Showing papers on "Transesterification published in 1997"

Kinetics of transesterification of soybean oil

Abstract: Transesterification of soybean oil with methanol was investigated. Three stepwise and reversible reactions are believed to occur. The effect of variations in mixing intensity (Reynolds number=3,100 to 12,400) and temperature (30 to 70°C) on the rate of reaction were studied while the molar ratio of alcohol to triglycerol (6:1) and the concentration of catalyst (0.20 wt% based on soybean oil) were held constant. The variations in mixing intensity appear to effect the reaction parallel to the variations in temperature. A reaction mechanism consisting of an initial mass transfer-controlled region followed by a kinetically controlled region is proposed. The experimental data for the latter region appear to be a good fit into a second-order kinetic mechanism. The reaction rate constants and the activation energies were determined for all the forward and reverse reactions.

Reaction of Dextran with Glycidyl Methacrylate: An Unexpected Transesterification

Abstract: It is found that the reaction of glycidyl methacrylate with dextran proceeds via transesterification and results in the direct attachment of methacryloyl groups at the 2- and 3-hydroxyl group of the glucopyranose ring, in a 1:1 ratio

Preparation of highly purified concentrates of eicosapentaenoic acid and docosahexaenoic acid

Abstract: Because of the complexity of marine lipids, polyunsaturated fatty acid (PUFA) derivatives in highly purified form are not easily prepared by any single fractionation technique. The products are usually prepared as the ethyl esters by esterification of the body oil of fat fish species and subsequent physicochemical purification processes, including short-path distillation, urea fractionation, and preparative chromatography. Lipase-catalyzed transesterification has been shown to be an excellent alternative to traditional esterification and short-path distillation for concentrating the combined PUFA-content in fish oils. At room temperature in the presence of Pseudomonas sp. lipase and a stoichiometric amount of ethanol without any solvent, efficient transesterification of fish oil was obtained. At 52% conversion, a concentrate of 46% eicosapentaenoic acid (EPA) plus docosahexaenoic acid (DHA) was obtained in excellent recovery as a mixture of mono-, di-, and triacylglycerols. The latter can be easily separated from the saturated and monounsaturated ethyl esters and converted into ethyl esters either by conventional chemical means or enzymatically by immobilized Candida antarctica lipase. Urea-fractionation of such an intermediary product can give an EPA+DHA content of approximately 85%.

How do additives affect enzyme activity and stability in nonaqueous media

Abstract: The catalytic activities of lyophilized powders of alpha-chymotrypsin and Candida antarctica lipase were found to increase 4- to 8-fold with increasing amounts of either buffer salts or potassium chloride in the enzyme preparation. Increasing amounts of sorbitol in the chymotrypsin preparation produced a modest increase in activity. The additives are basically thought to serve as immobilization matrices, the sorbitol being inferior because of its poor mechanical properties. Besides their role as supports, the buffer species were indispensable for the transesterification activity of chymotrypsin because they prevented perturbations of the pH during the course of the reaction. Hence, increasing amounts of buffer species yielded a 100-fold increase in transesterification activity. Effects of pH changes were not as predominant in the peptide synthesis and the lipase-catalyzed reactions. Immobilization of the protease on celite resulted in a remarkable improvement of transesterification activity as compared to the suspended protease, even in the absence of buffer species. Immobilization of the lipase caused a small improvement of activity. The activity of the immobilized enzymes was further enhanced 3-4 times by including increasing amounts of buffer salts in the preparation.The inclusion of increasing amounts of sodium phosphate or sorbitol to chymotrypsin rendered the catalyst more labile against thermal inactivation. The denaturation temperature decreased with 7 degrees C at the highest content of sodium phosphate, as compared to the temperature obtained for the denaturation of the pure protein. The apparent enthalpy of denaturation increased with increasing contents of the additives. The enhancement of hydration level and flexibility of the macromolecule upon addition of the compounds partly provides the explanation for the observed results.

