Գանգուր ավելուկի սերմերում ճարպաթթուների քիմիական կազմի ուսումնասիրությունը

We have previously measured the distribution and pharmacokinetics of biosynthetically radiolabeled endotoxin of Salmonella typhimurium following intraperitoneal (IP) dosing (200μg/kg) in Sprague-Dawley rats. In our experiments, the fatty acid residues were labeled with (3)H and the glucosamine residues were labeled with (14)C. To predict the dynamics of endotoxin exposure, we developed a physiological-based pharmacokinetic model using our measured distribution results. The model was validated with published low-dose (30μg/kg) IP exposure results in rats. Endotoxin pharmacokinetics depended on dose and route. At high IP doses, absorption was followed by biphasic decay over 48h in plasma. There were tissue accumulations of the fatty acid and glucosamine residues in various target organs, including the brain. We also found that the glucosamine and fatty acid components separated in vivo about 3h after IP injection. At the lower IP dose, a smaller fraction of the dose was distributed to the tissues, with most of the dose remaining in the blood. Each component had its own dynamic behavior and target tissue distribution in the rat. The fatty acid components tended to remain in the brain stem, caudate nucleus, cerebellum, frontal cortex, hippocampus, and hypothalamus. Other organs (spleen, kidney, meninges, and choroid plexus) had similar biphasic distribution. The liver had the unique accumulation of both glucosamine and fatty acid residues.

Selective elimination of saturated fatty acid (FA) residues from vegetable oils (sesame, borage, olive, and sunflower) produces lower acylglycerols rich in unsaturated and polyunsaturated FA residues. Novozym® 435 releases greater amounts of saturated FA residues than unsaturated residues relative to other biocatalysts. Highest selectivity is obtained for 50 wt‐% Novozym® 435 with respect to the oil and [ethanol]/[FA] = 25. Under these conditions, 88–90% of saturated residues are released versus only 44–45% of unsaturated residues. Product acylglycerols have ratios of unsaturated to saturated residues of 21.5–23.0 relative to 5.22–4.73 for the precursor oils. Ethanolysis is faster with Novozym® 435. This biocatalyst is much less susceptible to inactivation by ethanol than other biocatalysts. However, in excess ethanol ([EtOH]/[FA] = 4.5–25), the rate and conversion both increased when the ethanol concentration decreased. The best combination of conversion and selectivity is obtained with 50 wt‐% Novozym® 435 and [ethanol]/[FA] = 4.5. Under these conditions, the product obtained in 1 h contains ca. 48% triacylglycerols, 24% diacylglycerols and 28% monoacylglycerols; the mol percentage of unsaturated FA residues is 12.3 times greater than that of saturated residues. The sn‐2 position is essentially free of saturated FA residues. After use for ten reaction cycles, Novozym® 435 retains 80% of its initial activity.

Interesterification and Acidolysis of Butterfat with Oleic Acid by Mucor Javanicus Lipase: Changes in the Pool of Fatty Acid Residues

Sophorolipid biosynthesis by Candida bombicola from industrial fatty acid residues

Comparison of global-minimum-energy conformations of phospholipids

The original lipid content of the thylakoid membranes of moss Marchantia polymorpha has been determined for the first time. In particular, the content of SQDG is almost 3 times higher than those for both of the other classes. The ratios for DGDG and MGDG are just a little bit lower than those for green algae, but almost 2 times less than those for plants. The distribution of unsaturated bonds has changed in C18 ‐residues of fatty acids. The total content of C18‐residues in thylacoid lipids have been almost the same but the content of C18:1, C18:2 and C18:3 are altered in the fractions of DGDG, PG and PE. The light stress produces only the quantitative, but no qualitative, changes of the thylakoid lipid composition. The properties of the thylakoid lipids and corresponding fatty acids in the monolayers at the liquid/gas interfaces have been studied. The changes in distribution of unsaturated bonds in C18 residues of fatty acids at light stress have been confirmed by Langmuir method.

