New advances in the chemistry of methoxylated lipids

Methoxylated lipids have been reviewed emphasizing the alkylglycerol ethers and fatty acids bearing the methoxy group in the alkyl chain. The literature on methoxylated lipids and their derivatives has been divided into four main groups, namely 2-methoxylated alkyl glycerols, ω-methoxylated fatty acids, mid-chain methoxylated fatty acids, and -methoxylated fatty acids. The natural occurrence, biological activity, and synthesis of this interesting group of lipids are discussed. Most of these compounds have been isolated from either bacterial or marine sources, but others are mainly of synthetic origin. Among the interesting biological activities displayed by these compounds the most important are antibacterial, antifungal, antitumor, and antiviral.     

Partial characterization of glyceroglucolipids from human saliva

Glycolipids of human saliva have been isolated and partially characterized. The neutral glycolipids consisted of six compounds, composed of glucose, glyceryl ethers and fatty acids, and differed from each other primarily with respect to the number of glucose residues. The major acidic glycolipid contained glucose, glyceryl ethers, fatty acids and sulfate. Based on the data of chemical analyses we propose that the acidic glycolipid is a 1-0-alkyl-2-0-acylglycerol triglucoside sulfate and that the neutral glycolipids are mono-, di-, tri-, hexa- and octaglucoside derivatives of 1-0-alkyl-2-0-acylglycerol.     

Gas chromatography mass spectrometry of tert-butyldimethylsilyl ethers of phthiocerols and mycocerosic alcohols from Mycobacterium tuberculosis

Mycobacteria synthesize a variety of unusual long-chain fatty acid esters and the systematic analysis of these is of great potential in the classification and identification of these bacteria. This paper describes the extraction, reductive fission and derivatization to tert-butyldimethylsilyl ethers of beta-diesters, the phthiocerol dimycocerosates. The mass spectra of these ethers are characteristic of the parent alcohols and selected ion monitoring techniques have been applied to mixtures extracted from strains of Mycobacterium tuberculosis.     

Mechanisms in the modulation of the reactions of immune splenocytes by macroheterocyclic compounds

The effect of macroheterocyclic compounds possessing immunostimulating properties in vivo on the reactions of the immune splenocytes in vitro has been studied. It has been shown that the cell activity is determined by the medium ionic composition. In the medium with the optimal content of the bivalent cations the azacrown ethers decrease the intensity of the immune splenocytes reactions depending on the dose. In the media of the modified ionic composition the studied compounds in concentration 10 microM activate all the reactions of the spleen cells, in concentration 100 microM they suppress or do not change them.     

Composition of sugarcane waxes in rum factory wastes

Wastes produced during fermentation and distillation of crude sugarcane juice in rum factories were evaluated as a new source of waxes. The chemical composition of the crude wax extracted from adsorbat of the wastes on fuller's earth was studied by GC-mass spectrometry. Series of linear alkanes (C19-C33), and wax esters constitute the main components. In addition, phytosterols, triterpene methyl ethers, ethyl and methyl esters of fatty acids, and free fatty acids were found as minor components. Acid (predominance of C16 and C18) and alcohol portions (C26-C32) of the wax esters were analysed after saponification.     

Lipase-catalyzed conversions of trimethylsilyl ethers: deprotection, acetylation, epoxidation and one-pot-multi-step reactions

Unsaturated trimethylsilyl ethers are converted by lipase-catalyzed hydrolysis of ethyl acetate directly to alkenol acetates; the hydrolysis of diethyl carbonate yields unstable carbonic acid monoethylester, which deprotects trimethylsilyl ethers under mild conditions and without remaining acid. By the analogous lipase-catalyzed perhydrolysis of these esters with hydrogen peroxide, epoxyalkanol acetates and epoxyalkanols are obtained in one-pot reactions with selectivities of 90–97%. Using longer chain peroxy fatty acids, generated in-situ by lipase-catalyzed reaction of fatty acid and hydrogen peroxide, trimethylsilyl ethers are selectively (83–95%) epoxidized without removal of the protecting trimethylsilyl group.     

