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[Stability of the fatty acid composition of actinomycetes]. Konova I V,Rudakova L M,Pan'kina O I Mikrobiologiia The stability of fatty acid composition of total extractable lipids was studied in Streptomyces cultures. The type of fatty acid composition typical of the Streptomyces genus remains stable when the actinomycetes were grown as submerged cultures in various synthetic media: saturated fatty acids with methyl branching in the chain predominated in all of the cases, and fatty acids with an uneven number of carbon atoms in the chain prevailed in most of the cases. Fatty acids with the anteiso structure predominated among the acids with a branched chain, amounting to more than a half of the latter and reaching sometimes 50% of the total fatty acid content. Methyl branchings were located in the anteiso position in fatty acids with an uneven number of carbon atoms, and in the iso position in fatty acids with an even number of carbons. Unsaturated fatty acids were found as a minor component.
Reactions of Cl atoms with alkyl esters: kinetic, mechanism and atmospheric implications. Ifang Stefanie,Benter Thorsten,Barnes Ian Environmental science and pollution research international Rate coefficients have been measured for the reaction of Cl atoms with a series of alkyl esters at 298 ± 2 K and atmospheric pressure in a large volume photoreactor using the relative kinetic technique. The kinetic data have been used in conjunction with other literature studies on the reactions of Cl atoms with esters to revise the existing values for ester substituent factors in a structure activity relationship (SAR) for Cl reactions. Product studies are reported for the reactions of Cl atoms with isopropyl ethanoate and methyl-2-methyl-propanoate under NO x -free conditions. These studies highlight the types of products that can be expected when oxidation occurs at R groups on the acyl (-C(O)OR) and oxy (RC(O)O-) sides of the ester functionality where R is a straight or branched chain alkyl entity. Possible atmospheric repercussions of the atmospheric chemistry of esters are considered. 10.1007/s11356-014-2913-9
[Changes in amino acid and fatty acid contents as well as activity of some related enzymes in apple fruit during aroma production]. Nie Lan-Chun,Sun Jian-She,Di Bao Zhi wu sheng li yu fen zi sheng wu xue xue bao = Journal of plant physiology and molecular biology Aroma volatiles from apple (Malus domestica Borkh. var. Starkrimson) fruit at different stages of maturity were collected by solid adsorbent-Tenax-GC and determined by thermodesorption and GC-MS. Production of propyl acetate, butyl acetate, ethyl 2-methyl-butanoate and total ester volatiles and changes in concentration of the precursors of aroma biosynthsis--free amino acids and fatty acids and activities of lipoxygenases (LOX) and alcohol acetyltransferase (AAT) in apple fruits during ripening were studied. The results showed that propyl acetate and total esters were very low when the endogenous ethylene formation of the fruit was very low. At the stage of the increase in ethylene production, the rate of formation of propyl acetate and total esters increased. Butyl acetate appeared at the beginning of ethylene rise and increased thereafter. Ethyl 2-methyl-butanoate was produced at the beginning of climacteric stage and then increased sharply (Figs.1). These facts suggest that the aroma production is closely related to ethylene production. Among the 14 free amino acids detected in fruit, isoleucine which is considered to be the biosynthetic precursor of some branched chain esters showed a great increase during fruit ripening while the others decreased or remained stable (Table 1). The accumulation of isoleucine suggested that isoleucine supply in fruit may not limit the biosynthesis of esters with branched chain alkyl groups. Concentrations of free fatty acids such as palmitic, linolenic, oleic, linoleic, stearic acids increased before the increase of aroma production, decreased with the increase of aroma production and showed an increase at postclimacteric stages (Fig.2). LOX activity increased at climacteric stages and declined rapidly thereafter. AAT activity increased sharply at the early stage of fruit maturity when the aroma was very low and remained at a stable high level during fruit ripening (Fig.3) indicating that the AAT activity is not the limiting factor for aroma formation in apple fruit.
Lipophilic statins suppress cytotoxicity by freshly isolated natural killer cells through modulation of granule exocytosis. Tanaka Toru,Porter Cynthia M,Horvath-Arcidiacono Judith A,Bloom Eda T International immunology NK cells, a component of the innate immune system, provide a first line of defense against viral infections and malignancies, interact with the adaptive immune system and have a role in rejection of allogeneic bone marrow transplants and solid allo- and xenotransplants. Immunoregulatory activity by the anti-hypercholesterolemia agents, 3-hydroxy-3-methyl-glutaryl Coenzyme A (HMG-CoA) reductase inhibitors, known as statins, has recently been reported. We analyzed the effects of three statins on human NK cell cytotoxicity. Two lipophilic statins (simvastatin and fluvastatin) suppressed the cytotoxic activity of fresh and IL-2-stimulated NK cells, while pravastatin, a hydrophilic statin, did not. Suppression was not associated with changes in intracellular perforin, granzyme A or granzyme B levels, or with changes in expression of leukocyte function-associated antigen-1, an integrin known to regulate NK activity and reported to be altered by statin treatment. Decreased cytotoxicity was associated with decreased CD107a surface expression, indicating that the exocytosis pathway was compromised by simvastatin and fluvastatin but not by pravastatin. Mevalonate, the immediate downstream product of HMG-CoA reductase, partially reversed the effect of lipophilic statins on cytotoxicity and CD107a expression. Lipophilic statins also suppressed the release of the granule component, granzyme B, by IL-2-activated NK cells following stimulation with K562. That lipophilic statins suppress NK cell activity through inhibition of the exocytosis pathway suggest an additional potential role for statins in inhibition of transplantation responses. 10.1093/intimm/dxl133
Gangliosides of bovine buttermilk. Isolation and characterization of a novel monosialoganglioside with a new branching structure. Takamizawa K,Iwamori M,Mutai M,Nagai Y The Journal of biological chemistry Bovine buttermilk was found to contain 0.92 mumol of lipid-bound sialic acid/g dry weight. On ganglioside mapping, at least seven gangliosides were detected, and the structures of the five major molecules were determined by degradation with exoglycosidases and methylation analysis. GM3, GD3, and GT3 were found to comprise 80% of the total gangliosides. The other two gangliosides had a new core structure with a branched oligosaccharide chain. One was a novel monosialoganglioside with a 2----6 linked sialic acid residue with the following structure: (Formula, see text) There were 41 nmol of this ganglioside/g of buttermilk (4.5% of total gangliosides). The other was a trisialogangliosides with the above new core structure.
Combining results of two GC separations partly achieves determination of all cis and trans 16:1, 18:1, 18:2 and 18:3 except CLA isomers of milk fat as demonstrated using Ag-ion SPE fractionation. Kramer John K G,Hernandez Marta,Cruz-Hernandez Cristina,Kraft Jana,Dugan Michael E R Lipids Milk fat is a complex mixture of geometric and positional isomers of monounsaturated and polyunsaturated, including short-, long- and branch-chain fatty acids (FAs). There has been partial success to resolve this mixture of FAs using different GC temperature programs, or a combination of GC isothermal and temperature programs. To overcome the problem associated with overlapping isomers prior silver-ion separation was recommended. However, this procedure is time consuming and not practical for routine analysis. In addition, previous methods focused mainly on the trans and cis isomers of 18:1. The present method takes advantage of differences in the relative elution times between different types of FAs. The method involved analyzing each milk fat using the same highly polar 100-m capillary column and GC instrument, and conducting two separations using temperature programs that plateau at 175 and 150 degrees C. The relative shift among the geometric and positional isomers at these two temperature settings was enough to permit identification of most of the trans and cis 16:1, 18:1 and 20:1, the c/t-18:2 and the c/c/t-18:3 isomers found in milk fat. The identity of these FAs was confirmed by prior separation of the total fatty acid methyl esters (FAMEs) of milk fat using Ag(+)-SPE columns, and comparing the fractions to the total milk fat. The Ag(+)-SPE technique was modified to obtain pure saturated, trans- and cis-monounsaturated and diunsaturated FAMEs. By combining the results from these two separate GC analyses, knowing the elution order, it was possible to determine most of the geometric and positional isomers of 16:1, 18:1, 20:1, 18:2 and 18:3 without a prior silver-ion separation. Only few minor FAs could not be resolved, notable the conjugated linoleic acid isomers that still required the complimentary Ag(+)-HPLC separation. The two GC temperature programs have been successfully used to routinely analyze most FA isomers in total milk and beef fats in about 200 min without the use of prior silver-ion separations. 10.1007/s11745-007-3143-4
Effect of farming system and cheesemaking technology on the physicochemical characteristics, fatty acid profile, and sensory properties of Caciocavallo Palermitano cheese. Bonanno A,Tornambè G,Bellina V,De Pasquale C,Mazza F,Maniaci G,Di Grigoli A Journal of dairy science Caciocavallo Palermitano is a typical stretched-curd cheese that has been produced over the centuries in Sicily according to traditional cheesemaking technology and using raw milk from autochthonous cow breeds reared at pasture. The objective of this experiment was to evaluate the effects of the farming system and processing technology on the characteristics of Caciocavallo Palermitano cheese, with particular regard to the fatty acid profile. The farming system was either extensive, using autochthonous cows fed a pasture-based diet, or intensive, with specialized dairy cow breeds fed mainly hay and concentrate. The cheese-processing technology was either artisanal, using traditional wooden tools and endemic lactic bacteria, or advanced, using modern steel equipment and selected lactic bacteria. Twelve Caciocavallo Palermitano cheeses, 3 from each of the 4 experimental theses (2 farming systems × 2 cheesemaking technologies), were obtained and aged for 1, 30, 60, and 120 d. Milk of origin and cheeses were analyzed for the main chemical and rheological parameters. Fatty acids were methylated in lyophilized cheese and analyzed by gas chromatography. Sensory analysis was carried out by trained panelists. The PROC GLM of SAS 9.1.2 (SAS Institute Inc., Cary, NY) was used for the statistical analysis. The physical, chemical, and sensory characteristics of Caciocavallo Palermitano cheese were influenced more by the farming system than by the cheesemaking technology. Compared with cheese produced through intensive farming, cheese from extensive farming was richer in polyunsaturated, n-3, and odd- and branched-chain fatty acids, as well as in conjugated linoleic acid (cis-9,trans-11 C18:2), with accompanying improved human health benefits. The cheesemaking technology produced variation in the evolution of proteolysis during aging, due presumably to the different active microflora, which influenced the sensory profile of the resulting cheese. Indeed, cheese produced by artisanal manufacturing was described as less "bitter" and more "piquant" than cheese produced through the advanced process. 10.3168/jds.2012-5973
Both total chain length and position of dimethyl-branching effect the myocardial uptake and retention of radioiodinated analogues of 15-(p-iodophenyl)-3,3-dimethylpentadecanoic acid (DMIPP). Knapp F F,Goodman M M,Kirsch G,Reske S N,Kropp J,Biersack H J,Ambrose K R,Lambert C R,Goudonnet A Annals of nuclear medicine Introduction of geminal dimethyl-branching into the 3-position of 15-(p-iodophenyl) pentadecanoic acid (IPPA) significantly delays myocardial clearance in rats and dogs following intravenous administration. Several new analogues of DMIPP have been synthesized and evaluated in fasted rats. The effects of both the position of dimethyl-branching and the total chain-length of 3, 3-dimethyl analogues on heart uptake and clearance kinetics have been studied. In the first series of compounds, two methyl groups were introduced into the 3-, 4-, 6-, or 9- position. Tissue distribution studies of the 15-(p-[I-125] iodophenyl)-analogues demonstrated that the position of dimethyl-branching is an important factor affecting both myocardial specificity and retention. The [I-125] labeled 3,3- and 4,4-DMIPP analogues showed higher myocardial uptake and faster blood clearance than the 6,6- and 9,9-DMIPP analogues [heart, % dose/gm heart: blood), 30 min: 3,3-DMIPP = 5.06 (12:1); 4,4-DMIPP = 8.03 (16.7: 1); 6,6-DMIPP = 2.26 (3.1:1); 9,9-DMIPP = 3.06 (2.77)]. In the second series, the effects of total fatty acid chain length were evaluated with 3,3-dimethyl-substituted analogues with C11, C12, C13, C14, C15, and C19 chain lengths. The C14 and C15 chain length analogues showed the best properties [global heart: blood ratios): 30 min: C11, 0.70 (0.82); C12, 1.25 (0.68); C13, 0.47 (0.90); C14, 1.63 (3.54); C15, 5.06 (12); C19. 1.29 (0.82). These detailed studies have demonstrated that both total chain length and the position of geminal dimethyl-branching are important structural parameters which affect myocardial specificity and retention of omega-(p-iodophenyl)-substituted fatty acid analogues and that 3,3-DMIPP and 4,4-DMIPP are the best candidates with optimal properties for further study. 10.1007/bf03165050
Herbidospora yilanensis sp. nov. and Herbidospora daliensis sp. nov., from sediment. Tseng M,Yang S-F,Yuan G-F International journal of systematic and evolutionary microbiology Two actinomycete strains, 0351M-12(T) and 0385M-1(T), were isolated from sediment samples collected from Yilan County and Dali City in Taiwan, respectively. The two isolates displayed characteristics which were similar to those of the genus Herbidospora. They both produced branched and unfragmented substrate mycelia, and aerial hyphae were not produced on Bennett's, glucose-asparagine, Hickey-Tresner, sucrose-nitrate, yeast extract-malt extract, or inorganic salts-starch agars. Short spore-chains were borne on the tips of sporophores arising from the substrate mycelia on oatmeal and oatmeal-nitrate agars. The spore chains contained 10-20 non-motile, smooth-surfaced, oval spores. Galactose, glucose, mannose and madurose were the whole-cell sugars in both strains and meso-diaminopimelic acid was present in their peptidoglycans. The phospholipid pattern was PIV. The predominant menaquinone was MK-10(H(4)) in both strains. Mycolic acids were not detected. Major cellular fatty acids were iso-C(16 : 0) and 10-methyl C(17 : 0). The DNA G+C contents of the two new isolates were 70.6 mol% (0351M-12(T)) and 70.7 mol% (0385M-1(T)), respectively. The relatedness between the isolates and Herbidospora cretacea NBRC 15474(T) was 40.7-48.5 %. The value of DNA-DNA hybridization between strain 0351M-12(T) and strain 0385M-1(T) was 53.6-54.9 %. These two isolates could also be distinguished from each other and from H. cretacea NBRC 15474(T) by differences in several phenotypic characteristics. We therefore propose the names Herbidospora yilanensis sp. nov. and Herbidospora daliensis sp. nov. for these novel bacteria, with strains 0351M-12(T) (=FIRDI 003(T) =BCRC 16875(T) =LMG 24337(T)) and 0385M-1(T) (=FIRDI 004(T) =BCRC 16876(T) =LMG 24336(T)) as the type strains, respectively. 10.1099/ijs.0.014803-0
