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At least 433 records · Page 24Linked to original sources

PubMed2000

The nature of fatty acid modifies the equilibrium position in the esterification catalyzed by lipase.

The equilibrium position in lipase mediated esterification of various fatty acids and butanol was studied. The influence of the chain length and the presence of unsaturations in the fatty acids on the equilibrium position was measured and predicted. To predict equilibrium position the program TREP extended (TREPEX) based on the UNIFAC group contribution method was used. Using an equilibrium constant of 35, calculated on the basis of thermodynamic activities, the equilibrium position between butanol and saturated and/or unsaturated fatty acids with different chain lengths can be predicted. The ester mole fraction at equilibrium increases with the fatty acid chain length, and for fatty acids with the same carbon number, the highest values are found for unsaturated fatty acids. For reaction systems containing two saturated fatty acids, a slightly higher mole fraction is obtained for the fatty acid with the higher chain length, while for mixtures consisting of saturated and unsaturated fatty acids, the mole fractions of the unsaturated esters are lower than those of the saturated ones, regardless the chain length of the fatty acid. These experimental results are in good agreement with the calculations with TREPEX.

Biotechnology↗

PubMed2001

Mineral absorption by albino rats as affected by some types of dietary pectins with different degrees of esterification.

Male albino rats were fed diets contained 6.85% mineral salts for 2 weeks (adaptation condition). Then they were fed the dietary pectin administered diet for 6 weeks to evaluate the effect of administration of pectin on the absorption of some monovalent, bivalent and heavy metals in the serum of rats. The experimental parameters included, monovalent minerals (K, Na), bivalent minerals (Zn, Cu, Ca, Fe), heavy metals (Pb, Cd), serum uric acid and serum creatinine. The obtained results indicated that the serum contents of monovalent minerals were negatively affected by pectin administration. The low degree of esterification of pectin was more effective on the absorption of bivalent minerals. Also, the rat serum levels of lead and cadmium were reduced by pectin administration. Serum total proteins were reduced by pectin administration. The level of rat serum of uric acid and creatinine fed different sources of pectin were within normal levels and were insignificantly lower than that recorded for control samples.

Absorption↗

PubMed2001

Effect of water activity and immobilization on fatty acid selectivity for esterification reactions mediated by lipases.

The effect of water activity (a(w)) and immobilization on fatty acid (FA) selectivity of Burkholderia (formerly Pseudomonas) cepacia, Rhizomucor miehei, Candida antarctica (type B), and Candida rugosa lipases in esterification reactions was determined. Studies were based on measuring ester formation in multicompetitive reaction mixtures containing either the homologous series of even carbon number n-chain saturated FA (C4-C18) or a series of n-chain (un)saturated FA (C18:X, where X = 0-3 double bonds) as cosubstrates with 1,3-propanediol in ter-butyl methyl ether at a(w) of 0.19, 0.69, and 0.90. Activity and FA selectively patterns were similar for free and Celite-adsorbed lipases in response to changes in a(w'), although specific effects were observed for selectivity of B. cepacia and C. rugosa lipases toward C16 and C4/C6 FA, respectively. Also, selectivity toward unsaturated C18:X FA as a group was modulated by changes in a(w) for three of the four lipase studied. Resin-fixed lipases from R. miehei and C. antarctica exhibited profound differences in activity and FA selectively in response to changes in a(w'), relative to free and Celite-bound forms. These findings suggest that FA selectivity for lipid modification is influenced by a(w) and immobilization, but that each lipase has a characteristic response to these factors in a manner that cannot be predicted.

Anion Exchange Resins↗

PubMed2001

Influence of water activity on the enantioselective esterification of (R,S)-ibuprofen by crosslinked crystals of Candida antarctica lipase B in organic solvent media.

