tert‐butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic acid [(S)‐TBMBC‐OH] that can simultaneously determine the enantiomeric compositions and the absolute configuration of cyclohexane‐1,2‐diols and diamines as well as acyclic vicinal diols and amino alcohols were studied. Di‐O‐ or di‐N,O‐(S)‐TBMBC derivatives of acyclic terminal vicinal diols, 2‐hydroxy‐1‐amines, and nonterminal vicinal diols gave symmetrical exciton CD spectra between enantiomers, indicating their absolute configurations. However, Di‐N,O‐(S)‐TBMBC derivatives of 2‐amino‐1‐ols did not always give symmetrical exciton CD spectra between enantiomers, but their 2‐phthalimido‐1‐O‐(S)‐TBMBC derivatives gave symmetrical exciton CD spectra, indicating their absolute configurations. All these (S)‐TBMBC derivatives were separated by normal‐phase HPLC and unequivocally determined by the on‐line HPLC‐exciton CD analysis without recourse to reference samples. Chirality 11:149–159, 1999. © 1999 Wiley‐Liss, Inc.     

Histochemical analysis of glycoproteins in the unicellular glands in the epidermis of an Indian freshwater fish Mastacembelus pancalus (Hamilton)

Summary The unicellular glands in the epidermis of the Indian freshwater fish Mastacembelus pancalus consist of three types of mucous cells and sacciform cells. The histochemical properties of their secretory glycoproteins have been analysed by means of a battery of histochemical methods. These included methods for the identification and simultaneous visualization of oxidizable vicinal diols, O-acyl sugars, O-sulphate esters and sialic acid residues with or without side-chain O-acyl variants. Four general classes of glycoproteins (GPs) were identified. These included (i) GPs with O-sulphate esters and oxidizable vicinal diols, (ii) GPs with oxidizable vicinal diols and sialic acid residues with or without O-acyl substitution at C7, (iii) GPs mainly with O-sulphate esters, low moieties of GPs with oxidizable vicinal diols, O-acyl sugars and sialic acid residues with side-chain O-acyl variant predominantly at C8 (or which are di- or tri-substituted) or C9 and in traces of sialic acid residues without O-acyl substitution or with O-acyl substitution at C7, and (iv) GPs with traces of oxidizable vicinal diols, O-acyl sugars and sialic acid residues with O-acyl substitution at C8 (or which are di- or tri-substituted) or C9. The physiological significances of these GP classes and their release on the surface of the epidermis are discussed with special reference to their role in lubrication, protection and inhibition of the invasion and proliferation of pathogenic microorganisms in the epidermis, as adapted to the peculiar mode of life of the fish.     

Enzymatic Synthesis of Various Aromatic Polyesters in Anhydrous Organic Solvents

Lipases and proteases from various sources were tested in aromatic polyester synthesis in organic solvents. A commercial protease from Bacillus licheniformis efficiently catalyzed the transesterifica-tion of a diester of terephthalic acid and 1,4-butanediol in anhydrous tetrahydrofuran (THF). This protease was used as a catalyst in the synthesis of aromatic polyesters in THF. Oligomers with average molecular weights from 400 to 1000 daltons were obtained using various diols and aromatic diesters.     

Degradation pathways of phenanthrene by Sinorhizobium sp. C4

Sinorhizobium sp. C4 was isolated from a polycyclic aromatic hydrocarbon (PAH)-contaminated site in Hilo, HI, USA. This isolate can utilize phenanthrene as a sole carbon source. Sixteen metabolites of phenanthrene were isolated and identified, and the metabolic map was proposed. Degradation of phenanthrene was initiated by dioxygenation on 1,2- and 3,4-C, where the 3,4-dioxygenation was dominant. Subsequent accumulation of 5,6- and 7,8-benzocoumarins confirmed dioxygenation on multiple positions and extradiol cleavage of corresponding diols. The products were further transformed to 1-hydroxy-2-naphthoic acid and 2-hydroxy-1-naphthoic acid then to naphthalene-1,2-diol. In addition to the typical degradation pathways, intradiol cleavage of phenanthrene-3,4-diol was proposed based on the observation of naphthalene-1,2-dicarboxylic acid. Degradation of naphthalene-1,2-diol proceeded through intradiol cleavage to produce trans-2-carboxycinnamic acid. Phthalic acid, 4,5-dihydroxyphthalic acid, and protocatechuic acid were identified as probable metabolites of trans-2-carboxycinnamic acid, but no trace salicylic acid or its metabolites were found. This is the first detailed study of PAH metabolism by a Sinorhizobium species. The results give a new insight into microbial degradation of PAHs.     

Enantiomerically Pure Bithiophene Diphosphine Oxides as Catalysts for Direct Double Aldol Reactions

The direct aldol reaction between aryl methyl ketones with aromatic aldehydes in the presence of tetrachlorosilane and a catalytic amount of a chiral bithiophene diphosphine oxide was studied; the product of double aldol addition was isolated as diacetate in good diastereoselectivity (up to 95:5) and enantioselectivities up to 91%. The reaction with heteroaromatic aldehydes was also investigated leading to the corresponding 1,3 diols, in some cases with excellent stereoselectivities. Chirality 25:643–647:, 2013. © 2013 Wiley Periodicals, Inc.     