Partial syntheses of mixed functional phorbol- (12,13) -diesters with acetic acid and long-chain fatty acids at the α-glycol group of phorbol are described. Six of the phorbol diesters synthesized are identical with the irritant and tumorpromoting acetyl-phorbol-acylates A1 — A4, B4 and B7 isolated from croton oil. The isomeric phorbol- (12,13) -diesters A2 and B7 as well as A3 and B4 are pairs of positional isomers regarding the fatty acid residues. It may be generalized for all the eleven phorbol· (12,13) -diesters isolated so far from croton oil that compounds of the A group carry the long-chain fatty acid residue at C-13 and the short chain fatty acid residue at C-12. Compounds of the B group show inverse positions of these fatty acid residues. Isomeric phorbol-diesters of the types A and B may be differentiated by their Rf values in thin layer chromatography, their IR and mass spectra as well as the melting points of their 20- [4'-nitrophenylazobenzoic acid- (4)] - esters. Via the synthetic routes described phorbol- (12,13) -diesters with defined chemical structure are now easily accessible.

Mechanism of thiyl radical-catalyzed isomerization of unsaturated fatty acid residues in homogeneous solution and in liposomes

Formation of lysophospholipids from unsaturated phosphatidylcholines under the influence of hypochlorous acid

Nicotinoyl derivatives were used for the investigation of the structure of diacylglycerols with two different fatty acid residues by gas chromatography-mass spectrometry (GC-MS). Their electron ionisation mass spectra reveal the structures of diacid diacylglycerols in greater detail than the mass spectra of other diacylglycerol derivatives. The exact structure of the fatty acid alkyl chains, such as double bond and methyl branching positions, can be determined by characteristic features in fragmentation patterns which are induced by the pyridine nucleus. Besides, determination of fatty acid position in the glycerol backbone of diacid 1,2-diacylglycerols is simple. Caused by the two nicotinoyl-induced fragmentation patterns reflecting each of the two fatty acid residues, the mass spectra of diacid diacylglycerol derivatives are more complex than those of monoacid diacylglycerol derivatives. Since some of the diagnostic ions occur at identical masses, structural interpretation of the spectra may be critical in certain cases.

Menhaden oil, a rich source of n-3 fatty acids, was interesterified with conjugated linoleic acid (CLA) in a reaction medium composed solely of substrates and either free or immobilized commercial lipase preparations. Of five lipases tested, an immobilized preparation from Mucor miehei provided the fastest rate of incorporation of CLA into fish oil acylglycerols; however, and as observed with most of the lipases utilized, a significant proportion of the n-3 fatty acid residues were liberated in the process. A soluble lipase from Candida rugosa converted free CLA to acylglycerol residues while leaving the n-3 fatty acid residues virtually untouched. Even though the reaction rate was slower for this enzyme than for the other four lipase preparations, the specificity of the free C. rugosa lipase gives it the greatest potential for commercial use in preparing fish oils enriched in CLA residues but still retaining their original n-3 fatty acid residues.

Seed fatty acids composition of Lathyrus nissolia L., Lathyrus hirsutus L., Pisum sativum L. var. arvense (L.) Poiret., Onobrychis montana DC. subsp. cadmea (Boiss.) P.W.Ball., Trigonella monantha C.A.Mey. subsp. monantha, Trigonella foenum-graceum L. were analyzed by gas chromatography of the methyl esters of their fatty acids. The fatty acid composition of the studied taxa were found as identical qualitatively, but some quantitative differences were determined in interspecific and intergenus level. The fatty acid composition of studied plants showed different saturated and unsaturated fatty acid concentrations. The major fatty acids were found to be linoleic acid (11.94-53.09%), linolenic acid (7.70-47.05%), oleic acid (0.00-28.01%), palmitic acid (12.40-26.14%) and stearic acid (2.82-10.25%); while other fatty acids were found in minor percentages. As a result, in this research we detected that all taxa had the higher total unsaturated fatty acid (UFA) (68.11-80.67%) than saturated fatty acid (SFA) (19.33-31.89%) amounts. The higgest UFA detected to Trigonella monantha subsp. monantha (80.67%), lowest to Onobrychis montana DC. subsp. cadmea (68.11%). In this study, palmitic and stearic acid were found in the major saturated fatty acids; while oleic, linoleic and linolenic acids were found to be the major unsaturated fatty acids. Chemotaxonomic implications of the components of the studied plant taxa are discussed and the main components could be used as a chemotaxonomical marker.