The lipase B from Candida antarctica was purified from a commercial source and crystallized. The microcrystals were crosslinked using glutaraldehyde. The crosslinked crystals were then used to catalyze the esterification of (R,S)-ibuprofen with dodecanol in octane at various water activities. As for the commercial preparation immobilized on acrylic resin, Novozym 435, low water activities foster better enantioselectivity, and the maximum reaction rates are obtained for a(W) = 0.1.

Candida↗

PubMed2002

Efficient water removal in lipase-catalyzed esterifications using a low-boiling-point azeotrope.

High conversions in lipase-catalyzed syntheses of esters from free acyl donors and an alcohol requires efficient removal of water preferentially at temperatures compatible to enzyme activity. Using a lipase B from Candida antarctica (CAL-B)-mediated synthesis of sugar fatty-acid esters, we show that a mixture of ethyl methylketone (EMK) and hexane (best ratio: 4:1, vo/vo) allows efficient removal of water generated during esterification. Azeotropic distillation of the solvent mixture (composition: 26% EMK, 55% hexane, 19% water) takes place at 59 degrees C, which closely matches the optimum temperature reported for CAL-B. Water is then removed from the azeotrope by membrane vapor permeation. In case of glucose stearate, 93% yield was achieved after 48 h using an equimolar ratio of glucose and stearic acid. CAL-B could be reused for seven reaction cycles, with 86% residual activity after 14 d total reaction time at 59 degrees C. A decrease in fatty-acid chain length as well as increasing temperatures (75 degrees C) resulted in lower conversions. In addition, immobilization of CAL-B on a magnetic polypropylene carrier (EP 100) facilitated separation of the biocatalyst.

Bioreactors↗

PubMed2006

Effect of water activity on the lipase catalyzed esterification of geraniol in ionic liquid [bmim]PF6.

Enzymatic reactions in non-aqueous media have been shown to be effective in carrying out chemical transformation where the reactants are insoluble in water or water is a byproduct limiting conversion. Ionic liquids, liquid organic salts with infinitesimal vapor pressure, are potentially useful alternatives to organic solvents. It is known that the thermodynamic water activity is an important variable affecting the activity of enzymes in non-aqueous solvents. This study investigated the influence of water activity on the esterification of geraniol with acetic acid in ionic liquid [bmim]PF6 catalyzed by immobilized Candida antarctica lipase B. The conversion of geraniol in [bmim]PF6 was significant although the reaction rate was slower than in organic solvents. The profile of initial reaction rate-water activity was determined experimentally, and differed from the data reported for other non-aqueous solvents. A maximum in the initial reaction rate was found at aw = 0.6. The pseudo reaction equilibrium constant, Kx, was measured experimentally for the reaction. The average value of Kx in [bmim]PF6 was 12, 20-fold lower than the value reported for the same system in hexane.

Acyclic Monoterpenes↗

PubMed2002

Enantiopure building blocks for chiral drugs from racemic mixtures of secondary alcohols by combination of lipase catalysis and Mitsunobu esterification.

The racemic alcohols 3-chloro-1-(2-thienyl)-1-propanol, 3-chloro-1-phenylpropanol, and 1-chloro-3-(3,4-difluorophenoxy)-2-propanol were converted into a mixture of one enantiomer as butanoate and the other as alcohol by lipase catalysis. Subsequent Mitsunobu esterification without separation proceeded with inversion of the unreacted alcohols to give high yield and ee of the three enantiopure butanoates. The butanoates of opposite configuration were produced in a similar manner, but starting with lipase-catalyzed hydrolysis of the racemic butanoates.

Alcohols↗

PubMed1995

Esterification of 12(S)-hydroxy-5,8,10,14-eicosatetraenoic acid into the phospholipids of human peripheral blood mononuclear cells: inhibition of the proliferative response.