Thiol-functionalized copolymeric polyesters by lipase-catalyzed esterification and transesterification of 1,12-dodecanedioic acid and its diethyl ester,respectively, with 1-thioglycerol

Copolymeric polyoxoesters containing branched-chain methylenethiol functions, i.e., poly(1,12-dodecanedioic acid-co-1-thioglycerol) and poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol), were formed by lipase-catalyzed polyesterification and polytransesterification of 1,12-dodecanedioic acid and diethyl 1,12-dodecanedioate, respectively, with 1-thioglycerol (3-mercaptopropane-1,2-diol) using immobilized lipase B from Candida antarctica (Novozym 435) in vacuo without drying agent in the reaction mixture. After 360–480 h, both polyoxoesters were purified by extraction from the reaction mixtures followed by solvent fractionation. The precipitate of poly(1,12-dodecanedioic acid-co-1-thioglycerol) demonstrated a M_W of ~170,000 Da, whereas a M_W of ~7,100 Da only was found for poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol). Both polycondensates were analyzed by GPC/SEC, alkali-catalyzed transmethylation, NMR- and FTIR-spectrometry.     

芳香族化合物生物降解的研究进展

本文综述了以苯、取代苯、联苯和多环芳烃为代表的芳香族化合物的生物降解途径,其共同之处在于经过两步双加氧酶作用,生成二醇和开环。两步双加氧酶分别为芳环羟基化双加氧酶和芳环断裂双加氧酶。以甲苯途径为代表讨论了芳香族化合物的分子生物学研究情况。代谢工程研究是九十年代兴起的芳香族化合物生物降解的研究内容,通过对甲苯途径的代谢工程研究明确了途径中的关键酶,并通过对关键酶的活性提高使整个途径的代谢流增加。     

Design,synthesis, and properties of new biodegradable aromatic/aliphatic liquid crystalline copolyesters

Liquid crystalline copolyesters of high molecular weight were obtained by polycondensation of aromatic diols, diacyl dichlorides, oligolactides, and poly(ethylene glycol)s. Hydrophilicity of the copolyesters was controlled by the content of ethyleneoxy moieties as verified by contact angle measurements. Copolyesters with ethyleneoxy moieties showed significant enhancement of degradability under physiological conditions in comparison to copolyester without ethyleneoxy moieties, which makes these copolyesters promising materials for bone tissue engineering as also verified by hardness testing and mechanical testing.     

Carbohydrates in the epidermal mucous cells of a fresh-water fish Mastacembelus pancalus (mastacembelidae,Pisces) as studied by electron-microscopic cytochemical methods

Carbohydrates in the mucous cells of the epidermis of the fish Mastacembelus pancalus were studied by means of electron-microscopic cytochemical methods using physical development procedures. Three types of mucous cells (types A-C) were differentiated on the basis of the reactivities of the secretory products elaborated by them. The carbohydrate contents of mucous globules predominantly comprised sulfate esters and traces of oxidizable vicinal diols in type-A cells, oxidizable vicinal diols in type-B cells, and moderate amounts of both sulfate esters and oxidizable vicinal diols in type-C cells. Glycogen particles were also found to occur in the cytoplasm of these cells, and glycoproteins containing oxidizable vicinal diols were visualized in Golgi cisternae, rough endoplasmic reticulum, nuclear envelopes, and plasma membranes. In the type-A and type-B cells situated in the superficial layers of the epidermis, extensive cisternae of the Golgi apparatus and copious rough endoplasmic reticulum suggested the active syntheses of secretory contents, in contrast to the type-C mucous cells, which displayed poor development of these organelles, in the deeper layers.     

Microwave-assisted synthesis and characterization of optically active poly (ester-imide)s incorporating l-alanine

Pyromellitic dianhydride (1) was reacted with L-alanine (2) to result [N,N′-(pyromellitoyl)-bis-l-alanine diacid] (3). This compound (3) was converted to N,N′-(pyromellitoyl)-bis-l-alanine diacyl chloride (4) by reaction with thionyl chloride. The microwave-assisted polycondensation of this diacyl chloride (4) with polyethyleneglycol-diol (PEG-200) and/or three synthetic aromatic diols furnish a series of new PEIs and Co-PEIs in a laboratory microwave oven (Milestone). The resulting polymers and copolymers have inherent viscosities in the range of 0.31–0.53 dl g⁻¹. These polymers are optically active, thermally stable and soluble in polar aprotic solvents such as DMF, DMSO, NMP, DMAc, and sulfuric acid. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation and thermal analyses. Some structural characterizations and physical properties of these optically active PEIs and Co-PEIs have been reported.     