Catalysis of Hydrolysis and Transesterification Reactions of p-Nitrophenyl Esters by a Designed Helix−Loop−Helix Dimer

Abstract: KO-42, a polypeptide with 42 amino acid residues has been designed to fold into a hairpin helix−loop−helix motif that dimerizes and forms a four-helix bundle. The solution structure of the folded KO-42 dimer has been determined by NMR and CD spectroscopy and ultracentrifugation. On the surface of the folded polypeptide a reactive site has been engineered that is capable of catalyzing acyl-transfer reactions of reactive esters. The reactive site of KO-42 contains six histidine residues with perturbed pKa values. The pKas of His-15, His-30, and His-34 are close to 5, whereas those of His-11, His-19, and His-26 are close to 7, with nonideal titration curves. The second-order rate constant for the KO-42 catalyzed hydrolysis of mono-p-nitrophenyl fumarate at pH 4.1 and 290 K is 0.1 M-1 s-1, which is 1140 times larger than that of the 4-methylimidazole (4-MeIm) catalyzed reaction, 8.8 × 10-5 M-1 s-1. The second-order rate constant for the KO-42 catalyzed transesterification of mono-p-nitrophenyl fumarate to for...

Lipase-catalyzed glycerolysis of soybean oil in supercritical carbon dioxide

Abstract: The transesterification of soybean oil with glycerol, 1,2-propanediol, and methanol by an immobilized lipase in flowing supercritical carbon dioxide for the synthesis of monoglycerides is described. A lipase from Candida antarctica was used to catalyze the reaction of soybean oil with glycerol, 1,2-propanediol, ethylene glycol, and methanol. Reactions were performed in supercritical carbon dioxide at a density of 0.72 g/L and at a flow rate of 6 µL/min (expanded gas). The substrates were added at flows ranging from 2.5 to 100 µL/min. Monoglycerides were obtained at up to 87 wt%, and fatty acid methyl esters at nearly 100 wt%. The reactivity of the alcohols paralleled the solubility of the substrate in liquid carbon dioxide. Glycerol has the slowest reaction rate, only 2% of that of methanol.

Two-step synthesis of diphenyl carbonate from dimethyl carbonate and phenol using MoO3SiO2 catalysts

Abstract: The transesterification of dimethyl carbonate with phenol to produce methyl phenyl carbonate was carried out in an autoclave using a variety of solid catalysts. MoO 3 SiO 2 was found to have a very high activity for this transesterification. Thus, a 17.1% yield of methyl phenyl carbonate based on phenol was obtained at 433 K in the presence of MoO 3 SiO 2 . MoO 3 SiO 2 was also an active catalyst for the disproportionation of methyl phenyl carbonate into diphenyl carbonate and dimethyl carbonate. A 48% yield of diphenyl carbonate was attained over MoO 3 SiO 2 at 443 K. These yield values are probably very close to those at the thermodynamic equilibrium.

The preparation of concentrates of eicosapentaenoic acid and docosahexaenoic acid by lipase-catalyzed transesterification of fish oil with ethanol

Abstract: The objective of this study was to investigate the use of lipases as catalysts for producing concentrates of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) from fish oil as an alternative to conventional chemical procedures. Transesterification of fish oil with ethanol was conducted under anhydrous solvent-free conditions with a stoichiometric amount of ethanol. Among the 17 lipases tested, the results showed that Pseudomonas lipases had the highest activity toward the saturated and monounsaturated fatty acids in the fish oil, much lower activity toward EPA and DHA and, at the same time, good tolerance toward the anhydrous alcoholic conditions. With 10 wt% of lipase, based on weight of the fish oil triacylglycerol substrate (15% EPA and 9% DHA initial content), a 50% conversion into ethyl esters was obtained in 24 h at 20°C, in which time the bulk of the saturated and monounsaturated fatty acids reacted, leaving the long-chain n-3 polyunsaturated fatty acids unreacted in the residual mixture as mono-, di-, and triacylglycerols. This mixture comprised approximately 50% EPA+DHA. Total recovery of DHA and EPA was high, over 80% for DHA and more than 90% for EPA. The observed fatty acid selectivity, favoring DHA as a substrate, was most unusual because most lipases favor EPA.