Hepatic monoacylglycerol acyltransferase: ontogeny and characterization of an activity associated with the chick embryo

Hepatic monoacylglycerol acyltransferase is expressed during the perinatal period in rats and guinea pigs and appears to be related temporally to the availability of fatty acids and to the development of hepatic steatosis. In order to determine when monoacylglycerol acyltransferase activity is expressed in an avian species, its ontogeny was investigated in chick liver total particulate preparations. In livers from 11- to 21-day-old chick embryos, monoacylglycerol acyltransferase specific activity was 34.5 +/- 8.1 nmol/min per mg of total particulate protein. The specific activity decreased 93% to 2.6 +/- 1.3 nmol/min per mg by the 6th day after hatching. The specific activities of fatty acid CoA ligase, diacylglycerol acyltransferase, and microsomal and mitochondrial glycerol-P acyltransferases changed comparatively little during this time period. In the embryos, the monoacylglycerol acyltransferase activity per liver rose 28-fold between the 11th and 21st day, corresponding exactly to the increase in liver total particulate protein during this time. Monoacylglycerol acyltransferase activity in other tissues was 25- to 115-fold lower than observed in liver. Optimal activity was measured using 25 microM palmitoyl-CoA and 50 microM sn-2-monooleoylglycerol. The activity with the 1- and 2-monooleoylglycerol ethers and 1-monooleoylglycerol was very low. In contrast to microsomes from rat liver, about 70% of the product with the 1- and 2-monooleoylglycerol ethers was triradylglycerol, suggesting that the diacylglycerol acyltransferase from chick liver can acylate acyl, alkylglycerols. The activity with sn-2-monooleoylglycerol amide was 12.5% of that observed with the corresponding 2-monooleoylglycerol suggesting that the ester bond is important; the 1-monooleoylglycerol amide was not a substrate.(ABSTRACT TRUNCATED AT 250 WORDS)     

Sugar ester synthesis by a mycelium-bound Mucor circinelloides lipase in a micro-reactor equipped with water activity sensor

The mycelium-bound Mucor circinelloides lipase was used for the synthesis of esters of saccharides and fatty acids in 37 ml reactor equipped with magnetic stirrer and water activity sensor. Either di-n-pentyl ether or the mixture of di-n-pentyl and petroleum ethers were applied as reaction media. Water activity sensor provided on-line monitoring of this parameter and control of continuous processes of ester synthesis. It was found that two natural antioxidants, i.e. carotene and astaxanthin activated this lipase in organic solvents that could be beneficial for the synthesis of esters of compounds sensitive to oxidation, e.g. polyunsaturated fatty acids.     

Lipid composition of activated sludge in a pilot plant for anaerobic ammonium oxidation

The lipid composition of the microbial community inhabiting activated sludge in a pilot reactor for the anaerobic oxidation of ammonium (anammox) at the Kur’yanovo Treatment Plant (Moscow) has been studied. The fatty acid composition is mostly based on common fatty acids C₁₄–C₁₈ (95%) with both normal and isomeric structures. The biomass of activated sludge was found to contain lipids with the so-called ladderane substances (ladder alcohols and fatty acids) that are common for anammox bacteria: C₂₀-[3]-lad-derane and C₂₀-[5]-ladderane alcohols and C₁₈- and C₂₀-[3]-ladderane and C₁₈- and C₂₀-[5]-ladderane acids. In addition, the native extract contained both simple and compound ethers of the above-mentioned substances with residues of phosphocholine, phosphoethanolamine, and phosphoglycerine. The spectra of the electron impact and tandem mass spectrometry of certain substances have been obtained and published for the first time.     

New biologically active substances from protozoa and an evaluation of their action]

Novel biologically active substances were obtained from nonpathogenic for humans and free-living protozoa: Crithidia oncopelti, Trypanosoma lewisi, and Astasia longa. There were studied conditions of biosynthesis, composition and biological activity of the total lipid fraction from the protozoa species, sucrose ethers and fatty acids, the latter were isolated from A. longa--(astazilide preparation), reserve beta-1,3 glucan from A. longa (astazian preparation), and fraction of surface glycophospholipids and peptides from Crithidia oncopelti (GLP preparation). Two of three preparations studied (astazilide and GLP) are the complexes of natural substances with certain composition. Conditions of the protozoa cultivation were developed to provide standardization of the complex composition. Division of the complexes into separate components decreased or abolished the biological activity. It was established that the substances studied modify biological reactions, that is exert a systemic effect. They may be used for inhibiting the growth of experimental tumors and preventing the metastatic spreading in tumor-carrier animals. The substances obtained belong to the group of nonspecific stimulators for cellular immunity which can be used in medicine, veterinary medicine, food industry, pharmacologic industry and cosmetology.     

Divinyl ether fatty acid synthesis in late blight-diseased potato leaves

We conducted a study of the patterns and dynamics of oxidized fatty acid derivatives (oxylipins) in potato leaves infected with the late-blight pathogen Phytophthora infestans. Two 18-carbon divinyl ether fatty acids, colneleic acid and colnelenic acid, accumulated during disease development. To date, there are no reports that such compounds have been detected in higher plants. The divinyl ether fatty acids accumulate more rapidly in potato cultivar Matilda (a cultivar with increased resistance to late blight) than in cultivar Bintje, a susceptible cultivar. Colnelenic acid reached levels of up to approximately 24 nmol (7 microgram) per g fresh weight of tissue in infected leaves. By contrast, levels of members of the jasmonic acid family did not change significantly during pathogenesis. The divinyl ethers also accumulated during the incompatible interaction of tobacco with tobacco mosaic virus. Colneleic and colnelenic acids were found to be inhibitory to P. infestans, suggesting a function in plant defense for divinyl ethers, which are unstable compounds rarely encountered in biological systems.     