Serinicoccus marinus gen. nov., sp. nov., a novel actinomycete with L-ornithine and L-serine in the peptidoglycan. Yi Hana,Schumann Peter,Sohn Kyounghee,Chun Jongsik International journal of systematic and evolutionary microbiology A Gram-positive bacterial strain containing L-ornithine as the diagnostic diamino acid was isolated from a sea-water-sample from the East Sea, Korea. A phylogenetic analysis based on 16S rRNA gene sequences showed that strain JC1078T represents a phyletic line within the suborder Micrococcineae of the order Actinomycetales, adjacent to the genus Ornithinimicrobium. The highest sequence similarity values to the isolate were observed against Ornithinimicrobium humiphilum (94.3 %) and Kytococcus sedentarius (94.1 %). The strain was strictly aerobic and moderately halophilic with optimal growth at 2-3 % (w/v) NaCl. Cells were non-motile, non-sporulating and coccoid-shaped. The cell wall contains L-ornithine, glutamic acid, alanine, glycine and serine. The major menaquinone was MK-8(H4). The predominant cellular fatty acids were of the iso- and anteiso-methyl-branched types. The polar lipids were phosphatidylglycerol, diphosphatidylglycerol, phosphatidylinositol and an unknown glycolipid. The acyl type of the glycan chain of peptidoglycan is acetyl. The DNA G + C content was 72 mol%. The combination of physiological, biochemical and chemotaxonomical data clearly separated the marine isolate from other members of the suborder Micrococcineae. On the basis of polyphasic evidence, it is proposed to classify strain JC1078T in a novel genus and species, for which the name Serinicoccus marinus gen. nov., sp. nov. is proposed. The type strain is JC1078T (= IMSNU 14026T = KCTC 9980T = DSM 15273T). 10.1099/ijs.0.03036-0
The phenolic mycoside of Mycobacterium ulcerans: structure and taxonomic implications. Daffé M,Varnerot A,Lévy-Frébault V V Journal of general microbiology Mycobacterium ulcerans and some pathogenic mycobacterial species elaborate wax A consisting of related long-chain beta-diol components (phthiocerol and related compounds) esterified by multimethyl-branched fatty acids. With the exception of M. ulcerans, wax A-containing mycobacteria also synthesize glycosylated phenol phthiocerol diester and related compounds: the so-called phenolic mycosides. In a deliberate effort to characterize this latter class of compounds in M. ulcerans, 20 strains were examined. Phenolic mycosides were found in two strains. Application of chemical analyses, including one- and two-dimensional NMR spectroscopy, allowed the structural elucidation of glycolipids identified as 3-O-methyl-alpha-L-rhamnosyl phenol phthiocerol diphthioceranate investigators. As phenolic mycosides are highly species-specific molecules, this finding stresses the close phylogenetic link between M. marinum and M. ulcerans. Incidentally, a survey of the mycolate content of M. ulcerans showed that methoxymycolate could not be detected in three strains. 10.1099/00221287-138-1-131
Desertiactinospora gelatinilytica gen. nov., sp. nov., a new member of the family Streptosporangiaceae isolated from the Karakum Desert. Saygin Hayrettin,Ay Hilal,Guven Kiymet,Cetin Demet,Sahin Nevzat Antonie van Leeuwenhoek A novel, Gram-positive, spore-forming actinomycete, designated strain 7K107, was isolated from a soil sample collected from the Karakum Desert, Turkmenistan. Strain 7K107 forms extensively branched substrate mycelia and aerial mycelia which differentiate into short chains of spores. The novel strain contains meso-diaminopimelic acid as the diagnostic wall amino acid and glucose, galactose, madurose and ribose as whole cell sugars. The predominant menaquinones were identified as MK-10(H), MK-9(H), MK-10(H) and MK-9(H). The polar lipids were found to be diphosphatidylglycerol, phosphatidylethanolamine, glycolipids, phospholipids, unidentified lipids and an aminolipid. Major fatty acids were identified as C 10-methyl and C. The G + C content of the genomic DNA was determined to be 70.8%. Phylogenetic analysis based on 16S rRNA gene sequences showed that the strain is a member of the family Streptosporangiaceae. The strain shares high 16S rRNA gene sequence similarity (96.2%) with Sphaerisporangium album YIM 48782 followed by Sphaerisporangium corydalis NEAU-YHS15 (96.0%) and Nonomuraea candida HMC10 (95.9%). However, phylogenetic analyses based on 16S rRNA and gyrB genes, as well as whole genome comparison, confirmed the distinctiveness of the strain from closely related type strains of the genera Sphaerisporangium, Nonomuraea and Thermostaphylospora. On the basis of morphological, chemotaxonomic and phylogenetic as well as genomic analyses, strain 7K107 is concluded to represent a new genus within the family Streptosporangiaceae, for which the name Desertiactinospora gelatinilytica gen. nov., sp. nov is proposed. The type strain of D. gelatinilytica is 7K107 (= DSM 107423 = JCM 32585 = KCTC 49108). 10.1007/s10482-018-1169-7
New lubricants from vegetable oil: cyclic acetals of methyl 9,10-dihydroxystearate. Filley Jonathan Bioresource technology Potential new lubricants and fuel lubricity enhancers have been prepared from methyl 9,10-dihydroxystearate and long chain aldehydes to form the corresponding cyclic acetals. These materials are oils down to low temperatures, as compared to symmetric ketals derived from the same diol, which are waxes at room temperature. The acetals form in an equilibrium reaction (Keq approximately 60) which suggests they will be stable as fuel additives. The viscosities of the new oils are close to those predicted for normal paraffins with the same number of non-hydrogen atoms, but the acetal structure has subtle effects on viscosity as compared to branched alkanes. Acetals with long alkyl branches maintain higher viscosity on a molecular weight basis compared to branched alkanes. The qualitative relationship between branch length and viscosity is discussed. These acetals are potential candidates for novel biobased lubricants. 10.1016/j.biortech.2004.06.017
Stereochemical studies on the beta-oxidation of valproic acid in isolated rat hepatocytes. Shirley M A,Hu P,Baillie T A Drug metabolism and disposition: the biological fate of chemicals Stereochemical aspects of the biotransformation of valproic acid (VPA) to four compounds believed to represent products of mitochondrial beta-oxidation, viz. delta 2(E)-VPA, delta 3-VPA, 3-hydroxy-VPA, and 3-oxo-VPA, were examined in freshly isolated rat hepatocytes. Following incubation of the individual enantiomers of [5-13C]VPA and analysis of products by GC/MS techniques, it was possible to determine for each metabolite the relative populations of molecules that had been formed by oxidation on the pro-R vs. the pro-S propyl group of the drug. Metabolism was found to exhibit a slight preference (approximately 1.3:1) for attack on the pro-S side-chain for all four compounds, consistent with the hypothesis that this group shares a common metabolic origin. In contrast, the hepatotoxic terminal olefin, delta 4-VPA, was formed with marked enantiotopic differentiation (approximately 3.8:1) favoring the pro-R side-chain. The reason for the surprisingly low stereo-selectivity displayed by the products of beta-oxidation was investigated with the aid of [3-2H] delta 2(E)-VPA as metabolic substrate. Following incubation with rat hepatocytes, 35% of the substrate remaining after 2 hr was found to have been isomerized to [3'-2H] delta 2(E)-VPA. Because delta 2(E)-VPA is known to be formed from VPA-CoA through the action of 2-methyl-branched-chain acyl-CoA dehydrogenase, it is proposed that the three-carbon side-chains of both parent drug and delta 2(E)-VPA are interconverted as a consequence of reversibility in the second half-reaction of this enzymatic process.
Evidence that multifunctional protein 2, and not multifunctional protein 1, is involved in the peroxisomal beta-oxidation of pristanic acid. Dieuaide-Noubhani M,Asselberghs S,Mannaerts G P,Van Veldhoven P P The Biochemical journal The second (enoyl-CoA hydratase) and third (3-hydroxyacyl-CoA dehydrogenase) steps of peroxisomal beta-oxidation are catalysed by two separate multifunctional proteins (MFPs), MFP-1 being involved in the degradation of straight-chain fatty acids and MFP-2 in the beta-oxidation of the side chain of cholesterol (bile acid synthesis). In the present study we determined which of the two MFPs is involved in the peroxisomal degradation of pristanic acid by using the synthetic analogue 2-methylpalmitic acid. The four stereoisomers of 3-hydroxy-2-methylpalmitoyl-CoA were separated by gas chromatography after hydrolysis, methylation and derivatization of the hydroxy group with (S)-2-phenylpropionic acid, and the stereoisomers were designated I-IV according to their order of elution from the column. Purified MFP-1 dehydrated stereoisomer IV but dehydrogenated stereoisomer III, so by itself MFP-1 is not capable of converting a branched enoyl-CoA into a 3-ketoacyl-CoA. In contrast, MFP-2 dehydrated and dehydrogenated the same stereoisomer (II), so it is highly probable that MFP-2 is involved in the peroxisomal degradation of branched fatty acids and that stereoisomer II is the physiological intermediate in branched fatty acid oxidation. By analogy with the results obtained with the four stereoisomers of the bile acid intermediate varanoyl-CoA, stereoisomer II can be assigned the 3R-hydroxy, 2R-methyl configuration. 10.1042/bj3250367
Branched long-chain bases from the bivalve Corbicula sandai. Sugita M,Itasaka O,Hori T Chemistry and physics of lipids Long-chain bases were liberated from a crude mixture of sphingolipids from whole tissue of the fresh-water bivalve C. sandai, and conversion of the bases into N-acetyl-0-trimethylsily derivatives was accomplished. The derivatized bases were analyzed by combined gas-liquid chromatography and mass spectrometry. A portion of the sphingolipids was subjected to catalytic hydrogenation from whch saturated long-chain bases (sphinganines) were obtained. The saturated bases were oxidized with lead tetra-acetate and the aldehydes produced were analyzed by gas-liquid chromatography. The aldehydes were further oxidized to acids with silver oxide, the resulting fatty acids methylated and also analyzed by gas-liquid chromatography. By these analyses, altogether five long-chain bases were identified, consisting of hexadeca-4-sphingenine (15%), heptadeca-4-sphingenine (2%), iso-octadeca-4-sphingenine (13%), octadeca-4-sphingenine (39%) and anteiso-noadeca-4-sphingenine (31%). So far no branches have been found in shellfish spingolipid long-chain bases.
[Biochemistry of the developmental cycle of Triatoma infestans. VII. Lipid composition of the cuticle surface extracted with hexane]. Juárez P,Brenner R R,Labayén I L,Gros E G Acta physiologica et pharmacologica latinoamericana : organo de la Asociacion Latinoamericana de Ciencias Fisiologicas y de la Asociacion Latinoamericana de Farmacologia The lipid composition of Triatoma infestans (vinchuca) epicuticle was studied. The insect lipids were extracted with hexane and fractionated by chromatography. Long chain fatty alcohols, hydrocarbons, waxes, triacylglycerols, diacylglycerols, free fatty acids, cholesterol, cholesterol esters and monoacylglycerols were detected. The composition of fatty acids, hydrocarbons and alcohols was studied by gas-liquid chromatography and mass spectrography. Linear and branched hydrocarbons were separated. Both types had an uneven number of up to 41 carbons. The predominant straight-chain hydrocarbons were in the range of 27 to 33 carbons. The branched hydrocarbons identified were 2-methyl, 3-methyl and internally branched monomethyl-alkanes and dimethyl-alkanes. The fatty alcohols identified had a straight chain of 16 to 34 carbons with predominance of 28 to 34 specimens. In the different fractions of esterified fatty acids and in the free acids two groups were detected: one formed by acids of 16 to 18 carbons saturated and non-saturated, and another by very long chain saturated acids of 24 to 32 carbons. The presence of alcohols, hydrocarbons and waxes, constituted mainly by long and saturated chains, conveys to the cuticle high resistance to physical and chemical aggressors of the environment.
Thermocatellispora tengchongensis gen. nov., sp. nov., a new member of the family Streptosporangiaceae. Zhou En-Min,Yang Ling-Ling,Song Zhao-Qi,Yu Tian-Tian,Nie Guo-Xing,Ming Hong,Zhou Yu,Tang Shu-Kun,Li Wen-Jun International journal of systematic and evolutionary microbiology A novel Gram-positive, aerobic, spore-forming, thermophilic actinomycete, designated strain YIM 77521(T), was isolated from a sandy soil sample collected at Rehai National Park, Tengchong, Yunnan province, south-west China. The strain formed branched substrate mycelia and no fragmentation was found. Masses of short, straight or irregular chains of three to eight warty ornamented spores were borne from aerial mycelia. The strain contained meso-diaminopimelic acid in the cell wall and the whole-cell sugars contained mannose, galactose, glucose and ribose. The predominant menaquinones were MK-9(H(4)), MK-9(H(6)) and MK-9(H(8)). The diagnostic polar lipids were diphosphatidylglycerol, phosphatidylmethylethanolamine, phosphatidylethanolamine, hydroxyphosphatidylmonomethylethanolamine and N-acetylglucosamine-containing phospholipids. The major fatty acids were iso-C(16 : 0), C(17 : 0) 10-methyl and C(18 : 0). The DNA G+C content of strain YIM 77521(T) was 73.3 mol%. Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain YIM 77521(T) fell within the radiation of the suborder Streptosporangineae and formed a distinct monophyletic lineage adjacent to the family Streptosporangiaceae with a high bootstrap value. On the basis of combined data from the phenotypic and phylogenetic analyses, strain YIM 77521(T) represents a novel genus and species within the family Streptosporangiaceae, for which the name Thermocatellispora tengchongensis gen. nov., sp. nov. is proposed. The type strain is YIM 77521(T) ( = DSM 45615(T)  = CCTCC AA 2011013(T)). 10.1099/ijs.0.036897-0
Characterization of fatty acid and triacylglycerol composition in animal fats using silver-ion and non-aqueous reversed-phase high-performance liquid chromatography/mass spectrometry and gas chromatography/flame ionization detection. Lísa Miroslav,Netušilová Kateřina,Franěk Lukáš,Dvořáková Hana,Vrkoslav Vladimír,Holčapek Michal Journal of chromatography. A Fatty acid (FA) and triacylglycerol (TG) composition of natural oils and fats intake in the diet has a strong influence on the human health and chronic diseases. In this work, non-aqueous reversed-phase (NARP) and silver-ion high-performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry detection and gas chromatography with flame-ionization detection (GC/FID) and mass spectrometry detection are used for the characterization of FA and TG composition in complex samples of animal fats from fallow deer, red deer, sheep, moufflon, wild boar, cock, duck and rabbit. The FA composition of samples is determined based on the GC/FID analysis of FA methyl esters. In total, 81 FAs of different acyl chain length, double bond (DB) number, branched/linear, cis-/trans- and DB positional isomers are identified. TGs in animal fats contain mainly monounsaturated and saturated FAs. High amounts of branched and trans-FAs are observed in the samples of ruminants. In NARP mode, individual TG species are separated including the separation of trans- and branched TGs. Silver-ion mode provides the separation of TG regioisomers, which enables the determination of their ratios. Great differences in the preference of unsaturated and saturated FAs in the sn-2 position on the glycerol skeleton are observed among individual animal fats. Unsaturated FAs are preferentially occupied in the sn-2 position in all animal samples except for wild boar with the strong preference of saturated FAs in the sn-2 position. 10.1016/j.chroma.2011.07.032
Constitutive fatty acid and enzyme profiles of Mycobacterium species. Teng L J,Liaw S J,Hsueh P R,Fan J H,Luh K T,Ha S W Journal of the Formosan Medical Association = Taiwan yi zhi Sixty-one strains of Mycobacterium tuberculosis complex and 47 strains of nontuberculous mycobacteria were analyzed for fatty acids and enzyme profiles. Cellular fatty acids were extracted from bacteria, methylated and analyzed by gas liquid chromatography operated either manually (Perkin-Elmer) or by the automatic Microbial Identification System. The major cellular fatty acids in all mycobacterial species were C16:0 and C18:1. Tuberculostearic acid was found in all species with the exception of Mycobacterium gordonae. The fatty acids with a carbon-length longer than 20 could be detected only by conventional gas chromatography. Strains of M. tuberculosis had a high ratio of C26:0 to C24:0, and a relatively low ratio of C14:0 to C15:0. For determination of branched-chain fatty acids, the MIS provided more definitive results. The data indicated that the fatty acid profiles could provide rapid species identification. The results of the enzyme profile analysis using API-ZYM strips showed 39 different patterns from 59 strains of M. tuberculosis, and 41 different patterns from 46 nontuberculous mycobacteria strains, suggesting that enzyme profiles can also be used for strain characterization within the same species.
Biosynthesis of the novel fatty acid, 17-methyl-cis-9,10-methyleneoctadecanoic acid, by the parasitic protozoan, Herpetomonas megaseliae. Holz G G,Beach D H,Singh B N,Fish W R Lipids Herpetomonas megaseliae, a flagellate protozoan parasite of the gut of a dipteran, Megaselia scalaris, is shown by chromatographic, spectrometric and radiotracer methods to synthesize de novo an iso-branched chain cyclopropane fatty acid, 17-methyl-cis-9,10-methyleneoctadecanoic acid.