12-hydroxy-eicosatetraenoic acid (12-HETE), the lipoxygenase metabolite of arachidonic acid produced by activated platelets, has been shown to accumulate in peripheral blood mononuclear cells (PBMC) of elderly people. 12-HETE being antimitogenic for lymphocytes, its accumulation in blood cells might be involved in the well-known decline in immune function which accompanies aging. Because HETEs have been shown to be rapidly metabolized and/or incorporated into cellular lipids in a variety of cell types, we have investigated the uptake, metabolism, and intracellular distribution of exogenous 12-HETE by human PBMC. [3H]-12-HETE was dose and time dependently incorporated by PBMC and also metabolized to more polar products. These polar metabolites were mainly released extracellularly and only marginally esterfied in phospholipids. Although [3H]-12-HETE radiolabel was preferentially associated with phosphatidylcholine, especially after prolonged labeling incubations or following successive short labeling pulses, a substantial amount of radiolabel was also found associated with phosphatidylinositol (20-50% of the labeled phospholipids). The stability of 12-HETE in the phospholipid pool was comparable to that reported for most other cell types, with 50% of the initial radiolabel being still present after 18 hr. Upon exposure to mitogenic activation, 12-HETE-labeled PBMC released unmodified 12-HETE from phosphatidylinositol. In addition, 12-HETE dose dependently inhibited the proliferative response of PBMC to Con A stimulation. These results suggest that 12-HETE esterification in phospholipids might lead to the generation of unusual lipid second messengers with impaired capacity to transduce activation signals, thus decreasing lymphocyte function.

12-Hydroxy-5,8,10,14-eicosatetraenoic Acid↗

PubMed1990

Detailed study of oxidative esterification and elimination reactions undergone by a steroidal 17 alpha-benzoyloxy-20-oxo-21-aldehyde.

The reaction of 17 alpha-benzoyloxy-11 beta-hydroxy-3,20-dioxo-1, 4-pregnadien-21-al as the hemiacetal (1) with methanol:acetic acid:potassium cyanide:manganese dioxide followed by acetylation and preparative HPLC of the reaction mixture afforded 11 crystalline products. These products can be conveniently divided into three categories representing side-chain cleavage and oxidative esterification with or without elimination of the benzoyloxy group. Of special interest was the stereospecific formation of the C-17 cyanohydrin acetate 4a and the cis delta 17(20) enol acetate methyl ester 5. On the other hand, nonstereospecific addition of HCN to the side chain gave the C-20 epimeric cyanohydrin acetates 7a and 7b. The use of activated versus nonactivated MnO2 plays a major role in determining the quantitative distribution of the products. It was also discovered that even in the absence of MnO2, the reaction goes to completion. A proposed mechanism which explains the formation of all products is presented.

Chemical Phenomena↗

PubMed1986

Comparative rates of esterification of 5'-AMP with hydrophobic amino acids: relevance to the genetic-code assignments.

We have continued our program aimed at understanding the origin and evolution of the genetic code and the process of protein synthesis by comparing the rates of esterification of 5'-AMP by a series of hydrophobic N-acetylamino acids. The reaction clearly shows differences in reaction rate (AcPhe greater than AcLeu greater than AcVal greater than AcIle) among the amino acids having A as middle letter of their anticodons. However, there were no significant differences in reaction rate between AcLeu, AcNorleu, and Ac-alpha-aminobutyric acid, and AcGly reacted faster than all of these and AcPhe. Consequently, this simple reaction with AMP can distinguish only among those amino acids that actually have A as the middle anticodonic nucleotide. The relevance of these studies to the origins of the process of protein synthesis and of the genetic code is discussed in conjunction with results from other studies of a similar nature.

Acetylation↗

PubMed1993

The esterification of cholesterol in the yolk sac membrane of the chick embryo.