Mutagenicities of glycidyl ethers for Salmonella typhimurium: relationship between mutagenic potencies and chemical reactivity

The lethal and mutagenic effects of ethyl, benzyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl and 9-anthrylmethyl glycidyl ethers on Salmonella typhimurium (TA100, TA1535, TA98 and TA1538) were investigated. LD30-value became smaller with an increase in compound hydrophobicity. The mutagenicities of these compounds in TA100 increased in the order: 1-naphthylethyl glycidyl ether less than 2-naphthylethyl glycidyl ether less than benzyl glycidyl ether less than 2-naphthylmethyl glycidyl ether less than 1-naphthylmethyl glycidyl ether less than 9-anthrylmethyl glycidyl ether. 1-Naphthylmethyl and 2-naphthylmethyl glycidyl ethers were mutagenic toward TA1535. In TA98, 1-naphthylmethyl and 9-anthrylmethyl glycidyl ethers showed mutagenic activity and 9-anthrylmethyl glycidyl ether was more mutagenic than 1-naphthylmethyl glycidyl ether. 9-Anthrylmethyl glycidyl ether was also active in TA1538. In the reaction of glycidyl ethers with deoxyguanosine and related compounds, glycidyl ethers attacked at only N-7 of guanine. The alkylation rates of glycidyl ethers toward guanine residues in DNA were determined and the exciplex-formation ability of 7-substituted guanines was studied. The reactivity of glycidyl ethers with guanine residues in DNA has not provided a sufficient explanation for the variation in mutagenic potencies of glycidyl ethers.     

Regulation of triglyceride biosynthesis in adipose and intestinal tissue

The synthesis of phosphatidic acid and di- and triglycerides via the glycerol-3-phosphate pathway is markedly inhibited by 2-monooleyl ether in microsomal and whole cell preparations obtained from adipose and intestinal tissue. Monoglycerides are also inhibitors under conditions in which their hydrolysis is minimized. A correlation between inhibition by, and the hydrolysis of, monoglycerides has been demonstrated. 2-Monooleyl ether is the most effective inhibitor of the several mono- and di- ethers and esters studied. The specificity of the inhibition of glycerol-3-phosphate acylation by 2-monoethers or 2-monoesters has been demonstrated because microsomal NADH- and NADPH-cytochrome c reductase activities were not significantly inhibited. The reported control mechanism for triglyceride biosynthesis is discussed in relation to the regulation of fatty acid uptake and release in adipose tissue and the absorption and metabolism of triglycerides by the intestinal mucosa.     

Transprotection of silyl ethers of nucleosides in FeCl3 based ionic liquids

Ionic liquid mediated deprotection of tert-butyldimethyl silyl (TBDMS) ethers derived from various primary and secondary alcohols have been studied and the reaction conditions optimized. Deprotection of the silyl ethers in FeCl3 based ionic liquids in presence of acetic anhydride yielded the acetate esters of the corresponding alcohols in good yields. The transprotection methodology was extended to the silyl ethers of nucleosides to yield the corresponding acetylated products.     

Enzymatic activity of chymopsin of various origin]

A number of enzymatic properties of fish pylochymopsin and bull chymopsin have been studied. Hydrolysis of synthetic ethers of N-benzoyl-L-tyrosine and N-benzoyl-L-arginine by these chymopsins depending at the time and concentration of preparations has been studied. It was found that bull chymopsin is the most active one. It was shown that concentrations of 2 to 6 micrograms/ml of bull chymopsin and of 15 to 20 micrograms/ml of fish enzyme were optimal for synthetic substrate BTME hydrolysis. The significant trypsin activity was revealed in the both preparations on a number of synthetic amides. In contrast to the bull chymopsin the treatment of fish pylochymopsin by TPCK did not completely remove the chymotryptic activity of pylochymopsin. It was shown that tryptic activity in the both preparations was completely removed with TLCK. The time and concentration dependence of the autolysis in both chymopsins has been studied. It should be noted that this process is negligible for fish pylochymopsin in contrast to bull chymopsin. Stabilization of both proteases in aqueous solution at room temperature has been studied. Stabilization of the chymopsins in solution is achieved by the addition of various protein preparations including casein and serum albumin. The degree of stabilization by these proteins was achieved at 2% concentration.     