The mitochondrial unfolded protein response activator ATFS-1 protects cells from inhibition of the mevalonate pathway. Rauthan Manish,Ranji Parmida,Aguilera Pradenas Nataly,Pitot Christophe,Pilon Marc Proceedings of the National Academy of Sciences of the United States of America Statins are cholesterol-lowering drugs that inhibit 3-hydroxy-3-methyl-glutaryl-CoA (HMG-CoA) reductase, the rate-limiting enzyme in the synthesis of cholesterol via the mevalonate pathway. This pathway also produces coenzyme Q (a component of the respiratory chain), dolichols (important for protein glycosylation), and isoprenoids (lipid moieties responsible for the membrane association of small GTPases). We previously showed that the nematode Caenorhabditis elegans is useful to study the noncholesterol effects of statins because its mevalonate pathway lacks the sterol synthesis branch but retains all other branches. Here, from a screen of 150,000 mutagenized genomes, we isolated four C. elegans mutants resistant to statins by virtue of gain-of-function mutations within the first six amino acids of the protein ATFS-1, the key regulator of the mitochondrial unfolded protein response that includes activation of the chaperones HSP-6 and HSP-60. The atfs-1 gain-of-function mutants are also resistant to ibandronate, an inhibitor of an enzyme downstream of HMG-CoA reductase, and to gliotoxin, an inhibitor acting on a subbranch of the pathway important for protein prenylation, and showed improved mitochondrial function and protein prenylation in the presence of statins. Additionally, preinduction of the mitochondrial unfolded protein response in wild-type worms using ethidium bromide or paraquat triggered statin resistance, and similar observations were made in Schizosaccharomyces pombe and in a mammalian cell line. We conclude that statin resistance through maintenance of mitochondrial homeostasis is conserved across species, and that the cell-lethal effects of statins are caused primarily through impaired protein prenylation that results in mitochondria dysfunction. 10.1073/pnas.1218778110
Identification by gas chromatography and mass spectrometry of lipids from the rat Harderian gland. Harvey D J Journal of chromatography Lipids from rat Harderian glands were extracted with ethyl acetate, hydrolysed with base and examined by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) as trimethylsilyl (TMS), [2H9]TMS, methyl ester-TMS, picolinyl, nicotinate and nicotinylidene derivatives. The latter three derivatives were used to reveal the structures of the alkyl chains of fatty acids, alcohols and glycerol ethers, respectively. Forty-eight compounds were identified, representing about 97% of the total extracted lipids as measured by GC peak areas. The major constituents were fatty acids with chain lengths from 12 to 22 carbon atoms (mainly C18 and C20) and fatty alcohols (C16 to C26) derived from wax esters. Most of these acids and alcohols were unsaturated in the omega-7 position and were accompanied by smaller amounts of the saturated and omega-5 monounsaturated analogues. glycerol ethers were also identified for the first time in this secretion; the ether chains contained from 14 to 19 carbon atoms (mainly 16) and were straight-chain saturated, unsaturated (omega-5 and omega-7) and branched (iso). The only sterol found was cholesterol amounting to 1.24% of the total extract. 10.1016/0378-4347(91)80367-l
Developmental changes in the glycosylated phosphatidylinositols of Leishmania donovani. Characterization of the promastigote and amastigote glycolipids. McConville M J,Blackwell J M The Journal of biological chemistry In addition to utilizing glycosylated phosphatidylinositols (GPIs) as anchors for surface proteins, protozoan parasites of the genus Leishmania synthesize two novel classes of GPI: the polydisperse lipophosphoglycans (LPGs) and a family of low molecular weight glycoinositol phospholipids (GIPLs). We now show that LPG is expressed in high copy number (6 x 10(6) molecules/cell) in the promastigote (insect) stage of L. donovani but not in the amastigote stage, which infects mammalian macrophages. Detection of these molecules was by gas chromatography-mass spectrometric analyses and by a sensitive radiolabeling procedure. In contrast, a novel family of GIPLs was present in high copy number (approximately 10(7) molecules/cell) in both promastigote and amastigote stages of L. donovani. These glycolipids were purified and analyzed by gas chromatography-mass spectrometry, methylation analysis, and by chemical and enzymatic sequencing after deamination and NaB3H4 reduction. Promastigotes contained three major GIPLs species with the following generalized structure [formula: see text] where R = H for isoM2, Man alpha 1- for isoM3 or Man alpha 1-2Man alpha 1- for isoM4. Amastigotes contained two major GIPL species that lacked the alpha 1-3-linked mannose branch and had the linear structures Man alpha 1-6Man alpha 1-4GlcN (M2) and Man alpha 1-2Man alpha 1-6Man alpha 1-4GlcN (M3) linked to alkylacyl-PI. The 1-O-alkyl-2-acyl-PI moieties of all these species contained predominantly C18:0 alkyl chains and C16:0 or C18:0 fatty acids. Amastigotes contained, in addition, a GalNAc beta 1-3 terminating glycosphingolipid with homology to the mammalian para Forssman glycolipid. This glycolipid appeared to be a constituent of the parasite membrane but was not metabolically labeled with [3H]glucose, suggesting that it was acquired from host cells. These results suggest that LPG may not be required for amastigote survival in the mammalian host and that the GIPLs are likely to be major components on the surface membrane in both stages.
Total synthesis of 2-methoxy-14-methylpentadecanoic acid and the novel 2-methoxy-14-methylhexadecanoic acid identified in the sponge Agelas dispar. Carballeira Néstor M,Cruz Heidyleen,Ayala Norma L Lipids The phospholipid FA composition of the Caribbean sponge Agelas dispar was revisited and 40 different FA were identified. Among these a novel 2-methoxylated FA, namely, the anteiso methyl-branched 2-methoxy-14-methylhexadecanoic acid, was identified together with the recently discovered iso methyl-branched 2-methoxy-14-methylpentadecanoic acid and the normal-chain 2-methoxytetradecanoic acid. The structures of the iso and anteiso methyl-branched 2-methoxylated FA were confirmed by total syntheses, which were accomplished in seven steps and in 45-48% overall yields. Other phospholipid FA identified in A. dispar include the unusual methyl-branched 10,13-dimethyltetradecanoic acid, 3,7,11,15-tetramethylhexadecanoic (phytanic) acid, and the 11-methyloctadecanoic acid. In addition, the delta5,9 FA (5Z,9Z)-15-methyl-5,9-hexadecadienoic acid and (5Z,9Z)-5,9-octadecadienoic acid were characterized. These findings establish alternative FA biosynthetic possibilities for these marine organisms.
Nocardiopsis kunsanensis sp. nov., a moderately halophilic actinomycete isolated from a saltern. Chun J,Bae K S,Moon E Y,Jung S O,Lee H K,Kim S J International journal of systematic and evolutionary microbiology A moderately halophilic actinomycete, designated HA-9T, was isolated from a saltern in Kunsan, Republic of Korea, and was the subject of polyphasic identification. Analysis of 16S rDNA indicated that the isolate belonged to the genus Nocardiopsis, but differed genetically from other Nocardiopsis species. Strain HA-9T contained meso-diaminopimelic acid, no diagnostic sugars, hexa- or octa-hydrogenated menaquinones with 10 isoprene units, straight-chain saturated or monounsaturated, iso-, anteiso-, 10-methyl branched fatty acids with 13-18 carbons and type III phospholipids. All of these characters consistently assign the isolate to the genus Nocardiopsis. All of the validly described Nocardiopsis species, including moderately halophilic Nocardiopsis halophila, can be differentiated from the saltern isolate using morphological and physiological traits. On the basis of polyphasic evidence, the name Nocardiopsis kunsanensis sp. nov. is proposed for strain HA-9T (= KCTC 9831T), which is designated the type strain. 10.1099/00207713-50-5-1909
Comparative evaluation of [123I]14-p-iodophenyl-beta-methyltetradecanoic acid and thallium-201 in the detection of infarcted areas in the dog heart using SPECT. Kairento A L,Livni E,Mattila S,Harjula A,Porkka L,Lindroth L,Elmaleh D R International journal of radiation applications and instrumentation. Part B, Nuclear medicine and biology The concept of using beta-methyl-branched long-chain fatty acids for assessment of myocardial fatty acid uptake and perfusion was extended to the use of radioiodinated fatty acid with stabilization of iodine on the omega-phenyl ring. Beagle dogs were injected with thallium-201 and imaged 15 min after injection. The next day the dogs were infarcted by occluding the LAD, and 2 h later they were injected with [123I]14-p-iodophenyl-beta-methyltetradecanoic acid [123I]BMTDA and imaged for 90 min using a gated SPECT procedure. Maximum uptake of BMTDA in the heart was reached 2 min post injection and the activity level remained constant in the heart during the imaging period. The activity ratio of target to nontarget areas in the tomographic slices was significantly better for the BMTDA imaging compared to 201Tl (P greater than 0.01). 10.1016/0883-2897(88)90115-8
Annual evolution of fatty acid profile from muscle lipids of the common carp (Cyprinus carpio) in Madagascar inland waters. Rasoarahona Jean R E,Barnathan Gilles,Bianchini Jean-Pierre,Gaydou Emile M Journal of agricultural and food chemistry Annual evolution of muscle lipids fatty acid (FA) from common carp (Cyprinus carpio) has been determined in 2001 through monthly samplings in the reserve pond of Sisaony (SIS series) and Itasy Lake (ITA series) of the Madagascar highlands. Total lipids from muscle were extracted and quantified according to the Bligh and Dyer method. FA identification was performed by GC-MS of FA methyl esters and FA pyrrolidides and led to the identification of 41 FA; routine analyses of FA were made by capillary GC. Principal component analysis (PCA) was performed on the data set to compare FA profiles. Lipid content is low, ranging from 0.91 to 1.73% of wet muscle, with a low stage during the hot season (January-April) and a higher stage during the cold season (July-October). Three FA dominated the FA composition: oleic acid (17.0-21.5%), palmitic acid (13.1-16.1%), and linoleic acid (9.6-13.2%). Polyunsaturated fatty acids (PUFA) were present in appreciable amounts: arachidonic acid (AA; 2.9-5.9%), docosahexaenoic acid (DHA; 2.9-6.7%), eicosapentaenoic acid (EPA; 1.9-3.4%), and docosapentaenoic acid (DPA; 1.9-4.3%). Two opposite evolution schemes appear within two groups of FA; on the one hand PUFA (both n-3 and n-6 series) show a maximum in August-October and a minimum in January-April, and, on the other hand, oleic, palmitic, and linoleic acids show the opposite maxima and minima. PCA results give confirmation of these evolution schemes, the two groups of FA giving opposite high factor loadings on axis 1. The SIS and ITA series are differentiated by axis 2 by mean of minor FA, mostly odd- and branched-chain. Results indicate that common carp, the second most abundant freshwater fish in Madagascar highlands waters, may be an interesting source of dietary PUFA. 10.1021/jf048993y
Pharmacologic evaluation of various metabolites and analogs of valproic acid: teratogenic potencies in mice. Nau H,Löscher W Fundamental and applied toxicology : official journal of the Society of Toxicology A number of metabolites of the anticonvulsant drug valproic acid (VPA) as well as related substances were tested in regard to their teratogenicity in the mouse following single sc injections of 600 mg/kg on Day 8 of gestation. VPA was highly teratogenic at this dose level and over 60% of live fetuses had neural tube defects (exencephaly). Homologous compounds with shorter or longer alkyl chains were less teratogenic. Substitution of the alpha-H atoms in related branched carboxylic acids by methyl or ethyl groups abolished the teratogenic response. Introduction of a double bond in the omega-position of VPA (4-en-VPA) did not change the teratogenicity of VPA, while omega-2 double bond (2-en-VPA) abolished teratogenicity. The other VPA metabolites tested as well as two straight-chain acids (n-octanoic acid and 4-pentenoic acid) and the two clinically used substances valpromide (valproic acid amide) and ethosuximide did not induce neural tube defects, although some of them induced slightly increased resorption rates and fetal weight retardation. The serum protein binding capacities of the various compounds did not correlate with the teratogenic response. Also the concentrations reached in the gestational material did not predict the teratogenicity of the substances tested. Our results indicate that the teratogenicity of the class of compounds studied represents a more specific effect than the anticonvulsant activity which could lead to the development of alternative antiepileptic drugs with low embryotoxic potential.
Biochemical characteristics and fatty acid compositions of some armadillo-derived mycobacteria and their relation to Mycobacterium gordonae. Portaels F,Larsson L,Jimenez J,Cierkens C Journal of general microbiology The long-chain components of 75 strains of mycobacteria, cultivated from Mycobacterium leprae-infected or non-infected armadillos, and of eight clinical and 15 environmental isolates of M. gordonae, were compared. Four major groups could be distinguished based on the presence of 10-methyloctadecanoic (tuberculostearic) and 2-methyl 3-hydroxyeicosanoic acids and secondary alcohols (2-octadecanol and 2-eicosanol). Some heterogeneity was found in strains assigned to M. gordonae: the characteristic absence of tuberculostearic acid and secondary alcohols and the presence of the branched C14 and the hydroxylated C20 acids were seen in only 34 of the 49 strains studied. Three strains were identified as M. malmoense, one as M. kansasii, ten as belonging to the M. avium-M. intracellulare-M. scrofulaceum complex and eight as belonging to new groups of armadillo-derived mycobacteria (ADM 1, ADM 2 and ADM 3) by conventional bacteriological tests and fatty acid compositions, though M. malmoense was heterogeneous in its fatty acids composition. Four strains, identified as M. avium by conventional tests, differed from this species by their fatty acid compositions. Thirteen strains showed some similarity to M. simiae and ten strains differed from all other known mycobacteria. 10.1099/00221287-133-3-739
Devosia chinhatensis sp. nov., isolated from a hexachlorocyclohexane (HCH) dump site in India. Kumar Mukesh,Verma Mansi,Lal Rup International journal of systematic and evolutionary microbiology A Gram-negative, motile, rod-shaped and non-spore-forming bacterium was isolated from a soil sample collected from the area adjoining an India Pesticide Limited plant, Lucknow, India. Strain IPL18T was characterized on the basis of phenotypic and genotypic data. Based on 16S rRNA gene sequence analysis, this strain was shown to belong to genus Devosia, with highest sequence similarity of 97.5 % to Devosia riboflavina DSM 7230T. A neighbour-joining phylogenetic tree based on 16S rRNA gene sequence analysis revealed that strain IPL18T shows an evolutionary relationship with Devosia neptuniae J1T. Strain IPL18T contains C18 : 1 omega 7c, 11-methyl C18 : 1 omega 7c and C16 : 0 as the major fatty acids along with 3-OH C18 : 0, characteristic of the genus Devosia. The branched-chain fatty acid iso-H C18 : 1 (4.69 %), not present in any of the Devosia species known so far, has been reported in strain IPL18T. The results of DNA-DNA hybridization experiments (13 % relatedness with D. riboflavina DSM 7230T and 11 % with D. neptuniae J1T), phylogenetic analysis and biochemical tests confirm that strain IPL18T represents a novel species of the genus Devosia for which the name Devosia chinhatensis sp. nov. is proposed. The type strain is IPL18T (=CCM 7426T=MTCC 8593T). 10.1099/ijs.0.65574-0
Biochemical and structural characterization of an unusual group of gram-negative, anaerobic rods from human periapical osteitis. Haapasalo M,Ranta H,Shah H,Ranta K,Lounatmaa K,Kroppenstedt R M Journal of general microbiology The biochemical and chemotaxonomic properties of three previously undescribed strains from human dental root canal infections are presented. The strains were obligately anaerobic Gram-negative rods with fimbriae and a thick capsule-like structure. Carbohydrates were not fermented and agglutination tests were negative. The presence of alpha-galactosidase, alpha- and beta-glucosidase, beta-N-acetylglucosaminidase and beta-galactosidase was confirmed. The strains produced acetic and succinic acids as metabolic end products. They contained a peptidoglycan structure based upon meso-diaminopimelic acid (Al gamma) and lacked respiratory quinones. The cellular fatty acids were mainly straight-chain saturated and methyl-branched molecules. High interstrain DNA homology was observed and the DNA base compositions were between 56 and 59 mol % G + C. These three strains appear to comprise the nucleus of a new genus of anaerobic, Gram-negative rods from odontogenic infections. 10.1099/00221287-132-2-417
Identification of pristanal dehydrogenase activity in peroxisomes: conclusive evidence that the complete phytanic acid alpha-oxidation pathway is localized in peroxisomes. Jansen G A,van den Brink D M,Ofman R,Draghici O,Dacremont G,Wanders R J Biochemical and biophysical research communications Phytanic acid (3,7,11,15-tetramethylhexadecanoic acid) is a branched-chain fatty acid which, due to the methyl-group at the 3-position, can not undergo beta-oxidation unless the terminal carboxyl-group is removed by alpha-oxidation. The structure of the phytanic acid alpha-oxidation machinery in terms of the reactions involved, has been resolved in recent years and includes a series of four reactions: (1) activation of phytanic acid to phytanoyl-CoA, (2) hydroxylation of phytanoyl-CoA to 2-hydroxyphytanoyl-CoA, (3) cleavage of 2-hydroxyphytanoyl-CoA to pristanal and formyl-CoA, and (4) oxidation of pristanal to pristanic acid. The subcellular localization of the enzymes involved has remained enigmatic, with the exception of phytanoyl-CoA hydroxylase and 2-hydroxyphytanoyl-CoA lyase which are both localized in peroxisomes. The oxidation of pristanal to pristanic acid has been claimed to be catalysed by the microsomal aldehyde dehydrogenase FALDH encoded by the ALDH10-gene. Making use of mutant fibroblasts deficient in FALDH activity, we show that phytanic acid alpha-oxidation is completely normal in these cells. Furthermore, we show that pristanal dehydrogenase activity is not fully deficient in FALDH-deficient cells, implying the existence of one or more additional aldehyde dehydrogenases reacting with pristanal. Using subcellular localization studies, we now show that peroxisomes contain pristanal dehydrogenase activity which leads us to conclude that the complete phytanic acid alpha-oxidation pathway is localized in peroxisomes. 10.1006/bbrc.2001.4835
Fibroblast studies documenting a case of peroxisomal 2-methylacyl-CoA racemase deficiency: possible link between racemase deficiency and malabsorption and vitamin K deficiency. Van Veldhoven P P,Meyhi E,Squires R H,Fransen M,Fournier B,Brys V,Bennett M J,Mannaerts G P European journal of clinical investigation BACKGROUND:2-Methylacyl-CoA racemase interconverts the 2-methyl group of pristanoyl-CoA or the 25-methyl group of hydroxylated cholestanoyl-CoAs, allowing further peroxisomal desaturation of these compounds in man by the branched chain acyl-CoA oxidase, which recognise only the S-isomers. Hence, oxidation studies in fibroblasts, currently based on the use of racemic substrates such as [1-14C] pristanic acid, do not allow us to distinguish between a deficient racemase or an impaired oxidase. DESIGN:To evaluate the racemase activity directly, the 2R-isomer of[1-14C] pristanic acid, as well as the 2R-isomer of 2-methyl-[1-14C] hexadecanoic, a synthetic pristanic acid substitute, were prepared and their degradation by cultured human skin fibroblasts was compared to that of the racemic substrates. RESULTS:In fibroblasts in a young girl, presenting with elevated urinary levels of trihydroxycholestanoic acid metabolites but normal plasma levels of very long chain fatty acids, a partial deficient degradation of racemic [1-14C] pristanic acid was observed. Incorporation of 2R-[1-14C] pristanic acid in glycerolipids of the patient's fibroblasts proceeded normally, but breakdown was impaired. Similar findings were seen with the 2R-isomer of 2-methyl-[1-14C] hexadecanoic. These data, combined with the fact that the branched chain acyl-CoA oxidase, catalyzing the first oxidation step of pristanic acid and bile acid intermediates in man, appeared normal, suggested a peroxisomal beta-oxidation defect in the patient at the level of 2-methylacyl-CoA racemase. CONCLUSION:Carboxy-labelled 2R-methyl branched chain fatty acids might be useful tools to document cases of racemase deficiencies. Because a brother of the patient died with a diagnosis of vitamin K deficiency, an impaired racemase might be responsible for other cases of unexplicable malabsorption.