The uptake of lipid from the yolk by the yolk sac membrane of the chick embryo is accompanied by the rapid esterification of a large proportion of the yolk cholesterol. This could arise from enhanced acyl-CoA:cholesterol acyltransferase (ACAT) activity and/or inhibition of cholesteryl ester hydrolase (CEH) activity. The activity of ACAT was therefore measured in microsomes obtained from yolk sac membranes at various stages of development. A high level of activity (up to 929 pmol of cholesteryl oleate formed per min per mg protein) was found during the second half of this period. Supplementation with exogenous cholesterol stimulated ACAT activity in microsomes obtained from the tissue at the earlier, but not at the later, stages of development suggesting that the enzyme became saturated with microsomal cholesterol as development proceeded. Correlating with this, the concentration of cholesterol in the microsomes increased 4-fold between 9 and 20 d of development. The activity of CEH was very low in the microsomes and could not be detected in the cytosolic fraction. The activity of a protein, which has been shown to function as an inhibitor of CEH, was found to be present at all stages of development. The high activity of ACAT, together with the low activity of CEH and an active CEH inhibitor protein is a combination well suited to promote an essentially unidirectional conversion of cholesterol to cholesteryl ester. This process may be a major determinant of the rate of lipid transfer from the yolk to the embryo.

Animals↗

PubMed1998

Tissue-related changes in methyl-esterification of pectic polysaccharides in cauliflower (Brassica oleracea L. var. botrytis) stems.

Pectic substances are a major component of cell walls in vegetable plants and have an important influence on plant food texture. Cauliflower (Brassica oleracea L. var. botrytis) stem sections at different regions of the mature plant stem have been monitored for tissue-related changes in the native pectic polysaccharides. Chemical analysis detected appreciable differences in the degree of methyl-esterification (ME) of pectic polysaccharides. About 65% of galacturonic acid (GalpA) residues were methyl-esterified in floret tissues. Relative ME showed a basipetal decrease, from 94% in the upper stem to 51% in the lower-stem vascular tissues. The decrease was not related to a basipetal increase in glucuronic acid (GlcpA) residues. The monoclonal antibodies, JIM 5 and JIM 7, produced distinct labelling patterns for the relatively low-methylesterified and high-methyl-esterified pectin epitopes, respectively. Labelling was related to cell type and tissue location in the stem. Floret cell walls contained epitopes for both JIM 5 and JIM 7 throughout the wall. Stem vascular tissues labelled more strongly with JIM 5. Whereas pith parenchyma in the upper stem labelled more strongly with JIM 7, in the lower-stem pith parenchyma, JIM 5 labelling predominated. Localization of pectic polysaccharide epitopes in cell walls provides an insight into how structural modifications might relate to the textural and nutritional properties of cell walls.

Brassica↗

PubMed1998

Predominance of large low density lipoprotein particles and lower fractional esterification rate of cholesterol in high density lipoprotein in children with insulin-dependent diabetes mellitus.

UNLABELLED: Coronary artery disease (CAD) is a major cause of death in patients with insulin-dependent diabetes mellitus. Qualitative changes in low density lipoprotein (LDL) and high density lipoprotein (HDL) are thought to be important for evaluating the risk for CAD. In the present study, we evaluated LDL particle size (LDL-size) by 2%-16% gradient gel electrophoresis, along with conventional lipids and apolipoproteins, in 23 children with IDDM (10 males and 13 females) and 27 nondiabetic controls (12 males and 15 females). The fractional and molar esterification rates (FER and MER) of cholesterol in plasma and HDL were also determined. Plasma levels of triglyceride were significantly lower in diabetic children than in controls. Plasma apoA-I and apoA-II levels in female diabetic children were significantly higher and lower than those in controls respectively. Plasma levels of HDL-cholesterol and the ratio of apoA-I to apoA-II were significantly higher in diabetic children than in controls. Other lipid and apolipoprotein parameters in diabetic children were similar to those in controls. LDL-size in diabetic children was significantly greater than that in controls. FERHDL, which reflects the particle size distribution of HDL, was significantly lower in diabetic children than in controls, which suggests that diabetic children had larger HDL particles. CONCLUSION: The qualitative and quantitative changes in LDL and HDL in diabetic children are similar to those associated with a reduced risk for CAD. Intensive insulin therapy in children may help preventing coronary heart disease in adulthood.