Human urinary sulfatides in patients with sulfatidosis (metachromatic leukodystrophy)

The excretion of sulfatides in human urine was studied. 24-hr urine collections were filtered. Urinary glycolipids were extracted from the filter paper and fractionated on diethylaminoethyl cellulose and silicic acid columns, and by thin-layer chromatography. Fatty acids and long-chain bases were analyzed by gas-liquid chromatography of the corresponding esters and aldehydes. Glycosyl ceramide concentration was determined by gas-liquid chromatography of the trimethylsilyl ethers of the methyl glycosides. Normal females were found to excrete larger amounts of dihexosyl ceramides than males. Sulfatides were detected in all urine specimens. In sulfatidosis, a hereditary sulfatide storage disorder known as metachromatic leukcdystrophy, a large increase in sulfatide was readily apparent on a thin-layer chromatogram of the crude lipid extract. On comparing samples from normal individuals and patients with sulfatidosis, urinary sulfatide composition was remarkably similar to that previously reported in the kidney, including differences in fatty acid pattern. The determination of urinary sulfatides was a valuable confirmation of the deficiency in arylsulfatase A activity characteristic of sulfatidosis.     

Evidence for the existence of cholesteryl alk-1-enyl ethers in bovine and porcine cardiac muscle

Evidence is presented for the existence of cholesteryl alk-1-enyl ethers in bovine and porcine cardiac muscle. Several different fatty chains are present in the cholesteryl ethers, the major species having 16 and 18 carbon atoms. The cholesteryl alk-1-enyl ether concentration was found to be 0.08 and 0.01 micro moles/100 mg of neutral lipid in bovine and porcine cardiac muscle, respectively.     

Formation of oxylipins by CYP74 enzymes

Lipid peroxidation is common to all biological systems, both appearing in developmentally and environmentally regulated processes. Products are hydroperoxy polyunsaturated fatty acids and metabolites derived there from collectively named oxylipins. They may either originate from chemical oxidation or are synthesized by the action of various enzymes, such as lipoxygenases. Cloning of many lipoxygenases and other key enzymes metabolizing oxylipins revealed new insights on oxylipin functions, new reactions and the first hints on enzyme mechanisms. These aspects are reviewed with respect to metabolism of fatty acid hydroperoxides by an atypical P450 subfamily: the CYP74. Up to now this protein family contains three different enzyme activities: (i) allene oxide synthase leading to the formation of unstable allene oxides which react to ketol and cyclopentenone fatty acids, (ii) hydroperoxide lyase producing hemiacetals decomposing to aldehydes and ω-oxo fatty acids and (iii) divinyl ether synthase which forms divinyl ethers. Signalling compounds such as jasmonates, antimicrobial and antifungal compounds such as leaf aldehydes or divinyl ethers, and a plant-specific blend of volatiles including leaf alcohols are among their numerous products.     

Location of double bonds and cyclopropane rings in fatty acids by mass spectrometry

Electron-impact mass spectrometric procedures for locating the position of double bonds and cyclopropane rings in long-chain fatty acids are reviewed. Since unsaturation is not located directly by mass spectrometry, the properties of suitable derivatives are summarized. Epoxides are readily prepared from double bonds and on opening of the ring with various reagents useful derivatives are obtained, the most promising to date being hydroxymethoxy esters whose trimethylsilyl ethers give good mass spectra. Trimethylsilyl ethers of vicinal diols, prepared by direct hydroxylation, are recommended for the analysis of polyunsaturated fatty acid esters using combined gas chromatography-mass spectrometry. Oxymercuration-demercuration techniques are very convenient and one particular procedure can specifically locate unsaturation up to five carbons distant from the carboxyl group. An alternative approach enables the location of double bonds and cyclopropane rings in fatty acids by direct mass spectrometry of pyrrolidides. Cyclopropane rings can be positively located in fatty acid esters by mass spectrometry of isomeric ketones or methoxy derivatives prepared by chromium trioxide oxidation on poron trifluoride-catalysed methoxylation, respectively. A variety of other procedures are also considered and some guidelines are given for choosing a method to suit a particular unsaturated acid.     

A simple method for the synthesis of cholesteryl ethers

A novel method for the synthesis of cholesteryl ethers is described. The mesylates of fatty alcohols were treated with the sodium salt of cholesterol in toluene at 80 degrees C in the presence of anhydrous dimethyl formamide. The hexyl, tetradecyl, and oleyl cholesteryl ethers were synthesized in yields varying between 55 and 70%. Tritiated cholesteryl oleyl ether was also synthesized in good chemical (45%) and radiochemical (45%) yields.