Increase of the activity state and loss of total activity of the branched-chain 2-oxo acid dehydrogenase in rat diaphragm during incubation. Wagenmakers A J,Schepens J T,Veerkamp J H The Biochemical journal Actual and total branched-chain 2-oxo acid dehydrogenase activities were determined in homogenates of incubated diaphragms from fed and starved rats. Incubation in Krebs-Ringer buffer increased the activity state, but caused considerable loss of total activity. Palmitate oxidation rates and citrate synthase activities did not significantly change on incubation. Starved muscles showed a higher extent of activation after 15 min of incubation (not after 30 and 60 min) and a smaller loss of total activity. Experiments with the transaminase inhibitor amino-oxyacetate confirm that the contribution of endogenous amino acids to the oxidation precursor pool is also smaller in diaphragms from starved rats on incubation in vitro. These phenomena together cause the higher 14CO2 production from 14C-labelled branched-chain amino acids and 2-oxo acids in muscles from starved than from fed rats. High concentrations of branched-chain 2-oxo acids, and the presence of 2-chloro-4-methyl-pentanoate, octanoate or ketone bodies, increase the extent of activation of the dehydrogenase complex; glucose and pyruvate had no effect. The observed changes of the activity state by these metabolites are discussed in relation to their interaction with branched-chain 2-oxo acid oxidation in incubated hemidiaphragms. 10.1042/bj2240491
Unusual lipid composition of a Bacillus sp. isolated from Lake Pomorie in Bulgaria. Carballeira N M,Guzmán A,Nechev J T,Lahtchev K,Ivanova A,Stefanov K Lipids The lipid composition of a Bacillus sp., isolated from Lake Pomorie in Bulgaria, was unusual and consisted of 26 different fatty acids between C12 and C26, with anteiso C15-C17 saturated fatty acids predominating. The furan fatty acid, 10,13-epoxy-11-methyloctadeca-10,12-dienoic acid, was also identified, a new finding for this genus. The hydrocarbons consisted of 30 different monounsaturated hydrocarbons, between C25 and C30, with the iso-iso, iso-anteiso, anteiso-anteiso, iso-normal, and anteiso-normal methyl branching for odd-numbered chains, and the iso-iso, iso-anteiso, iso-normal, and anteiso-normal methyl branching for even-numbered chains. The double bond positions in these hydrocarbons were determined by dimethyl disulfide derivatization followed by GC-MS, and the double-bond cis configuration was confirmed by infrared spectroscopy. Some previously unknown hydrocarbons in bacteria, such as (Z)-3,21-dimethyl-9-tricosene, (Z)-3,21-dimethyl-10-tricosene, (Z)-2,24-dimethyl-11-pentacosene, and (Z)-2,25-dimethyl-13-hexacosene were identified. Sterols were detected and were based on the sitosterol nucleus.
Actinomadura sediminis sp. nov., a marine actinomycete isolated from mangrove sediment. He Jie,Xu Ying,Sahu Maloy Kumar,Tian Xin-Peng,Nie Guo-Xing,Xie Qiong,Zhang Si,Sivakumar Kannan,Li Wen-Jun International journal of systematic and evolutionary microbiology In this study, the taxonomic position of an actinobacterium, strain YIM M 10931(T), which was isolated from a mangrove sediment sample collected in Dugong Creek, Little Andaman, India, was determined by a polyphasic approach. This gram-positive, aerobic strain produced branched substrate mycelium and aerial hyphae, which differentiated into short, hooked or spiral spore chains. The organism contained meso-diaminopimelic acid as the diagnostic diamino acid in the cell-wall peptidoglycan. The whole cell sugars consisted of mannose, ribose, glucose, galactose and madurose. The cellular fatty acid profile mainly consisted of iso-C(16 : 0), 10-methyl C(18 : 0) and C(16 : 0). The quinone system was predominantly composed of MK-9(H(8)) (45.5 %) and MK-9(H(6)) (39 %). The phospholipids detected were diphosphatidylglycerol, phosphatidylglycerol, phosphatidylinositol mannoside, phosphatidylinositol and two unknown phospholipids. The organism showed a combination of morphological and chemotaxonomic properties typical of members of the genus Actinomadura. Moreover, phylogenetic analysis based on a 16S rRNA gene sequence generated from the strain identified its closest relatives as Actinomadura cremea DSM 43676(T) (98.4 % sequence similarity), Actinomadura rifamycini DSM 43936(T) (97.4 %) and Actinomadura apis IM17-1(T) (96.9 %). It was obvious from the resulting phylogenetic trees that strain YIM M 10931(T) belongs to a distinct subclade within the evolutionary radiation of the genus Actinomadura. DNA-DNA hybridizations of strain YIM M 10931(T) with A. cremea DSM 43676(T) and A. rifamycini DSM 43936(T) were performed and further confirmed that the isolate represents a separate genomic species. Based on the phenotypic and genotypic characteristics presented, it is proposed that strain YIM M 10931(T) represents a novel species within the genus Actinomadura, for which the name Actinomadura sediminis sp. nov. is proposed; the type strain is YIM M 10931(T) ( = CCTCC AA 2010009(T) = DSM 45500(T)). 10.1099/ijs.0.032979-0
Lapillicoccus jejuensis gen. nov., sp. nov., a novel actinobacterium of the family Intrasporangiaceae, isolated from stone. Lee Soon Dong,Lee Dong Wan International journal of systematic and evolutionary microbiology A novel, yellow-pigmented actinobacterium was isolated from a small stone collected in Jeju, Republic of Korea. The cells of the organism, designated strain R-Ac013(T), were Gram-positive, aerobic, non-motile cocci that occurred singly or in pairs. The strain showed growth at 10-37 degrees C and pH 4.1-11.1, and tolerated 2 % NaCl. On the basis of the 16S rRNA gene sequence, the organism was phylogenetically related to members of the genera Tetrasphaera (94.6-97.1 % sequence similarity), Terrabacter (96.5 %), Knoellia (96.4 %), Terracoccus (96.4 %), Oryzihumus (96.4 %), Janibacter (96.1-96.4 %) and Intrasporangium (96.2 %). The chemotaxonomic results for the organism were as follows: ll-diaminopimelic acid as the diagnostic diamino acid in the peptidoglycan, acetyl-type murein, MK-8(H(4)) as the major menaquinone, a DNA G+C content of 74.1 mol%, and a polar lipid profile that comprised diphosphatidylglycerol and phosphatidylinositol. The fatty acid profile consisted of iso- and anteiso-methyl-branched, straight-chain saturated and monounsaturated types, the major components being iso-C(16 : 0), C(17 : 1)omega8c and iso-C(15 : 0). The combination of the phenotypic and phylogenetic data revealed that this strain represents a novel genus and species of the family Intrasporangiaceae, for which the name Lapillicoccus jejuensis gen. nov., sp. nov. is proposed. The type strain is strain R-Ac013(T) (=KCTC 19200(T)=DSM 18607(T)). 10.1099/ijs.0.64911-0
Metabolism substrate with negative myocardial uptake of iodine-123-BMIPP. Kudoh T,Tamaki N,Magata Y,Konishi J,Nohara R,Iwasaki A,Ono S,Ohtake Y,Sugihara H,Sugihara H,Kuze K,Tsujimura Y,Miyazaki T Journal of nuclear medicine : official publication, Society of Nuclear Medicine UNLABELLED:Iodine-123-BMIPP is an iodinated methyl-branched-chain fatty acid. Low uptake of BMIPP relative to thallium or other perfusion tracer indicates metabolically damaged but viable myocardium (for example, ischemic but viable myocardium). In some cases, however, negative myocardial uptake of BMIPP is observed. The main purposes of this study were to assess the frequency of such BMIPP findings and to clarify metabolism of such cases by using PET. METHODS:Among the 1258 patients who underwent BMIPP scintigraphy, 11 patients (0.9%) showed negative myocardial uptake of BMIPP. Under fasting condition, PET using [11C]palmitate, 2-[18F]fluoro-2-deoxy-D-glucose ([18F]FDG) and [11C]acetate was performed in nine of these 11 patients. RESULTS:Global myocardial uptake of [11C]palmitate, expressed as the standardized uptake value, was significantly lower in the patients than in control (3.62 +/- 0.44 versus 5.49 +/- 1.62; p < 0.01). However, the early phase clearance rate of [11C]palmitate and oxidative metabolism was not significantly different. In the fasting state, PET studies showed increased FDG accumulation in seven of nine patients (high group) and decreased accumulation in two patients (low group). In the high group patients, glucose metabolism in the fasting state was similar to that in the normal volunteers after glucose loading (Kcomplex: 0.050 +/- 0.016 versus 0.038 +/- 0.015; p = ns). However, low glucose metabolism was noted in the low group patients (Kcomplex: 0.007 and 0.005). CONCLUSION:Negative myocardial uptake of BMIPP is occasionally, but not often, observed. Global uptake of [11C]palmitate was decreased in these patient. The majority of these patients showed "metabolic switching" from normal free fatty acid metabolism to abnormally enhanced glucose metabolism in the fasting state. However, some patients showed decreases in both exogenous glucose utilization and free fatty acid uptake in the fasting state.
Regulation and phase equilibria of membrane lipids from Bacillus megaterium and Acholeplasma laidlawii strain A containing methyl-branched acyl chains. Rilfors L,Hauksson J B,Lindblom G Biochemistry Phosphatidylethanolamine (PE) was isolated from Bacillus megaterium grown at 20 and 55 degrees C (PE-20 and PE-55). Iso and anteiso methyl-branched, saturated acyl chains are predominant in B. megaterium, and the value of the molar ratio of iso/anteiso acyl chains is more than 20-fold higher in PE-55 than in PE-20. Moreover, about 21 mol% of the acyl chains of PE-20 are monounsaturated. The phase equilibria differ between the two PE preparations: (1) PE-20 is more prone to form reversed nonlamellar phases than PE-55; (2) PE-20 forms both reversed cubic (I2) and reversed hexagonal (H(II)) phases while PE-55 forms only an HII phase; and (3) the lamellar liquid-crystalline (L alpha) phase of PE-20 takes up about 70% more water than the L alpha phase of PE-55. These differences can be explained by the differences in the acyl chain composition. When the growth temperature is raised, PE molecules with a reduced tendency to form nonlamellar phases are probably synthesized by B. megaterium in order to counteract the bilayer destabilizing effect of the temperature. The regulation of the acyl chain composition is not needed in order to regulate the temperature for the transition between gel/crystalline and L alpha phases of the membrane lipids. Acholeplasma laidlawii strain A-EF22 was grown at 37 degrees C on 15-(1,1,1(-2) H3)methylhexadecanoic acid, 14-(1,1,1(-2)H3)methylhexadecanoic acid or 13-(1,1,1(-2)H3)methylhexadecanoic acid, and these acids constituted 84-89 mol% of the acyl chains in the membrane lipids. The molar ratio between the two dominating lipids, monoglucosyldiacylglycerol (MGLcDAG) and diglucosyldiacylglycerol (DGlcDAG), decreased, and the molar fraction of the anionic lipids increased, when the methyl branch was moved from position 15 to position 13. Concomitantly, the order of the methyl branch increased in cells as well as in total lipid extracts. The phase equilibria of total lipid extracts (neutral lipids removed) were studied with 20 wt % of water, and HII and I2 phases were formed above 63-67 degrees C. These results indicate that the regulation of the polar head-group composition compensates for the difference in acyl chain packing introduced into the bilayer by the three branched-chain fatty acids. The regulation of the polar head-group composition of the A. laidlawii lipids cannot regulate the temperature for the transition between gel/crystalline and L alpha phases of the lipids, i.e. the transition to fluid acyl chains.(ABSTRACT TRUNCATED AT 400 WORDS) 10.1021/bi00186a010
Temperature- and growth-phase-regulated changes in lipid fatty acid structures of psychrotolerant groundwater Proteobacteria. Männistö M K,Puhakka J A Archives of microbiology Cellular fatty acid compositions of five psychrotolerant groundwater isolates representing alpha- and beta-Proteobacteria were studied at temperatures ranging from 8 to 25 degrees C. Unsaturation of straight-chain fatty acids was the most common response to decreasing temperature and was detected in four of the isolates. On solid media, decrease of temperature resulted in a decrease of cyclopropane fatty acids in beta-proteobacterial isolates. The formation of cyclopropane fatty acids depended, however, to a greater extent on the growth phase than the temperature and increased drastically as the cells entered stationary phase. The alpha-proteobacterial isolates contained a branched C(19:1) fatty acid. The formation of the branched C(19:1) increased during growth in the same way as the cyclopropane fatty acids in beta-proteobacterial strains, indicating possibly an analogous formation of the branched fatty acid by methylation of the 18:1 fatty acid. Sphingomonas sp. K6 possessed a novel temperature-induced modification of lipid fatty acids. As temperature decreased from 25 to 8 degrees C, the fatty acid composition shifted from predominantly even-carbon fatty acids to odd-carbon fatty acids. The results show completely different fatty acid modifications in two strains of the same genus Sphingomonas. 10.1007/s00203-001-0356-4
Effect of monounsaturation of a branched fatty acid on organ selectivity. Zaknun J,Elmaleh D R,Guan J H,Fischman A J Journal of nuclear medicine : official publication, Society of Nuclear Medicine UNLABELLED:1-[11C]-3-R,S-methylheptadecanoic acid (BMHA) is a branched chain fatty acid analog that is transported into the myocardium. Due to incomplete metabolism, however, radiolabeled products are trapped within myocytes. Recently, we demonstrated that this compound is an excellent tracer to monitor fatty acid metabolism. METHOD:To evaluate the effect of mono-unsaturation on myocardial substrate utilization, we prepared 1-[11C]-3-R,S-methyl-trans--heptadec-7-enoic acid (t-7-BMHA) and measured its biodistribution in rats. In addition, preliminary PET studies were performed on dogs. RESULTS:Biodistribution studies demonstrated that myocardial-to-lung and myocardial-to-blood ratios for t-7-BMHA are higher than those for BMHA. Fifteen minutes after injection, heart-to-lung ratios were 5.23 compared to 2.92 and heart-to-liver ratios were 3.07 compared to 1.41 for t-7-BMHA and BMHA. By 30 min postinjection heart-to-lung ratios were 7.03 compared to 5.88 and heart-to-liver ratios were 4.43 compared to 1.09. The heart-to-blood ratio of t-7-BMHA was greater than 11:1. PET imaging with 1-[11C]-t-7-BMHA demonstrated high myocardial extraction, prolonged retention of radioactivity and excellent image quality. Accumulation of radioactivity in the myocardium reached a plateau within 10 min postinjection, with heart-to-blood ratios exceeding 20:1 and heart-to-lung ratios exceeding 10:1. Blood clearance of radioactivity was biphasic with half-times of 1.46 and 14.7 min, respectively. CONCLUSION:These data suggest that introduction of a trans-double bond in BMHA improves myocardial selectivity and results in a potentially superior imaging agent.