Synthesis and characterization of novel organosoluble and optically active aromatic polyesters containing <Emphasis Type="SmallCaps">l</Emphasis>-methionine and phthalimide pendent groups

5-(4-Methylthio-2-phthalimidylbutanoylamino)isophthalic acid (5) as a novel diacid monomer containing phthalimide and flexible chiral groups was prepared by dehydration of l-methionine and phthalic anhydride followed by reacting with thionyl chloride and then treating with 5-aminoisophthalic acid (5AIPA) in dry N,N-dimethylacetamide (DMAc). A series of novel polyesters (PEs) containing phthalimide group was prepared by the reaction of diacid monomer 5 with several aromatic diols via direct polyesterification with tosyl chloride/pyridine/dimethylformamide (DMF) system as condensing agent. The resulting new polymers were obtained in good yields and inherent viscosities ranging between 0.21 and 0.51 dLg⁻¹ were characterized with FT-IR, ¹H NMR, elemental and thermogravimetric analysis techniques. These polymers are readily soluble in polar organic solvents such as DMAc, DMF, dimethyl sulfoxide and protic solvents such as sulfuric acid. Specific rotation experiments demonstrate the optical activity induction due to successful insertion of l-methionine in the structure of pendent groups. Thermogravimetric analysis showed that the 10% weight loss temperature in a nitrogen atmosphere were more than 315°C, which indicates that the resulting PEs have good thermal stability.     

Synthesis of optically active diols using an efficient polymer bound cinchona alkaloid derivative

A new insoluble polymer containing a Cinchona alkaloid derivative has been synthesized and used as chiral ligand in the heterogeneous enantioselective dihydroxylation of olefins. It is shown that the enantioselectivity of the optically active diols obtained from both aliphatic and aromatic substrates is always comparable to that observed in the homogeneous phase under the same reaction conditions. A method for evaluating the enantiomeric excesses of the optically active products is also described. © 1995 Wiley-Liss, Inc.     

Enzymatic synthesis of alkyds

Lipases were used as catalysts in the synthesis of "all-trans" polyester oligomers in organic solvents. Esters of fumaric acid and 1,4-butane diol served as the substrates in the enzyme-catalyzed polytransesterification. No isomerization of the double bond was found under the mild conditions of enzymatic catalysis used by us, as opposed to the extensive isomerization found during chemical polycondensation. The alkoxy leaving group of the ester fumarate was found to be responsible for the rate of transesterification. Low (M(w) approximately 600-800) and high (M(w) = 1250) molecular weight alkyds were synthesized depending on whether tetrahedrofuran or acetonitrile, respectively, was used as the solvent.     

Enzyme-catalyzed polycondensation reactions for the synthesis of aromatic polycarbonates and polyesters.

Aromatic polymers are widely used in products ranging from optical lenses to milk bottles because of their strength, thermal durability, and high glass transition temperatures. All of the commonly used routes employed to generate aromatic polycarbonates and polyesters generate large amounts of waste as by-products and require high energy input. For these reasons, alternate routes to aromatic polymers which involve either less energy input or less waste generation are being investigated. One such route may be enzymatic. Herein we describe enzyme-catalyzed AA-BB condensation polymerizations to form aromatic polycarbonates and polyesters with six different aromatic diols and molecular weights of up to 5,200 Daltons are generated. In addition, for reactions with benzenedimethanol the enzyme exhibits regioselectivity for parahydroxyls over meta- and orthohydroxyls.     

Acyloin condensation of acyclic unsaturated aldehydes byMucor species

Summary 2E,6Z-Nonadienal, 2E,4E-nonadienal, citral and geraniol as precursors of geranial from acyloins enzymatically by reaction with activated acetate during fermentation by Mucor circinelloides CBS 39 468. The acyloins were reduced immediately by the fungus to (2S,3R)-diols. Reduction of the aldehyde group, including hydrogenation of the conjugated C-C double bond, hydroxylation of these alcohols and of the formed diols and some cyclizations are found as side reactions.     

Application of Urethane Prepolymers to Immobilization of Biocatalysts: Δ1Dehydrogenation of Hydrocortisone by Arthrobacter simplex Cells Entrapped with Urethane Prepolymers

Acetone-dried cells of Arthrobacter simplex having appreciable steroid Δ¹-dehydrogenase activity were immobilized by mixing the cell suspension with water-miscible urethane prepolymers synthesized from toluene diisocyanate and polyether diols. The entrapped cell activity in the transformation of hydrocortisone to prednisolone was affected by the properties of urethane prepolymers, such as the isocyanate group content in prepolymers, the molecular weight of polyether diols and the ethylene oxide content in diols. The addition of 10% of organic solvents, such as methanol and glycols, to the aqueous reaction mixture enhanced the solubility of the substrate greatly and the reaction rate of the immobilized cells. The activity of immobilized cells remained high even in the system containing 30% of methanol, which drastically inhibited the activity of free cells. The presence of an electron acceptor, phenazine methosulfate or 2,6-dichlorophenolindophenol, significantly stimulated the steroid conversion with entrapped cells, as well as free cells. The stability of the cells over repeated reactions was greatly improved by immobilization.     

Synthesis and modification of triterpenoids with two lupan backbones

The first derivatives containing two lupan backbones were synthesized by the interaction of betulonic acid chloride with diols (ethylene glycol and diethylene glycol) and monoethanolamine. A modification of ring A of ethylene-1,2-bis(betulonnate) led to its bis(3β-aminopropyloxy) and bis(3,4-seco-2-cyano) derivatives.