Continuous operation of lipase-catalyzed reactions in nonaqueous solvents: Influence of the production of hydrophilic compounds.

Abstract: In the field of biocatalysis in nonaqueous media, water has been identified as a crucial parameter which has to be carefully controlled. This article studies the continuous operation of a water-producing enzymatic reaction, here the esterification of oleic acid by ethanol in n-hexane catalyzed by Lipozyme(TM). The conversion decreased significantly over time, eventually coming to a lower steady-state level. This would be due to the accumulation of the produced water into the enzyme fixed-bed reactor, n-hexane being unable to evacuate this water out of the reaction vessel, because of the low polarity of this solvent. Therefore the conversion decreased until the produced water could be eliminated by the solvent achieving a steady state with a lower conversion. In supercritical carbon dioxide, a more hydrophilic solvent, steady state is at once obtained. This approach has been extended to reaction producing a hydrophilic compound, here glycerol during the transesterification between triolein and ethanol, and similar conclusions can be made. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 56: 232-237, 1997.

Characterization of partially saturated poly(propylene fumarate) for orthopaedic application

Abstract: A partially saturated linear polyester based on poly(propylene fumarate) (PPF) was synthesized for potential application in filling skeletal defects. The synthesis was carried out according to a two-step reaction scheme. Propylene glycol and fumaryl chloride were first combined to form an intermediate fumaric diester. The intermediate was then subjected to a transesterification to form the PPF-based polymer. This method allowed for production of a polymer with a number average molecular weight up to 1500 and a polydispersity index of 2.8 and below. The polymeric backbone structure was investigated through the use of FTIR and NMR. Kinetic studies of the transesterification allowed mapping of the molecular weight increase with reaction time. The final product was also characterized by thermal and solubility analysis.

Determination of fat content and fatty acid composition through 1-min transesterification in the food sample; principles

Abstract: Base-catalysed transesterification can occur in water-containing foods, such as ice-cream or milk, because it happens much faster than saponification. Under the conditions proposed, it takes 1 min at ambient temperature. The reaction must be stopped before relevant saponification occurs, reducing the pH. The method enables the determination of the fat content through the sum of all fatty acids as well as the fatty acid composition without previous extraction from the foodstuff. Some foods, such as meat or cheese, are heated for a short while in dimethylformamide (DMF) in order to solubilize the fat in the reaction medium. A system of four internal standards verifies the completeness of the transesterification for every analysis and checks for relevant saponification or discrimination by GC analysis.

Process for making PEN/PET blends and transparent articles therefrom

Abstract: Process for controlling the change of intrinsic viscosity and transesterification during solid stating of a polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) blend, with an effective amount of an ethylene glycol compound. The process enables the production of a copolymer based on predefined initial and final IV's and final transesterification level, by varying the solid-stating time and/or effective amount of ethylene glycol. In one embodiment, a relatively greater amount of post-consumer PET (e.g., 70%) having an IV of on the order of 0.72-0.73, is incorporated in the blend to provide a final IV on the order of 0.80-0.85, and a moderate, controlled level of transesterification; the blend is used to injection mold a sleeve layer of a preform. In another embodiment, a substantially transparent neck finish for a preform is made from a PEN/PET blend having an amount of ethylene glycol which enables substantial transesterification, without excessive increase in IV.

Synthesis and characterization of fumarate-based polyesters for use in bioresorbable bone cement composites

Abstract: Fumarate-based polyesters were prepared by the transesterification polycondensation of diethyl fumarate and diols: (±)-1,2-propanediol, (S)-(+)-1,2-propanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol Different polyester microstructures were observed by 1H-NMR and 13C-NMR spectroscopy when the reaction was conducted in the presence of p-toluenesulfonic acid monohydrate or metal containing catalysts—aluminum trichloride, titanium tetrachloride, titanium tetrabutoxide, and zinc chloride The extent of formation of branched structures associated with hydroxyl end groups' addition to the unsaturated polyester double bonds depends on the acidity of the catalyst The bone cement composites were prepared by mixing the fumarate polyesters with an inorganic filler, CaSO4 · 2H2O, and N-vinyl pyrrolidone, which crosslinks on the addition of a radical initiator, benzoyl peroxide, at ambient temperatures The compressive strength and hydrolytic stability of the cement compositions was correlated with structure of the polyesters © 1997 John Wiley & Sons, Inc J Appl Polym Sci 66: 1123–1137, 1997