Characterization of microbial communities of biofilters by phospholipid fatty acid analysis and rRNA targeted oligonucleotide probes. von Keitz V,Schramm A,Altendorf K,Lipski A Systematic and applied microbiology The microbial community of a biofilter for waste gas treatment of an animal rendering plant was characterized by the analyses of the phospholipid fatty acids (PLFAs) of the filter material. For these analyses five samples of one filter were taken in intervals between one and two months. The main components of the PLFA profiles were straight chain saturated, monounsaturated and cyclopropyl fatty acids. Terminally branched and 10-methyl branched fatty acids were present in minor amounts. The structure and succession of the microbial community was interpreted by the presence and quantitative changes of diagnostic fatty acids. The stability of diagnostic fatty acids in relation to varying incubation parameters was tested for a number of bacterial isolates from biofilters representing different phylogenetic branches. For two samples, the data from the PLFA-analyses were compared with data obtained by hybridization with fluorescently labeled, rRNA-targeted oligonucleotide probes specific for the alpha-, beta- and gamma-subclass of the Proteobacteria, the Actinobacteria (Firmicutes with high G+C content) and the Firmicutes with low G+C content. These data indicated a dominating number of Proteobacteria (54% and 35% of DAPI-stained cells), in which the gamma-Proteobacteria represented the main fraction. Actinobacteria were detected in minor amounts, the number of Firmicutes with low G+C content was near the detection limit of the method. About half of the cells detected with a probe specific for Bacteria did not hybridize with the probes specific for the alpha-, beta- and gamma subclass of the Proteobacteria and the two subgroups of the Firmicutes. The results of both methods, the fluorescence in situ hybridization (FISH) and the PLFA analyses corresponded well and were best suited to confirm and complement each other. 10.1016/S0723-2020(99)80016-2
Acyl-CoA thioesterase 9 (ACOT9) in mouse may provide a novel link between fatty acid and amino acid metabolism in mitochondria. Cellular and molecular life sciences : CMLS Acyl-CoA thioesterase (ACOT) activities are found in prokaryotes and in several compartments of eukaryotes where they hydrolyze a wide range of acyl-CoA substrates and thereby regulate intracellular acyl-CoA/CoA/fatty acid levels. ACOT9 is a mitochondrial ACOT with homologous genes found from bacteria to humans and in this study we have carried out an in-depth kinetic characterization of ACOT9 to determine its possible physiological function. ACOT9 showed unusual kinetic properties with activity peaks for short-, medium-, and saturated long-chain acyl-CoAs with highest V max with propionyl-CoA and (iso) butyryl-CoA while K cat/K m was highest with saturated long-chain acyl-CoAs. Further characterization of the short-chain acyl-CoA activity revealed that ACOT9 also hydrolyzes a number of short-chain acyl-CoAs and short-chain methyl-branched CoA esters that suggest a role for ACOT9 in regulation also of amino acid metabolism. In spite of markedly different K ms, ACOT9 can hydrolyze both short- and long-chain acyl-CoAs simultaneously, indicating that ACOT9 may provide a novel regulatory link between fatty acid and amino acid metabolism in mitochondria. Based on similar acyl-CoA chain-length specificities of recombinant ACOT9 and ACOT activity in mouse brown adipose tissue and kidney mitochondria, we conclude that ACOT9 is the major mitochondrial ACOT hydrolyzing saturated C2-C20-CoA in these tissues. Finally, ACOT9 activity is strongly regulated by NADH and CoA, suggesting that mitochondrial metabolic state regulates the function of ACOT9. 10.1007/s00018-013-1422-1
Fatty acid discrimination and omega-hydroxylation by cytochrome P450 4A1 and a cytochrome P4504A1/NADPH-P450 reductase fusion protein. Alterman M A,Chaurasia C S,Lu P,Hardwick J P,Hanzlik R P Archives of biochemistry and biophysics The omega-hydroxylation of fatty acids by certain cytochrome P450 enzymes shows a degree of chain-length and regionspecificity which is remarkable in view of the conformational flexibility of these substrates, the strong similarity in properties among homologs, and the lack of polar groups (other than the carboxy terminus) with which to guide and strength enzyme-substrate interactions. To investigate the chemical basis for these features of omega-hydroxylation we designed and synthesized a series of lauric acid analogs and evaluated them as substrates and inhibitors of omega-hydroxylation catalyzed by cytochrome P4504A1 and a cytochrome P450 4A1/NADPH-P450 reductase fusion protein. Among n-alkanoic acids, lauric acid was found to have the optimum chain length for the fusion protein, as it does for native cytochrome P450 4A1. With both enzymes, chain shortening caused a precipitous drop in turnover while chain lengthening caused a gradual drop in turnover. The fusion protein omega-hydroxylated methyl laurate and lauryl alcohol about 1/10th as efficiently as lauric acid, but it did not hydroxylate lauramide. 10-Methoxydecanoic acid underwent O-demethylation (via omega-hydroxylation). The branched substrate 11-methyllauric acid was hydroxylated efficiently and selectively at the omega-position. In contrast, the cyclopropyl analog 11,12-methanolauric acid was not detectably hydroxylated, although it induced Type I binding spectrum and inhibited lauric acid omega-hydroxylation by 43% at equimolar concentrations. omega-(Imidazolyl)-decanoic acid induced a Type II heme-binding spectrum and was an especially potent inhibitor of lauric acid hydroxylation. Collectively these data suggest that the active site of cytochrome P450 4A1 has an elongated tubular shape of definite length (ca. 14 A) with a recognition site for polar groups (including but not limited to carboxyl) at its entrance and the (oxo)heme group at its terminus. 10.1016/0003-9861(95)90012-8
Studies of trans-3-methyl-2-hexenoic acid in normal and schizophrenic humans. Gordon S G,Smith K,Rabinowitz J L,Vagelos P R Journal of lipid research The report that sweat of certain schizophrenics contains the branched chain fatty acid, trans-3-methyl-2-hexenoic acid (TMHA), stimulated an investigation to evaluate the relationship between this fatty acid and schizophrenia. A sensitive and specific gas-liquid chromatography-mass spectroscopic procedure was developed for analyzing biological fluids for TMHA. Analysis of sweat samples from normal and schizophrenic subjects indicated that the sweat of both groups contains comparable quantities of this fatty acid. In addition, the fate of intravenously administered (14)C-labeled TMHA was shown to be similar in normal and schizophrenic subjects. It is concluded that there is no relationship between TMHA and schizophrenia.
Structure of cerebroside in Aspergillus oryzae. Fujino Y,Ohnishi M Biochimica et biophysica acta Structural studies on cerebroside isolated from Aspergillus oryzae were carried out using mainly gas-liquid chromatography-mass spectrometry. The major component fatty acids were 2-hydroxystearic and 2-hydroxy-trans-octadecenoic acid; branched 17?-methyl nonadecasphingadienine isomers were the predominant long-chain bases. The component sugar was only glucose. The structure of the major cerebrosides was assumed to be N-2'-hydroxystearoyl-1-O-glucosyl-17?-methyl sphingadienine and N-2'-hydroxyoctadecenoyl-1-O-glucosyl-17?-methyl sphingadienine.
Kinetics of iodomethylated hexadecanoic acid metabolism in the rat myocardium: influence of the number and the position of methyl radicals. Fagret D,Bontemps L,Apparu M,Keriel C,Mathieu J P,Pernin C,Vidal M,Comet M,Cuchet P International journal of nuclear medicine and biology The methyl-branched fatty acids, if radioiodine labelled in alpha position, are potentially adapted to a selective study of FA myocardial uptake. To determine the position and the number of methyl radicals that are necessary to obtain a maximal uptake and a minimal degradation, we measured time-activity evolution of isolated and perfused rat hearts after an injection of iodinated fatty acids which are mono- or dimethylated in alpha or beta position. Except for dimethyl fatty acid, the uptake is similar for all fatty acids studied to that of the straight chain analogue; beta mono- or dimethyl fatty acids seem best adapted to a study of the uptake because alpha monomethyl fatty acids undergo a metabolic degradation and alpha mono- and dimethyl fatty acids induce ventricular fibrillations.
Actinomadura apis sp. nov., isolated from a honey bee (Apis mellifera) hive, and the reclassification of Actinomadura cremea subsp. rifamycini Gauze et al. 1987 as Actinomadura rifamycini (Gauze et al. 1987) sp. nov., comb. nov. Promnuan Yaowanoot,Kudo Takuji,Ohkuma Moriya,Chantawannakul Panuwan International journal of systematic and evolutionary microbiology A Gram-reaction-positive aerobic actinomycete, designated strain IM17-1(T), was isolated from a honey bee (Apis mellifera) hive in Chiang Mai Province, Thailand. The strain formed a branched substrate mycelium and mature aerial mycelium bore short chains of arthrospores with warty surfaces. The cell wall contained meso-2,6-diaminopimelic acid (cell-wall type III) and the whole cell sugars were fucose, galactose, glucose, madurose, mannose and ribose. The major isoprenoid quinone was hexahydrogenated menaquinone with nine isoprene units and the predominant cellular fatty acids were C₁₆:₀ (33.8 %), C₁₈:₁ω9c (32.7 %), summed feature 3 (C₁₆:₁ω7c and/or iso-C₁₅:₀ 2-OH) (8.7 %) and 10-methyl C₁₈:₀ (8.2 %). The phospholipids were diphosphatidylglycerol, phosphatidylinositol and phosphatidylinositol mannosides. These morphological and chemotaxonomic characteristics were consistent with the classification of IM17-1(T) within the genus Actinomadura. Based on 16S rRNA gene sequence analysis, strain IM17-1(T) was closely related to the type strains of Actinomadura cremea subsp. cremea (98.1 %) and Actinomadura cremea subsp. rifamycini (98.6 %); however, it represented a distinct phylogenetic lineage from the other species within this genus. The unique genetic characteristics were reaffirmed by low levels of DNA-DNA relatedness between strain IM17-1(T) and the two most closely related type strains, A. cremea subsp. cremea JCM 3308(T) (56.5±4.9 %) and A. cremea subsp. rifamycini JCM 3309(T) (31.0±22.6 %), and further supported the proposal of IM17-1(T) as a novel species. Strain IM17-1(T) ( = JCM 16576(T)  = TISTR 1980(T)) thus represents a novel species of the genus Actinomadura, for which the name Actinomadura apis sp. nov. is proposed. In addition, the genotypic and phenotypic data suggested the reclassification of Actinomadura cremea subsp. rifamycini Gauze et al. 1987 as a separate species, Actinomadura rifamycini sp. nov., comb. nov. 10.1099/ijs.0.026633-0
Further branching of valproate-related carboxylic acids reduces the teratogenic activity, but not the anticonvulsant effect. Bojic U,Elmazar M M,Hauck R S,Nau H Chemical research in toxicology In the present study, compounds derived from the anticonvulsant drug valproic acid (VPA, 2-n-propylpentanoic acid) and analogues known to be teratogenic were synthesized with an additional carbon-branching in one of the side chains. The substances were tested for their ability to induce anticonvulsant activity and sedation in adult mice, and neural tube defects (exencephaly) in the offspring of pregnant animals (Han:NMRI mice). In all cases, the rates of exencephaly, embryolethality, and fetal weight retardation induced by the methyl-branched derivatives were very low when compared to those of the parent compounds. These novel compounds exhibited anticonvulsant activity which was not significantly different from that of VPA. Neurotoxicity was considerably lower for some compounds as compared to VPA. Anticonvulsant activity and neurotoxicity of branched short chain fatty acids are far less structure-dependent and not related to teratogenic potency. Within this series of compounds, (+/-)-4-methyl-2-n-propyl-4-pentenoic acid and (+/-)2-isobutyl-4-pentenoic acid exhibited the most favorable profile in regard to high anticonvulsant effect, low sedation, and teratogenicity. Valproic acid analogues with additional methyl branching may be valuable antiepileptic agents with low teratogenic potential. 10.1021/tx950216s
Isolation and structural analysis of three neutral glycosphingolipids from a mixed population of Caenorhabditis elegans (Nematoda:Rhabditida). Gerdt S,Lochnit G,Dennis R D,Geyer R Glycobiology The free-living nematode, Caenorhabditis elegans, has been proposed and analyzed as a prototypic model for parasitic nematodes. In order to study whether there is a structural basis for the proposed analogy with respect to nematode glycoconjugates, we have analyzed Caenorhabditis elegans glycosphingolipids. Three, simple neutral glycosphingolipid components of the neutral glycolipid fraction were isolated by high-performance liquid chromatography. Structural analysis was performed by methylation analysis, exoglycosidase cleavage, matrix-assisted laser desorption/ ionization time-of-flight mass spectrometry, and ceramide analysis. The chemical structures have been determined as Glc beta 1Cer, Man beta 4Glc beta 1Cer and GlcNAc beta 3Man beta 4Glc beta 1Cer; that are characterized as belonging to the arthroseries of protostomial glycosphingolipids. The ceramide moiety of the parent glycosphingolipid-ceramide mono-hexoside was dominated by 2-hydroxy fatty acids, and a d17:1 spingoid-base with an iso- or anteiso-branched chain. The chemical composition of the three glycosphingolipids from Caenorhabditis elegans displayed close structural coincidence with the equivalent structures from the porcine parasitic nematode, Ascaris suum (G.Lochnit, R.D. Dennis, U.Zähringer, and R.Geyer, Glycoconjugate J., 1997), in support of this organism as a prototypic glycosphingolipid model for parasitic nematodes. 10.1093/glycob/7.2.265
Peroxisomal beta-oxidation. Purification of four novel 3-hydroxyacyl-CoA dehydrogenases from rat liver peroxisomes. Novikov D K,Vanhove G F,Carchon H,Asselberghs S,Eyssen H J,Van Veldhoven P P,Mannaerts G P The Journal of biological chemistry Peroxisomes are capable of beta-oxidizing a variety of substrates including the CoA esters of straight chain fatty acids, 2-methyl-branched fatty acids and the bile acid intermediates di- and trihydroxycoprostanic acids. The first reaction of peroxisomal beta-oxidation is catalyzed by an acyl-CoA oxidase. Rat liver peroxisomes contain three acyl-CoA oxidases: 1) palmitoyl-CoA oxidase, oxidizing straight chain acyl-CoAs; 2) pristanoyl-CoA oxidase, oxidizing 2-methyl-branched acyl-CoAs; and 3) trihydroxycoprostanoyl-CoA oxidase, oxidizing the CoA esters of the bile acid intermediates (Van Veldhoven, P.P., Vanhove, G., Asselberghs, S., Eyssen, H. J., and Mannaerts, G. P. (1992) J. Biol. Chem. 267, 20065-20074). We have now investigated whether the third step of peroxisomal beta-oxidation, catalyzed by a 3-hydroxyacyl-CoA dehydrogenase, is also catalyzed by multiple enzymes, using the 3-hydroxyacyl-CoA derivatives of palmitic acid, 2-methylpalmitic acid, and trihydroxycoprostanic acid as the substrates to monitor the dehydrogenase activities. In order to avoid contamination with mitochondrial 3-hydroxyacyl-CoA dehydrogenases, highly purified peroxisomes from untreated rats were employed as the enzyme source. Subfractionation of the peroxisomes revealed that the major portion of the dehydrogenase activities with all three substrates was present in the peripheral membrane protein fraction. Separation of this fraction on various chromatographic columns resulted in the purification of the well known multifunctional protein, a 78-kDa monomeric protein that displays 3-hydroxyacyl-CoA dehydrogenase plus hydratase activity, as well as of four additional novel dehydrogenases with different substrate specificities. Three of the enzymes are monomeric proteins of 35 kDa, 56 kDa, and 79 kDa, respectively. The latter enzyme also displays hydratase activity. The fourth enzyme is a dimer of 89 kDa, the subunits of which form a doublet at 40 kDa. The exact physiological role of each of the 3-hydroxyacyl-CoA dehydrogenases requires further investigation.