The glycoinositol phospholipid membrane anchor of human erythrocyte acetylcholinesterase (EC 3.1.1.7) contains a novel inositol phospholipid which in this and the accompanying paper (Roberts, W.L., Santikarn, S., Reinhold, V.N., and Rosenberry, T.L. (1988) J. Biol. Chem 263, 18776-18784) is shown to be a plasmanylinositol that is palmitoylated on the inositol ring. The inositol phospholipid was radiolabeled with the photoactivated reagent 3-(trifluoromethyl)-3-(m-[125I] iodophenyl)diazirine and characterized by various chemical and enzymatic cleavage procedures whose products were analyzed by thin layer chromatography and autoradiography or gas chromatography. Acidic methanolysis of human erythrocyte acetylcholinesterase (Ehu AChE) revealed 18:0 and 18:1 alkylglycerols (0.55 and 0.20 mol/mol AChE, respectively). Acetolysis was shown by TLC to release alkylacylglycerol acetates from Ehu AChE. Analysis by gas chromatography revealed that 83% of the alkylacylglycerol acetates contained an 18:0 or 18:1 1-alkyl group and a 22:4 (n - 6), 22:5 (n - 3), or 22:6 (n - 3) 2-acyl group. The inositol phospholipid is linked to the anchor by a glucosamine in glycosidic linkage, and deamination with nitrous acid cleaved the glycosidic linkage and released the phospholipid. The deamination and acetolysis products from Ehu AChE were purified by high performance liquid chromatography, and fatty acid analysis following acidic methanolysis of the purified products revealed that 2 fatty acid residues were associated with the deamination product and only one with the alkylacylglycerol acetolysis product. The other fatty acid residue was primarily palmitate and was indicated to be in ester linkage to an inositol hydroxyl(s). This linkage was shown to be responsible for the resistance of the inositol phospholipid to cleavage by Staphylococcus aureus phosphatidylinositol-specific phospholipase. Deacylation of the inositol phospholipid deamination product by treatment with base removed this palmitoyl group and facilitated release of alkyl- and alkylacylglycerol species by phosphatidylinositol-specific phospholipase C with concomitant formation of inositol 1-phosphate. In contrast, digestion of Ehu AChE with a recently reported anchor-specific phospholipase D resulted in release of plasmanic acids from the intact palmitoylated plasmanylinositol.

Mice require testicular glycosphingolipids (GSLs) for proper spermatogenesis. Mutant mice strains deficient in specific genes encoding biosynthetic enzymes of the GSL pathway including Galgt1 (encoding GM2 synthase) and Siat9 (encoding GM3 synthase) have been established lacking various overlapping subsets of GSLs. Although male Galgt1-/- mice are infertile, male Siat9-/- mice are fertile. Interestingly, GSLs thought to be essential for male spermatogenesis are not synthesized in either of these mice strains. Hence, these GSLs cannot account for the different phenotypes. A novel class of GSLs was observed composed of eight fucosylated molecules present in fertile but not in infertile mutant mice. These GSLs contain polyunsaturated very long chain fatty acid residues in their ceramide moieties. GSLs of this class are expressed differentially in testicular germ cells. More importantly, the neutral subset of this new GSL class strictly correlates with male fertility. These data implicate polyunsaturated, fucosylated GSLs as essential for spermatogenesis and male mouse fertility.

Lipo-alkaloid (LA) is a kind of C19 -norditerpenoid alkaloid in Aconitum species, which usually contains an aconitane skeleton and one or two fatty acid residues. To qualify and quantify the fatty acids and lipo-alkaloids in Aconitum carmichaelii. An ultra-high performance liquid chromatography-triple quadrupole-mass spectrometry (UHPLC-QQQ-MS) method was established to quantify LAs, while the free fatty acids were identified by gas chromatography-mass spectrometry (GC-MS) and ultra-high performance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UHPLC-Q-TOF-MS). Six major LAs (1-6) containing linoleic, palmitic, and oleic acid residues as side chains were quantified. Eighteen fatty acids were determined by GC-MS, and 15 were detected as the side chains of LAs. The LAs containing these 15 fatty acid residues accounted for about a third of the total identified LAs. Moreover, the contents of linoleic, palmitic, and oleic acids were highest. In addition, 12 oxygenated fatty acids were also identified by UHPLC-Q-TOF-MS for the first time. The positive correlation between free fatty acids and LAs in A. carmichaelii indicated that the types and contents of LAs were influenced by free fatty acids.