Adolescent↗

PubMed2003

Influence of temperature and high dietary linoleic acid content on esterification, elongation, and desaturation of PUFA in Atlantic salmon hepatocytes.

The esterification, desaturation, and elongation of [1-14C]18:3n-3, [1-14C]18:2n-6, and [1-14C]20:5n-3 at 5 and at 12 degrees C were studied using cultivated hepatocytes from Atlantic salmon. The salmon were fed diets, in which 0, 50, or 100% of the supplementary fish oil had been replaced by soybean oil, for 950 day-degrees at 5 and 12 degrees C. The endogenous percentage of 18:2n-6 in hepatocyte lipids was 2% in cells from fish fed a diet with 100% of the supplemental lipid from fish oil, and it was slightly less than 25% in cells from fish fed the diet with 100% of the supplemental lipid from soybean oil. Furthermore, the percentages of 20:3n-6 and 20:4n-6 were significantly higher in hepatocytes from fish fed on soybean oil than they were in those of fish fed on fish oil. The percentages of 20:5n-3 and 22:6n-3, on the other hand, were lower. The endogenous levels of n-6 FA were not significantly correlated with the total amounts of radiolabeled FA esterified in hepatocyte lipids. The main radiolabeled products formed from 18:2n-6 were 20:2n-6 and 20:3n-6. The level of the important eicosanoid precursor 20:4n-6 was twice as high in hepatocyte phospholipids from fish fed the 100% soybean oil diet as it was in hepatocytes from fish fed the diet with 100% of supplemental lipid from fish oil. The main products formed from 18:3n-3 were 20:4n-3, 20:5n-3, and 22:6n-3. High levels of dietary 18:2n-6 do allow, or even seem to increase, the production of 22:6n-3 from 18:3n-3 in hepatocytes. The main products formed from 20:5n-3 were 22:5n-3 and 22:6n-3. The production of 22:6n-3 from 20:5n-3 was higher at 5 degrees C than at 12 degrees C. The percentage of 24:5n-3 was higher at 5 degrees C than it was at 12 degrees C, as was the ratio of 24:5 to 22:5. These results suggest that the elongation rate of 22:5n-3 to 24:5n-3 is higher at the lower temperature.

Animals↗

PubMed1997

Impaired cholesterol esterification in the plasma in patients with breast cancer.

An important factor which determines the movement of cholesterol in and out of the cells is the free cholesterol (FC)/esterified cholesterol (EC) ratio in the plasma. Although this ratio has been shown to be increased in several types of malignancies in humans as well as experimental animals, it is not known whether such an abnormality is found in breast cancer patients. Furthermore, the reasons for such an increase in cancer patients are unknown. We studied the plasma lipid composition and the activity of lecithin-cholesterol acyltransferase (LCAT), the enzyme responsible for the formation of most of EC in human plasma, in 12 women with breast cancer and 9 age-matched control women. The plasma EC concentration was found to be significantly decreased in cancer patients, whereas the FC concentration was unchanged, leading to increased FC/EC ratios (P < 0.05). The concentration of phosphatidylcholine, the acyl donor in the LCAT reaction, was decreased significantly, whereas all other phospholipids were unaffected. The cholesterol-esterifying activity of LCAT was significantly lower in cancer patients, whether assayed with endogenous substrates (P < 0.05), or with an exogenous substrate (P < 0.01). However, another function of the enzyme, namely the lysolecithin acyltransferase activity, was increased (P < 0.02), indicating that the enzyme concentration in plasma may not be decreased. These results show that the increase in the FC/EC ratio in cancer patients is due to an impaired esterification of cholesterol by plasma LCAT, probably due to an alteration in the composition of substrate lipoproteins, or the presence of an inhibitory factor.