Novel long-chain anteiso-alkanes and anteiso-alkanoic acids in Antarctic rocks colonized by living and fossil cryptoendolithic microorganisms. Matsumoto G I,Friedmann E I,Watanuki K,Ocampo-Friedmann R Journal of chromatography Saponified extracts of rock samples colonized by cryptoendolithic microbial communities from the McMurdo Dry Valleys of Southern Victoria Land, Antarctica, were separated into hydrocarbon and fatty acid fractions by silica gel column chromatography. Hydrocarbons and methyl esters of fatty acids were analyzed by capillary gas chromatography-mass spectrometry. Unusually, a suite of long-chain anteiso-alkanes (a-C20 to a-C30) and anteiso-alkanoic acids (a-C20 to a-C30) were detected in many samples, together with straight-chain, branched and/or cyclic and acyclic isoprenoid compounds. These novel compounds are probably derived from unidentified heterotrophic bacteria or symbiotic processes in a unique microbial community in the Antarctic cold desert and suggest the occurrence of a special biosynthetic pathway. Long-chain anteiso-alkanes are probably formed through microbial decarboxylation of corresponding anteiso-alkanoic acids. They may serve as new biomarkers in environmental and geochemical studies. 10.1016/0021-9673(92)85056-y
Lipid biomarker signatures as tracers for harmful cyanobacterial blooms in the Baltic Sea. PloS one The recent proliferation of harmful cyanobacterial blooms (cyanoHABs) in the Baltic and other marginal seas poses a severe threat for the health of infested ecosystems as e.g. the massive export and decay of cyanobacterial biomass facilitates the spread of bottom water hypoxia. There is evidence that cyanoHABs occurred repeatedly in the Baltic Sea but knowledge of their spatiotemporal distribution and the cyanobacteria that contributed to them is limited. In this study, we examined representatives of the major bloom-forming heterocystous cyanobacteria (i.e. Aphanizomenon, Dolichospermum (formerly Anabaena) and Nodularia) to establish lipid fingerprints that allow tracking these environmentally important diazotrophs in the modern and past Baltic Sea. The distribution of normal and mid-chain branched alkanes, fatty acid methyl esters, bacteriohopanepolyols and heterocyst glycolipids permitted a clear chemotaxonomic separation of the different heterocystous cyanobacteria but also indicated a close phylogenetic relationship between representatives of the genera Aphanizomenon and Dolichospermum. Compared to the discontinuous nature of phytoplankton surveys studies, the distinct lipid profiles reported here will allow obtaining detailed spatiotemporal information on the frequency and intensity of Baltic Sea cyanoHABs as well as their community composition using the time-integrated biomarker signatures recorded in surface and subsurface sediments. As heterocystous cyanobacteria of the genera Aphanizomenon, Dolichospermum and Nodularia are generally known to form massive blooms in many brackish as well as lacustrine systems worldwide, the chemotaxonomic markers introduced in this study may allow investigating cyanoHABs in a great variety of contemporary environments from polar to tropical latitudes. 10.1371/journal.pone.0186360
Sexual dimorphism of lipids in Harderian glands of golden hamsters. Seyama Y,Otsuka H,Ohashi K,Vivien-Roels B,Pevet P Journal of biochemistry The Harderian gland of golden hamsters excretes alkyldiacylglycerol (ADG), the fatty acid and alkyl compositions of which differ between males and females. ADG in males contains mostly straight chain fatty acids, even- and odd-numbered, the major one being 15:0, while ADG in females contains iso- and anteiso-branched chain acids (34.0%). Iso-branching was found in both even- and odd-numbered acids, but anteiso-branching was found mostly in odd-numbered acids. The presence of propionic acid at the 3 position of the glycerol moiety in male ADG, and of isovaleric and 2-methylbutyric acids at the same position in female ADG was demonstrated by NMR spectrometry. Alkyl portions also exhibited sexual dimorphism in these lipids. ADG from males consisted of straight aliphatic chains, but branched chain components occupied almost half (45%) in ADG from females, and the branching resided at the iso- and anteiso-positions. The ADGs in glands from the two sexes were separated by Iatrobeads column chromatography into three and two subfractions, respectively. The fatty acid and alkyl compositions of these subfractions coincided with the above-mentioned results and with the behavior of the ADGs on thin-layer plates. These findings suggest that a sex hormone affects the metabolism of valine, leucine and isoleucine, and sexual dimorphism of ADGs occurs in the Harderian gland. 10.1093/oxfordjournals.jbchem.a124760
Anaerobic degradation of n-hexane in a denitrifying bacterium: further degradation of the initial intermediate (1-methylpentyl)succinate via C-skeleton rearrangement. Wilkes Heinz,Rabus Ralf,Fischer Thomas,Armstroff Antje,Behrends Astrid,Widdel Friedrich Archives of microbiology The anaerobic degradation pathway of the saturated hydrocarbon n-hexane in a denitrifying strain (HxN1) was examined by gas chromatography-mass spectrometry of derivatized extracts from cultures grown with unlabeled and deuterated substrate; several authentic standard compounds were included for comparison. The study was focused on possible reaction steps that follow the initial formation of (1-methylpentyl)succinate from n-hexane and fumarate. 4-Methyloctanoic, 4-methyloct-2-enoic, 2-methylhexanoic, 2-methylhex-2-enoic and 3-hydroxy-2-methylhexanoic acids (in addition to a few other methyl-branched acids) were detected in n-hexane-grown but not in n-hexanoate-grown cultures. Labeling indicated preservation of the original carbon chain of n-hexane in these acids. Tracing of the deuterium label of 3- d1-(1-methylpentyl)succinate in tentative subsequent products indicated a deuterium/carboxyl carbon exchange in the succinate moiety. This suggests that the metabolism of (1-methylpentyl)succinate employs reactions analogous to those in the established conversion of succinyl-CoA via methylmalonyl-CoA to propionyl-CoA. Accordingly, a pathway is proposed in which (1-methylpentyl)succinate is converted to the CoA-thioester, rearranged to (2-methylhexyl)malonyl-CoA and decarboxylated (perhaps by a transcarboxylase) to 4-methyloctanoyl-CoA. The other identified fatty acids match with a further degradation of 4-methyloctanoyl-CoA via rounds of conventional beta-oxidation. Such a pathway would also allow regeneration of fumarate (for n-hexane activation) from propionyl-CoA formed as intermediate and hence present a cyclic process. 10.1007/s00203-001-0381-3
Actinomadura barringtoniae sp. nov., an endophytic actinomycete isolated from the roots of Barringtonia acutangula (L.) Gaertn. Rachniyom Hathairat,Matsumoto Atsuko,Inahashi Yuki,Take Akira,Takahashi Yoko,Thamchaipenet Arinthip International journal of systematic and evolutionary microbiology A novel actinomycete strain, designated GKU 128, isolated from the roots of an Indian oak tree [Barringtonia acutangula (L.) Gaertn.] at Khao Khitchakut district, Chantaburi province, Thailand, was characterized by using a polyphasic approach. The strain formed a branched substrate and aerial mycelia which differentiated into straight to flexuous chains of smooth-ornamented spores. Analysis of the cell wall revealed the presence of meso-diaminopimelic acid and N-acetylmuramic acid in the peptidoglycan. The whole-cell sugars were glucose, madurose, mannose, rhamnose and ribose. Mycolic acids were absent. The major phospholipids were diphosphatidylglycerol, phosphatidylglycerol, phosphatidylinositol and phosphatidylinositolmannoside. The predominant menaquinones were MK-9(H6), MK-9(H8), MK-9(H0) and MK-9(H4). The major fatty acids were C16 : 0, C18 : 1ω9c and 10-methyl C18 : 0 (tuberculostearic acid). The genomic DNA G+C content was 70.5 mol%. Based on 16S rRNA gene sequence analysis, strain GKU 128 was closely related to the type strains of Actinomadura nitritigenes NBRC 15918 (99.2 % sequence similarity) and Actinomadura fibrosa JCM 9371 (98.7 %). The levels of DNA-DNA relatedness between strain GKU 128 and the closely related type species were less than 19 %. On the basis of phenotypic and genotypic characteristics, strain GKU 128 could be distinguished from its closely related type strains and represents a novel species of the genus Actinomadura, for which the name Actinomadura barringtoniae sp. nov. (=TBRC 7225=NBRC 113074) is proposed. 10.1099/ijsem.0.002714
Pseudonocardia thailandensis sp. nov., an actinomycete isolated from a subterranean termite nest. Sujarit Kanaporn,Sujada Nikhom,Kudo Takuji,Ohkuma Moriya,Pathom-Aree Wasu,Lumyong Saisamorn International journal of systematic and evolutionary microbiology A novel Gram-stain-positive bacterium designated CMU-NKS-70T was isolated from a subterranean termite nest and characterized using a polyphasic approach. The strain exhibited branching, pinkish-cream aerial mycelium and cream-brown substrate mycelium, and formed chains of rod-like spores. The 16S rRNA gene sequence analyses indicated that strain CMU-NKS-70T belonged to the genus Pseudonocardia, showing high similarity with Pseudonocardia oroxyli D10T (98.9 % 16S rRNA gene sequence similarity), Pseudonocardia xishanensis YIM 63638T (98.9 %) and Pseudonocardia kujensis A4038T (98.5 %). However, DNA-DNA relatedness values between strains CMU-NKS-70T and the closest phylogenetically related species ranged from 40.5±2.9 to 48.6±0.7 %. Whole-cell hydrolysates of strain CMU-NKS-70T consisted of meso-diaminopimelic acid, glucose, galactose, arabinose, mannose, ribose and rhamnose. The predominant menaquinone was MK-8(H4). The major cellular fatty acids (>10 %) were iso-C16 : 0, C16 : 0, C16 : 1ω7c and/or iso-C15 : 0 2-OH and 10-methyl C16 : 0. The polar lipids detected were phosphatidylethanolamine, phosphatidylmethylethanolamine, hydroxyphosphatidylethanolamine, phosphatidylglycerol, phosphatidylinositol, three unidentified glycolipids and two unidentified phospholipids. The G+C content of genomic DNA was 71.9 mol%. The physiological and biochemical properties also supported the phenotypic distinction of strain CMU-NKS-70T from its closely related species. On the basis of evidence from this study using a polyphasic approach, strain CMU-NKS-70T represents a novel species of the genus Pseudonocardia for which the name Pseudonocardia thailandensis sp. nov. is proposed. The type strain is CMU-NKS-70T (=JCM 31292T=TBRC 2000T). 10.1099/ijsem.0.002017
Characterization of neutral glycosphingolipids in human cataractous lens. Ogiso M,Irie A,Kubo H,Komoto M,Matsuno T,Koide Y,Hoshi M The Journal of biological chemistry Neutral glycosphingolipids were purified from human senile cataractous lenses by a combination of solvent extraction, Folch's partition, acetylation, and column chromatography using DEAE-Sephadex and Iatrobeads. Six major glycosphingolipids (A-F) from monohexosylceramide to pentahexosylceramide were identified by sugar composition analysis, methylation analysis, secondary ion-mass spectrometry, glycosidase digestion, and chromium trioxide oxidation. Their structures suggested that they were closely related in their metabolism: their sugar chains were in sequence and their ceramide moieties were similarly composed, namely C16:0 and C24:1 constituted most of the fatty acids, and long-chain base components were mostly C18-dihydrosphingosine with a small portion of C18-sphingosine. The sugar chains implied two pathways branching from lactosylceramide: one to globotriaosylceramide and the other to lactotriaosylceramide, which leads to the production of Le(x) glycolipid via neolacto type 2 core chain.
Influence of terminal branching on the transdermal permeation-enhancing activity in fatty alcohols and acids. Klimentová Jana,Kosák Petr,Vávrová Katerina,Holas Tomás,Hrabálek Alexandr Bioorganic & medicinal chemistry In order to investigate the effect of terminal chain branching in the skin permeation enhancers, seven alcohols and seven acids with the chain length of 8-12 carbons and terminal methyl or ethyl branching were prepared. Their transdermal permeation-enhancing activities were evaluated in vitro using theophylline as a model permeant and porcine skin, and compared to those of the linear standards. Terminal methyl branching increased the enhancing activity only in 12C acid, no effect was seen in the shorter ones. Terminal ethyl however produced a significant increase in activity. In the alcohols, the branching was likely to change the mode of action, due to a different relationship between the activity and the chain length. 10.1016/j.bmc.2006.08.013
Hepatic lipid profiling of deer mice fed ethanol using ¹H and ³¹P NMR spectroscopy: a dose-dependent subchronic study. Fernando Harshica,Bhopale Kamlesh K,Boor Paul J,Ansari G A Shakeel,Kaphalia Bhupendra S Toxicology and applied pharmacology Chronic alcohol abuse is a 2nd major cause of liver disease resulting in significant morbidity and mortality. Alcoholic liver disease (ALD) is characterized by a wide spectrum of pathologies starting from fat accumulation (steatosis) in early reversible stage to inflammation with or without fibrosis and cirrhosis in later irreversible stages. Previously, we reported significant steatosis in the livers of hepatic alcohol dehydrogenase (ADH)-deficient (ADH⁻) vs. hepatic ADH-normal (ADH⁺) deer mice fed 4% ethanol daily for 2 months [Bhopale et al., 2006, Alcohol 39, 179-188]. However, ADH⁻ deer mice fed 4% ethanol also showed a significant mortality. Therefore, a dose-dependent study was conducted to understand the mechanism and identify lipid(s) involved in the development of ethanol-induced fatty liver. ADH⁻ and ADH⁺ deer mice fed 1, 2 or 3.5% ethanol daily for 2 months and fatty infiltration in the livers were evaluated by histology and by measuring dry weights of extracted lipids. Lipid metabolomic changes in extracted lipids were determined by proton (¹H) and ³¹phosphorus (³¹P) nuclear magnetic resonance (NMR) spectroscopy. The NMR data was analyzed by hierarchical clustering (HC) and principle component analysis (PCA) for pattern recognition. Extensive vacuolization by histology and significantly increased dry weights of total lipids found only in the livers of ADH⁻ deer mice fed 3.5% ethanol vs. pair-fed controls suggest a dose-dependent formation of fatty liver in ADH⁻ deer mouse model. Analysis of NMR data of ADH⁻ deer mice fed 3.5% ethanol vs. pair-fed controls shows increases for total cholesterol, esterified cholesterol, fatty acid methyl esters (FAMEs), triacylglycerides and unsaturation, and decreases for free cholesterol, phospholipids and allylic and diallylic protons. Certain classes of neutral lipids (cholesterol esters, fatty acyl chain (-COCH₂-) and FAMEs) were also mildly increased in ADH⁻ deer mice fed 1 or 2% ethanol. Only small increases were observed for allylic and diallylic protons, FAMEs and unsaturations in ADH⁺ deer mice fed 3.5% ethanol vs. pair-fed controls. PCA of NMR data showed increased clustering by gradual separation of ethanol-fed ADH⁻ deer mice groups from their respective pair-fed control groups and corresponding ethanol-fed ADH⁺ deer mice groups. Our data indicate that dose of ethanol and hepatic ADH deficiency are two key factors involved in initiation and progression of alcoholic fatty liver disease. Further studies on characterization of individual lipid entities and associated metabolic pathways altered in our deer mouse model after different durations of ethanol feeding could be important to delineate mechanism(s) and identify potential biomarker candidate(s) of early stage ALD. 10.1016/j.taap.2012.07.026
[Analysis of fatty acids in Gmnocypris przewalskii oil by gas chromatography/mass spectrometry with base-catalyzed transesterification]. Bo Haibo,Wang Xia,Zhai Zongde,Li Yongmin,Chen Liren Se pu = Chinese journal of chromatography The composition of fatty acids (FA) in Gymnocypris przewalskii oil was identified and quantified by gas chromatography (GC)/electron impact (EI) mass spectrometry (MS). A base-catalyzed transesterification method was used to convert fatty acids to methyl esters. The lipids were extracted using petroleum ether and the total lipids in dried meat and skin of Gymnocypris przewalskii were about 25%. Forty-seven fatty acids were identified in the current study. Main types of fatty acids found in the oils were normal saturated, mono-branched, multi-branched, cyclopropane, furanoid, normal monounsaturated and polyunsaturated fatty acids. Saturated fatty acids were approximately 25. 7% of the total, and the main components were C(14:0) (3.4%), C(16:0) (19.4%) and C(18:0) (1.1%). Unsaturated fatty acids were totally 73.6%, and the major components of monounsaturated fatty acids were C(16:1 (9)) (19.8%), C(18:1) (9)) (18. 6%) and C(18:1 (11)) (7.3%); polyunsaturated fatty acids were mainly composed of C(18:2 (9,12)) (4.8%), C(18:3 (9, 12, 15)) (3.1%), C(20:4 (5, 8, 1, 14)) (1.2%), C(20:5 (5, 8, 11, 14, 17)) (EPA, 9.4%) and C(22:6 (4, 7, 10, 13, 16, 19)) (DHA, 6.7%). Especially, furyl-, cyclopropane- and several odd and branched chain fatty acids were found in Gymnocypris przewalskii oil. It is thus an important dietary resource of functional fatty acids.