Thermoplastic processable starch or starch derivative polymer mixtures

Abstract: The invention relates to thermoplastic processable transesterification or esterification products of starch or starch derivatives with, for example, lactones, fatty acids, esteramides and the like, wherein the starch or the starch derivative is brought to melt using the appropriate softeners or plasticizers before esterification or transesterification.

Synthesis and Characterization of a Block Copolymer Consisting of Poly(propylene fumarate) and Poly(ethylene glycol)

Abstract: Poly(propylene fumarate-co-ethylene glycol) has been synthesized in an effort to develop a cross-linkable biomaterial for use as a vascular implant. This copolymer has been fabricated in a block configuration with two to three homopolymer units in series through a transesterification reaction between the linear polyester and the terminal hydroxyl functionalities of the poly(ethylene glycol) (PEG). A number of design parameters including the molecular weights of the two homopolymers, the copolymer reaction time, and the weight percent of PEG were varied in order to assess their effects on the properties of the resulting copolymer. This material has been characterized in terms of structure and composition as well as thermal properties and solubility behavior. All formulations of the copolymer exhibited a single glass transition temperature and a single melting temperature, with a degree of crystallinity which was dependent upon the relative amount of PEG. The copolymers were water soluble and demonstrated e...

Evaluation of different approaches for lipase catalysed synthesis of citronellyl acetate

Abstract: Three different approaches for lipase catalysed synthesis of citronellyl acetate by a commercial available immobilized lipase have been studied: a) direct esterification reaction of citronellol with acetic acid; b) alcoholysis of butyl acetate with citronellol and c) transesterification of citronellyl butyrate with butylacetate. Heptane was used as solvent for all the experiments. The extent of reaction occurred in the order alcoholysis>transesterification>esterification. Substrate partitioning between the immobilization support and the organic medium seems to greatly influence the catalytic performance of this enzyme preparation. Production of citronellyl acetate, was found to be dependent on the partition coefficient of the acyl donor which account the greatest value for the acetic acid.

Selection of salt hydrate pairs for use in water control in enzyme catalysis in organic solvents.

Abstract: The water activities (a(w)) of 13 salt hydrate pairs were determined from vapor pressure measurements; a(w) values for a subset were also estimated from a study of water transfer to isopropylether. The application of salt hydrates as water buffers was investigated in two models: (i) effect of hydration on the initial rate of subtilisincatalyzed transesterification of the nitrophenol ester of CBZ-alanine with butanol; and (ii) effect of hydrates on the equilibrium concentrations of reactants in the esterification of dodecanol and decanoic acid, catalyzed by lipase. Transfer of ions from salt to enzyme particles was also demonstrated. The implications of the results for the successful use of salt hydrates as water buffers are discussed. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 367-374, 1997.

Production of trimethylolpropane esters of rapeseed oil fatty acids by immobilized lipase

Abstract: The polyol, trimethylolpropane (2-ethyl-2-hydroxymethyl-1,3-propanediol), and a mixture of rapeseed oil fatty acid methyl esters were transesterified by immobilized lipases without additional organic solvent. The conversion to the polyol tri-ester with immobilized Rhizomucor mieheilipase Lipozyme IM 20 was about 75% after 24 h at 58°C, 5.3 kPa, with no added water, and the highest conversion of about 90% was reached in 66 h.

Lipases have similar water activity profiles in different reactions

Abstract: The shape of the profiles of enzyme activity versus water activity for four different lipases were independent of the reaction used to determine the activity. The profile for each lipase (Rhizopus arrhizus, Pseudomonas sp., Candida rugosa and Lipozyme) in esterification, hydrolysis and transesterifications profiles were the same. In transesterification the yield was unaffected by the water activity but the hydrolysis yield increased with increasing aW .