1-Acylglycerophosphocholine O-Acyltransferase↗

PubMed1998

Vitamin E reduces cholesterol esterification and uptake of acetylated low density lipoprotein in macrophages.

The effects of vitamin E on cholesteryl ester (CE) metabolism in J774 cells were examined. Pretreatment of J774 cells with vitamin E at concentrations above 50 microM significantly decreased acetylated low density lipoprotein (LDL)-induced incorporation of [14C]oleate into CE in cells in a dose-dependent manner. This was partly due to vitamin E also significantly inhibiting the uptake of [3H]CE-labeled acetylated LDL by J774 cells. A trend existed toward suppression of acyl-CoA:cholesterol acyltransferase (ACAT) activity in the cell lysate at high vitamin E concentration, but there was no effect on hydrolysis of CE. These data indicate that vitamin E reduces the uptake of modified LDL and suppresses ACAT activity, resulting in less cholesterol esterification in macrophages: a novel mechanism underlying the antiatherogenic properties of vitamin E.

Animals↗

PubMed1980

Effect of local anesthetics on sterol biosynthesis and sterol esterification in rat liver in vitro.

Various local anesthetics were found to inhibit sterol esterification by acyl-CoA:cholesterol acyltransferase (EC 2.3.1.26) in the microsomal fraction from rat (and rabbit) liver and to inhibit sterologenesis in rat liver slices. The enzyme was assayed in isolated microsomes by following the incorporation of [1-14C]oleoyl-CoA into steryl esters; the order of inhibitory potency on the enzyme was dibucaine > benzocaine > tetracaine > lidocaine > procaine. In liver slices, the incorporation of labeled acetate and mevalonate into C27 sterols, digitonin-precipitable sterols, and squalene was inhibited in the order dibucaine > tetracaine > lidocaine. A comparison of incorportion patterns from labeled acetate and mevalonate suggest that inhibition of sterologenesis occurs at more than one post-mevalonate step in the pathway.

Anesthetics, Local↗

PubMed1986

Essential fatty acid uptake and esterification in primary culture of rat hepatocytes.

Primary cultures of adult rat hepatocytes were used to compare the uptake and esterification of essential polyunsaturated fatty acids (18:2, 20:3 and 20:4 of the n-6 series) with those of palmitic and oleic acids. The uptake of unesterified fatty acids was linearly related to the free fatty acid/albumin molar ratio for 14 h and did not depend on the unbound free fatty acid level. Whatever the initial free fatty acid/albumin molar ratio, it dropped to 0.5 +/- 0.1 mM after 14 h, thus showing that hepatocytes have a high capacity for clearing free fatty acids from the medium at high free fatty acid/albumin molar ratios. The free fatty acid uptake become saturable when the free fatty acid and albumin concentrations were raised and the free fatty acid/albumin ratio remained constant. This strongly suggests that albumin-hepatocyte interaction mediates free fatty acid uptake. This uptake was identical whatever the fatty acid tested and did not depend on the relative amounts of fatty acids when they were added simultaneously. Triacylglycerol accumulation and synthesis, monitored by labelled fatty acids, were related to the free fatty acid/albumin molar ratio and exhibited no specificity for the series of fatty acids tested. Triacylglycerols were enriched in all the fatty acids tested by up to 60%, and fatty acid incorporation into diacylglycerols and triacylglycerols reflected the free fatty acid composition of the medium. By contrast, neither the level nor the synthesis of phospholipids varied with free fatty acid/albumin, but the rate of phospholipid turnover depended on the fatty acids tested. Accumulation of these acids was smaller in phospholipids than in triacylglycerols. When linoleic and arachidonic acids were added together, phospholipids (especially phosphatidylethanolamine and phosphatidylinositol) were more enriched in arachidonic acid than triacylglycerols. This might be due to the specificity for fatty acid of the enzymes involved in phospholipid metabolism.

Animals↗