Stereoselectivity in the 2-methylbutyrate incorporation into anteiso fatty acids in Bacillus subtilis mutants. Kaneda T Biochimica et biophysica acta Two Bacillus subtilis mutants defective in branched-chain alpha-ketoacid dehydrogenase can grow when 2-methylbutyrate is provided in trypticase soy medium. Both enantiomers of the acid supported growth of the mutants but the (S)-(+)-isomer (natural) was more active than the (R)-(-)-isomer (unnatural). The mutants utilized these isomers as primer to specifically synthesize either enantiomer of anteiso fatty acids. No racemization of the isomer primers was observed during the synthesis. Thus, cells grown with (-)-isomer possessed anteiso fatty acids (over 80%) of the total fatty acids, being entirely the unnatural enantiomer. The stereospecific synthesis was found to be controlled at the step of 2-methylbutyryl-CoA synthesis. In a wild strain, only (+)-specific acyl-CoA synthetase was detected. In the mutants, either enantiomer of 2-methylbutyrate could simultaneously induce both types, (+)-specific and (-)-specific, of acyl-CoA synthetase. (+)-Specific synthetase had a higher activity and affinity towards substrate than (-)-specific synthetase. The detailed preparative procedures for (R)-(-)- and 2-[3,4-3H]methylbutyric acid are described. 10.1016/0005-2760(88)90003-3
Isolation and characterization of a novel Forssman active acidic glycosphingolipid with branched isoglobo-, ganglio-, and neolacto-series hybrid sugar chains. Yamamoto H,Iida-Tanaka N,Kasama T,Ishizuka I,Kushi Y,Handa S Journal of biochemistry Equine kidney and spleen contain a Forssman active glycosphingolipid, and the structure of this glycolipid has been reported to be that of a globopentaosylceramide (GalNAcalpha-1,3GalNAcbeta-1,3Galalpha-1, 4Galbeta-1,4Glcbeta-1,1'Ceramide). We found that equine kidney contains several other anti-Forssman antibody-reactive glycosphingolipids. One of these acidic Forssman active glycosphingolipids was isolated and characterized by means of NMR, mass spectrometry, permethylation studies, and TLC-immunostaining. This glycolipid contains three moles of galactose, one mole of glucose, three moles of N-acetylgalactosamine, one mole of N-acetylglucosamine, and one mole of N-acetylneuraminic acid, and is stained on TLC with anti-Forssman antibodies and anti-GM2 ganglioside antibodies. HOHAHA and ROESY experiments and permethylation studies showed this glycolipid oligosaccharide to be branched at the innermost galactose; one chain has an isoglobo structure with a terminal Forssman disaccharide and the other chain is branched through the linkage of N-acetylglucosaminebeta-1,6 to the inner galactose. The nonreducing end of the GM2 trisaccharide is linked to this glucosamine. The structure of the oligosaccharide of the glycolipid presented here is a novel type, having branched isoglobo-, ganglio-, and neolacto-series oligosaccharides. Mass spectrometric analyses indicated the ceramide moiety of the glycolipid to be composed predominantly of hydroxy fatty acids (C20:0, C22:0, C23:0, C24:0, and C25:0) and hydroxysphinganine. GalNAcalpha-1,3GalNAcbeta-1,3Galalpha-1,3[GalNAcbet a-1, 4(NeuAcalpha-2,3)Galbeta-1,4GlcNAcbeta-1,6]Galbeta+ ++-1,4Glcbeta-1, 1'Ceramide 10.1093/oxfordjournals.jbchem.a022370
Analysis of the free fatty acid component of meibomian secretions in chronic blepharitis. Dougherty J M,McCulley J P Investigative ophthalmology & visual science Meibomian secretions were collected from 43 patients with chronic blepharitis and 8 normal controls. Patients were divided into six clinically distinct groups of chronic blepharitis. Individual secretions were weighed and separated into specific lipid classes by thin-layer chromatography. The free fatty acid (FFA) fraction was recovered, methylated, and analyzed by gas-liquid chromatography. Quantitation was achieved through the use of an internal standard, and qualitative analyses were aided by the use of commercial external standards. Carbon numbers were expressed in terms of their equivalent chain lengths (E.C.L.). For statistical comparisons, specific acid weights were expressed as nanograms per milligram of secretion. Data from individual subjects were tabulated by group and analyzed by a nonparametric analysis of variance. The FFA portion made up from 0.21% to 1.3% of the total meibomian secretion. Acids ranged in length from 12 to 29 carbon atoms. Iso-branched and anteisobranched carbon chains made up approximately 33% of the FFA fraction. E.C.L.'s corresponding to C16:0, C18:0, and C18:1 together made up a major portion of the total FFA fraction (mean = 49%). When compared to normals, a significantly decreased amount of C12:0 was seen in the mixed seborrheic/staphylococcal group and the meibomian seborrhea group. A significantly decreased amount of anteiso-branched C15:0 was seen in the mixed seborrheic/staphylococcal group. Significantly decreased amounts of anteiso-branched C23:0 were seen in all of the seborrheic blepharitides. A significantly increased amount of isobranched C22:0 was seen in the meibomian keratoconjunctivitis group. No significant differences were seen in the staphylococcal group.
Nocardioides aquiterrae sp. nov., isolated from groundwater in Korea. Yoon Jung-Hoon,Kim In-Gi,Kang Kook Hee,Oh Tae-Kwang,Park Yong-Ha International journal of systematic and evolutionary microbiology A bacterial strain, GW-9T, which was isolated from groundwater in Korea, was subjected to a polyphasic taxonomic study using phenotypic characterization and phylogenetic and genetic methods. Phylogenetic analysis based on 16S rDNA sequences showed that strain GW-9T forms an evolutionary lineage within the radiation enclosing Nocardioides species and, in particular, a coherent cluster with Nocardioides pyridinolyticus. The cell-wall peptidoglycan type of strain GW-9T was based on LL-diaminopimelic acid as the diamino acid, indicating wall chemotype I. The predominant menaquinone was MK-8(H4). Strain GW-9T had a cellular fatty acid profile containing straight-chain, branched, unsaturated and 10-methyl fatty acids. The major fatty acid was iso-C(16:0). The DNA G+C content of strain GW-9T was 73 mol%. The 16S rDNA of strain GW-9T was 99.2% similar to that of the type strain of Nocardioides pyridinolyticus and 94.9-96.0% similar to sequences of the type strains of other Nocardioides species. Differences in phenotypic characteristics and genetic distinctiveness indicate that strain GW-9T is separate from previously described Nocardioides species. Therefore, on the basis of the data presented, a novel species of the genus Nocardioides, Nocardioides aquiterrae sp. nov., is proposed. The type strain is strain GW-9T (=KCCM 41647T=JCM 11813T). 10.1099/ijs.0.02585-0
Sensitivity of phospholipase C (Bacillus cereus) activity to phosphatidylcholine structural modifications. el-Sayed M Y,DeBose C D,Coury L A,Roberts M F Biochimica et biophysica acta The structural features of a phosphatidylcholine molecule important for binding to phospholipase C (Bacillus cereus) have been examined using kinetic analyses of a series of short-chain phosphatidylcholines and analogues. Lipids examined had varying chain lengths, methyl branched chains, phenyl alkanoate chains, and a single fatty acyl chain (lysophosphatidylcholines). A comparison of Vmax and Km for monomolecularly dispersed dibutyroyl-, dihexanoyl- and diheptanoylphosphatidylcholine indicates that the length of the fatty acyl chains must be at least six carbons for efficient binding of the phosphatidylcholine to the enzyme. Enzymatic rates of hydrolysis for pure short-chain phosphatidylcholine micelles of different chain lengths or detergent mixed micelles with comparable concentrations of short- and long-chain phosphatidylcholines show no dependence on substrate chain length greater than six carbons. Methyl branching of short-chain phosphatidylcholines only inhibits phospholipase C activity when the methyl group is adjacent to the carbonyl (e.g., di(2-methyl)hexanoylphosphatidylcholine). In a similar fashion, phosphatidylcholines with phenylalkanoate chains become poor substrates when the phenyl group is near the acyl linkage. As the phenyl group is moved from C-4 to C-2 a large increase in the micellar apparent Km is observed. Chain specificity (sn-1 and/or sn-2 ester linkages) for binding is not absolute, since phospholipase C will hydrolyze micellar short-chain lysophosphatidylcholines at rates one tenth of phosphatidylcholines. In contrast, substitution of ester linkages with ether moieties yields phosphatidylcholine analogues which are even poorer substrates and not good inhibitors of phospholipase C. These results suggest that the carbonyl group and its immediate environment are important for phospholipid interacting with this water-soluble lipolytic enzyme. 10.1016/0005-2760(85)90056-6
Explorative characterization and taxonomy-aligned comparison of alterations in lipids and other biomolecules in Antarctic bacteria grown at different temperatures. Environmental microbiology reports Temperature significantly impacts bacterial physiology, metabolism and cell chemistry. In this study, we analysed lipids and the total cellular biochemical profile of 74 fast-growing Antarctic bacteria grown at different temperatures. Fatty acid diversity and temperature-induced alterations aligned with bacterial classification-Gram-groups, phylum, genus and species. Total lipid content, varied from 4% to 19% of cell dry weight, was genus- and species-specific. Most bacteria increased lipid content at lower temperatures. The effect of temperature on the profile was complex and more species-specific, while some common for all bacteria responses were recorded. Gram-negative bacteria adjusted unsaturation and acyl chain length. Gram-positive bacteria adjusted methyl branching (anteiso-/iso-), chain length and unsaturation. Fourier transform infrared spectroscopy analysis revealed Gram-, genus- and species-specific changes in the total cellular biochemical profile triggered by temperature fluctuations. The most significant temperature-related alterations detected on all taxonomy levels were recorded for mixed region 1500-900 cm , specifically the band at 1083 cm related to phosphodiester groups mainly from phospholipids (for Gram-negative bacteria) and teichoic/lipoteichoic acids (for Gram-positive bacteria). Some changes in protein region were detected for a few genera, while the lipid region remained relatively stable despite the temperature fluctuations. 10.1111/1758-2229.13232
Nocardioides dilutes sp. nov. isolated from soil in Bigeum Island, Korea. Dastager Syed G,Lee Jae-Chan,Ju Yoon-Jung,Park Dong-Jin,Kim Chang-Jin Current microbiology A short coccoid-rod-shaped, nonmotile actinobacteria strain MSL-11T was isolated from soil in Bigeum Island, Korea. A polyphasic study was undertaken to establish the taxonomic position of this strain. Phylogenetic analysis based on the 16S rRNA gene sequence revealed that strain MSL-11T forms an evolutionary lineage within the radiation of the genus Nocardioides. The cell wall peptidoglycan of strain MSL-11T contained LL-diaminopimelic acid, indicating wall chemotype I. The predominant menaquinone was MK-8(H4). Strain MSL-11T had a cellular fatty acid profile containing straight-chain, branched, unsaturated, and 10-methyl fatty acids, with iso-C16:0 as a major fatty acid component detected. The DNA G + C content of the strain was 71.8 mol%. Comparative 16S rRNA gene sequencing revealed that the strains constituted a distinct subclade within the genus Nocardioides, displaying a 16S rRNA gene sequence similarity of about 95.68% with Nocardioides jensenii DSM 20641T. On the basis of both phenotypic and phylogenetic evidence, the strain is separated from previously described Nocardioides species and should be assigned to represent a novel species of the genus Nocardioides, for which the name Nocardioides dilutes sp. nov. is proposed. The type strain is strain MSL-11T (= KCTC 19288T = DSM 19318T). 10.1007/s00284-008-9125-9
Purification and characterization of rat pancreatic fatty acid ethyl ester synthase and its structural and functional relationship to pancreatic cholesterol esterase. Kaphalia Bhupendra S,Ansari G A S Journal of biochemical and molecular toxicology Formation of fatty acid ethyl esters (FAEEs, catalyzed by FAEE synthase) has been implicated in the pathogenesis of chronic pancreatitis. In previous studies, we demonstrated that FAEE synthase, purified from rat liver microsomes, is identical to rat liver carboxylesterase (pI 6.1), and structurally and functionally different than that from pancreas. In this study, we purified and characterized rat pancreatic microsomal FAEE synthase, and determined its relationship with rat pancreatic cholesterol esterase (ChE). Since most of the serine esterases express p-nitrophenyl acetate (PNPA)-hydrolyzing activity as well as synthetic activity to form fatty acid esters or amides with a wide spectrum of alcohols and amines, respectively, we used PNPA-hydrolyzing activity to monitor the purification of FAEE synthase during various chromatographic purification steps. Synthesizing activity towards FAEEs, fatty acid methyl esters, and fatty acid anilides was measured only in the pooled fractions. At each step of purification (ammonium sulfate saturation, Q Sepharose XL, and heparin-agarose column chromatographies, and high performance liquid chromatography (anion exchange and gel filtration)) synthetic as well as hydrolytic activities copurified. Using ethanol, methanol, or aniline as substrates, the ester or anilide synthesizing activity of the purified protein was found to be 8709, 13000, and 2201 nmol/h/mg protein, respectively. The purified protein displayed a single band with an estimated molecular mass of approximately 68 kD upon SDS-PAGE under reduced denaturing conditions, cross-reacted with antisera against rat pancreatic ChE and showed 100% N-terminal sequence homology of the first 15 amino acids to that of rat pancreatic ChE. These results suggest that the purified protein has broad substrate specificity towards the conjugation of endogenous long chain fatty acids with substrates having hydroxyl and amino groups and is identical to ChE. 10.1002/jbt.10097
Identification of undescribed medium-chain acylcarnitines present in urine of patients with propionic and methylmalonic acidemias. Libert R,Van Hoof F,Thillaye M,Vincent M F,Nassogne M C,de Hoffmann E,Schanck A Clinica chimica acta; international journal of clinical chemistry In urine of patients with propionyl-CoA carboxylase deficiency or with methylmalonic acidemia, carnitine esters of 2-methyl-branched fatty acids of all chain lengths between 4 and 9 atoms of carbon were identified during the acute phase of the diseases. The chemical structure of these compounds was obtained by gas chromatography-mass spectrometry analysis of their fatty acid moieties in their free and picolinyl ester forms. We suggest mechanisms for the biosynthesis of these branched fatty acids, and their accumulation in urine during episodes of caloric imbalance. 10.1016/s0009-8981(00)00195-9
Nonpolar lipids of a halotolerant species of Staphylococcus epidermidis. Kushwaha S C,Kates M Canadian journal of biochemistry The nonpolar lipids of a halotolerant Staphylococcus epidermidis, isolated in pure culture from a growth medium for extreme halophiles containing 25% sodium chloride, were found to contain squalene, menaquinone-7, free fatty acids (mainly anteiso-15:0 and anteiso-17:0), undecaprenol, nonaprenol with predominately cis-isoprene residues, heptaprenol, with predominately trans-isoprene residues, and 1,2- and 1,3-diglycerides containing anteiso- 15:0 and anteiso-17:0 branched chain fatty acid residues. The above compounds were isolated in pure form by column and thin-layer chromatography and were characterized by ultraviolet, proton magnetic resonance, and mass spectra. Fatty acid moieities were characterized by gas-liquid chromatographic retention times of their methyl esters.
Altered fatty acid metabolism due to rifampicin-resistance conferring mutations in the rpoB Gene of Mycobacterium tuberculosis: mapping the potential of pharmaco-metabolomics for global health and personalized medicine. du Preez Ilse,Loots Du Toit Omics : a journal of integrative biology Abstract We investigated the use of gas chromatography mass spectrometry (GC-MS) metabolomics to better characterize rifampicin-resistance by comparing the fatty acid metabolomes of two rpoB mutant Mycobacterium tuberculosis strains (S522L and S531L) to that of a fully susceptible wild-type parent strain. Using the generated GC-MS metabolite data, principal component analysis (PCA) showed a clear differentiation between all three sample groups analyzed. We subsequently identified those metabolites contributing most to the variation in the data using PCA and partial least squares discriminant analysis (PLS-DA). The altered metabolite markers detected in the rifampicin-resistant mutants indicate a decreased synthesis of various 10-methyl branched-chain fatty acids and cell wall lipids, and an increased use of the shorter-chain fatty acids as carbon sources. Furthermore, the rpoB S531L mutant, previously reported to occur in well over 70% of all clinical rifampicin-resistant M. tuberculosis strains, potentially showed a better capacity for using these alternative energy sources, compared to the less frequently detected rpoB S522L mutant. This study is the first of its kind to associate rifampicin resistance, rpoB mutations, and the β-subunit of RNA polymerase in M. tuberculosis, with an altered fatty acid metabolism, thereby demonstrating the role that pharmaco-metabolomics can play in identifying new markers associated with drug resistance. 10.1089/omi.2012.0028
Direct assignment of the relative configuration in 1,3,n-methyl-branched carbon chains by (1)H NMR spectroscopy. Schmidt Yvonne,Breit Bernhard Organic letters On the basis of the assignment of methylene proton signals in (1)H NMR and determination of the chemical shift difference (Deltadelta), the relative configuration of 1,3,n-methyl-branched deoxypropionates can be determined directly. Comparison of the chemical shifts in the corresponding syn- and anti-configured compound pairs shows remarkable differences, while the absolute values depend on the presence and nature of adjacent functional groups. The determination of the Deltadelta values provides a reliable assessment of the relative configuration in 1,3,n-methyl-branched polypropionate chains and is even valid for macrocycles. 10.1021/ol1005399
Actinomadura syzygii sp. nov., an endophytic actinomycete isolated from the roots of a jambolan plum tree (Syzygium cumini L. Skeels). Rachniyom Hathairat,Matsumoto Atsuko,Indananda Chantra,Duangmal Kannika,Takahashi Yoko,Thamchaipenet Arinthip International journal of systematic and evolutionary microbiology The taxonomic position of an endophytic actinomycete, strain GKU 157T, isolated from the roots of a jambolan plum tree (Syzygium cumini L. Skeels) collected at Khao Khitchakut National Park, Chantaburi province, Thailand, was determined using a polyphasic taxonomic approach. 16S rRNA gene sequence analysis revealed that strain GKU 157T belongs to the genus Actinomadura and formed a distinct phyletic line with Actinomadura chibensis NBRC 106107T (98.6 % similarity). Strain GKU 157T formed an extensively branched, non-fragmenting substrate mycelium and aerial hyphae that differentiated into hooked to short spiral chains of about 20 non-motile spores with a warty surface. The cell wall contained meso-diaminopimelic acid and the whole-cell sugars were galactose, glucose, madurose, mannose and ribose. The N-acyl type of muramic acid was acetyl. Mycolic acids were absent. The phospholipids included phosphatidylglycerol (PG), diphosphatidylglycerol (DPG), phosphatidylinositol (PI), phosphatidylinositolmannoside (PIM) and two unknown phospholipids (PLs). The major menaquinone was MK-9(H6) and the predominant fatty acids were C16:0, iso-C16:0, C18:1ω9c, C18:0 and 10-methyl C18:0 (tuberculostearic acid). The genomic DNA G+C content was 73.1 mol%. A combination of DNA-DNA hybridization results and significant differences from related species in cultural, physiological and chemical characteristics indicated that strain GKU 157T represents a novel species of the genus Actinomadura, for which the name Actinomadura syzygii sp. nov. is proposed. The type strain is GKU 157T ( = BCC 70456T = NBRC 110399T). 10.1099/ijs.0.000203
Lipids as indicators of eutrophication in marine coastal sediments. Pinturier-Geiss L,Méjanelle L,Dale B,Karlsen D A Journal of microbiological methods Total organic carbon (TOC) and sedimentary lipid contents were investigated in the Bunnefjord, the most inner part of the Oslofjord (Norway). The Bunnefjord is an intermittent anoxic basin and has undergone major eutrophication since the early 1800s. A core from this fjord was collected at 100 m depths under anoxic remnant waters. The first 15 cm corresponding to deposits from 1500 to present were considered for analysis. Lipid classes were quantified by TLC-FID and the molecular composition of selected lipid classes was investigated by GC and GC-MS. Lipids were dominated by two main classes, phospholipids and hydrocarbons. The hydrocarbons represented up to 7.4% of total lipids in the sediment layers covering the period when the most extensive cultural eutrophication took place (1900 to 1970). The higher fluxes of organic carbon produced during this period may have controlled hydrocarbon inputs into the sediments, due to the hydrophobic character of these pollutants. The hydrocarbon concentration reversed toward pre-industrial levels in the more recent layers, which suggests an improvement of the water quality, possibly in response to improved treatment of the sewage in the cities around Bunnefjord. The second most abundant pool of lipids consists in phospholipids, mostly contributed by bacteria. Even though the concentration decreased with depth, their relative proportions to total lipids remained high, mainly in the deepest layers (>80% of total lipids). A rapid decrease of the polyunsaturated fatty acid methyl esters (FAME) from the phospholipid fraction in the upper 4 cm suggests a rapid biodegradation of planktonic inputs and meiofauna. Odd branched fatty acids were more probably contributed by bacteria linked to the high sedimentary hydrocarbon content. The down core distribution of 16:1omega7, 18:1omega7, 18:1omega5 esterified to phospholipids suggests a vertical zonation of the microbial community in relation to redox conditions and available organic matter. In addition to bacterial sulphur biomass, the presence of hopanoic acids in the phospholipids fraction suggests the contribution of bacteria growing on methane. According to the sterol composition, dominated by 4alpha(H)-methylsterols, dinoflagellates represent the major contributors to the organic matter produced in the water column, particularly during the period of extensive eutrophication. Long-chain diols (1,13-C(26), 1,15-C(30) and 1,15-C(32)) and long-chain keto-ols (1,15-C(30) and 1,15-C(32)) are reported for the first time at high latitudes. Their relative distributions (diol and keto-ol indexes of Versteegh et al. [Org. Geochem. 27 (1997)]) have allowed depicting a particular event during the eutrophication period, a freshwater intrusion with inputs of land-derived organic matter. This is in accordance with the downcore distribution of freshwater/terrestrial markers as sitosterol, dehydroabietic acid and iso- and anteiso-pimaric acids. The diol and keto-ol indexes have also underlined the general transition trend from marine to more brackish waters in the Bunnefjord. These last observations provide confidence into the use of these compounds in paleoenvironmental reconstruction. 10.1016/s0167-7012(01)00326-8
Correlations between surface area and the rate of enzymatic desaturation with methyl branched 8, 11, 14-eicosatrienoic acid. Patil G S,Sprecher H,Cornwell D G Lipids Methyl-branched derivatives of methyl 8,11,14-eicosatrienoate form stable liquid-expanded monolayers. Surface areas are expanded by the methyl branch. The expansion effect is a function of surface pressure. At high surface pressure, the greatest expansion occurs with a mid-point methyl branch. At low surface pressure, surface area increases continuously as the methyl group is moved along the carbon chain from carbon 19 to carbon 5. Desaturase activity varies inversely with surface area, and a linear correlation exists between surface area at low surface pressure and the desaturation rate. These data support the concept that lipid structure and its effect on short range forces between molecules is an important factor in desaturase activity.
Fatty acid composition of myelin isolated from the brain of a patient with cellular deficiency of co-enzyme forms of vitamin B12. Ramsey R B,Scott T,Banik N L Journal of the neurological sciences Myelin fractionation and subsequent lipid isolation have been carried out on a brain from a patient who suffered from a cellular deficiency of the adenosylcobalamin and methylcobalamin co-enzyme forms of vitamin B12. Examination of the fatty acid composition of choline and ethanolamine glycerophospholipids indicated a relative enrichment of odd-chain fatty acids which were identified by gas-liquid chromatography-mass spectroscopy as C15, C15:1, C17 and C17:1. A mixture of methyl branched C17 fatty acids was also identified. Odd-chain fatty acids accounted for 9.8% of the total fatty acid in the myelin choline phospholipid conpared to control values of 1.2%. The affected brain myelin phospholipids had a lower unsaturated fatty acid content. Examination of the myelin sphingolipids, sphingomyelin, cerebroside and sulfatide, yielded abnormal fatty acid profiles. The sphingomyelin contained only small amounts of C24:1 fatty acid. Both normal and hydroxy fatty acid containing cerebroside and sulfatide had reduced levels of C24 fatty acid. Determination of the relative hydroxy and normal fatty acid content of the galactolipids indicated an abnormally high hydroxy fatty acid level. Abnormal fatty acid profiles of brain cerebral sphingolipids have not been previously described in cases of vitamin B12 deficiency. Whether or not these alterations are characteristic will only be established by estimating sphingolipids in other such cases. 10.1016/0022-510x(77)90070-3
Targeted replacement of the mycocerosic acid synthase gene in Mycobacterium bovis BCG produces a mutant that lacks mycosides. Azad A K,Sirakova T D,Rogers L M,Kolattukudy P E Proceedings of the National Academy of Sciences of the United States of America A single gene (mas) encodes the multifunctional enzyme that catalyzes the synthesis of very long chain multiple methyl branched fatty acids called mycocerosic acids that are present only in slow-growing pathogenic mycobacteria and are thought to be important for pathogenesis. To achieve a targeted disruption of mas, an internal 2-kb segment of this gene was replaced with approximately the same size hygromycin-resistance gene (hyg), such that hyg was flanked by 4.7- and 1.4-kb segments of mas. Transformation of Mycobacterium bovis BCG with this construct in a plasmid that cannot replicate in mycobacteria yielded hygromycin-resistant transformants. Screening of 38 such transformants by PCR revealed several transformants representing homologous recombination with single crossover and one with double crossover. With primers representing the hyg termini and those representing the mycobacterial genome segments outside that used to make the transformation construct, the double-crossover mutant yielded PCR products expected from either side of hyg. Gene replacement was further confirmed by the absence of the vector and the 2-kb segment of mas replaced by hyg from the genome of the mutant. Thin-layer and radio-gas chromatographic analyses of the lipids derived from [1-14C]propionate showed that the mutant was incapable of synthesizing mycocerosic acids and mycosides. Thus, homologous recombination with double crossover was achieved in a slow-growing mycobacterium with an intron-containing RecA. The resulting mas-disrupted mutant should allow testing of the postulated roles of mycosides in pathogenesis. 10.1073/pnas.93.10.4787
Overexpression of peroxisome proliferator-activated receptor-alpha (PPARalpha)-regulated genes in liver in the absence of peroxisome proliferation in mice deficient in both L- and D-forms of enoyl-CoA hydratase/dehydrogenase enzymes of peroxisomal beta-oxidation system. Jia Yuzhi,Qi Chao,Zhang Zhongyi,Hashimoto Takashi,Rao M Sambasiva,Huyghe Steven,Suzuki Yasuyuki,Van Veldhoven Paul P,Baes Myriam,Reddy Janardan K The Journal of biological chemistry Peroxisomal beta-oxidation system consists of peroxisome proliferator-activated receptor alpha (PPARalpha)-inducible pathway capable of catalyzing straight-chain acyl-CoAs and a second noninducible pathway catalyzing the oxidation of 2-methyl-branched fatty acyl-CoAs. Disruption of the inducible beta-oxidation pathway in mice at the level of fatty acyl-CoA oxidase (AOX), the first and rate-limiting enzyme, results in spontaneous peroxisome proliferation and sustained activation of PPARalpha, leading to the development of liver tumors, whereas disruptions at the level of the second enzyme of this classical pathway or of the noninducible system had no such discernible effects. We now show that mice with complete inactivation of peroxisomal beta-oxidation at the level of the second enzyme, enoyl-CoA hydratase/L-3-hydroxyacyl-CoA dehydrogenase (L-PBE) of the inducible pathway and D-3-hydroxyacyl-CoA dehydratase/D-3-hydroxyacyl-CoA dehydrogenase (D-PBE) of the noninducible pathway (L-PBE-/-D-PBE-/-), exhibit severe growth retardation and postnatal mortality with none surviving beyond weaning. L-PBE-/-D-PBE-/- mice that survived exceptionally beyond the age of 3 weeks exhibited overexpression of PPARalpha-regulated genes in liver, despite the absence of morphological evidence of hepatic peroxisome proliferation. These studies establish that peroxisome proliferation in rodent liver is highly correlatable with the induction mostly of the L- and D-PBE genes. We conclude that disruption of peroxisomal fatty acid beta-oxidation at the level of second enzyme in mice leads to the induction of many of the PPARalpha target genes independently of peroxisome proliferation in hepatocytes, raising the possibility that intermediate metabolites of very long-chain fatty acids and peroxisomal beta-oxidation act as ligands for PPARalpha. 10.1074/jbc.M306363200
Trichostatin A effects on gene expression in the protozoan parasite Entamoeba histolytica. Ehrenkaufer Gretchen M,Eichinger Daniel J,Singh Upinder BMC genomics BACKGROUND:Histone modification regulates chromatin structure and influences gene expression associated with diverse biological functions including cellular differentiation, cancer, maintenance of genome architecture, and pathogen virulence. In Entamoeba, a deep-branching eukaryote, short chain fatty acids (SCFA) affect histone acetylation and parasite development. Additionally, a number of active histone modifying enzymes have been identified in the parasite genome. However, the overall extent of gene regulation tied to histone acetylation is not known. RESULTS:In order to identify the genome-wide effects of histone acetylation in regulating E. histolytica gene expression, we used whole-genome expression profiling of parasites treated with SCFA and Trichostatin A (TSA). Despite significant changes in histone acetylation patterns, exposure of parasites to SCFA resulted in minimal transcriptional changes (11 out of 9,435 genes transcriptionally regulated). In contrast, exposure to TSA, a more specific inhibitor of histone deacetylases, significantly affected transcription of 163 genes (122 genes upregulated and 41 genes downregulated). Genes modulated by TSA were not regulated by treatment with 5-Azacytidine, an inhibitor of DNA-methyltransferase, indicating that in E. histolytica the crosstalk between DNA methylation and histone modification is not substantial. However, the set of genes regulated by TSA overlapped substantially with genes regulated during parasite development: 73/122 genes upregulated by TSA exposure were upregulated in E. histolytica cysts (p-value = 6 x 10(-53)) and 15/41 genes downregulated by TSA exposure were downregulated in E. histolytica cysts (p-value = 3 x 10(-7)). CONCLUSION:This work represents the first genome-wide analysis of histone acetylation and its effects on gene expression in E. histolytica. The data indicate that SCFAs, despite their ability to influence histone acetylation, have minimal effects on gene transcription in cultured parasites. In contrast, the effect of TSA on E. histolytica gene expression is more substantial and includes genes involved in the encystation pathway. These observations will allow further dissection of the effects of histone acetylation and the genetic pathways regulating stage conversion in this pathogenic parasite. 10.1186/1471-2164-8-216
Bilophila wadsworthia, gen. nov. and sp. nov., a unique gram-negative anaerobic rod recovered from appendicitis specimens and human faeces. Baron E J,Summanen P,Downes J,Roberts M C,Wexler H,Finegold S M Journal of general microbiology Strongly catalase-positive Gram-negative anaerobic rods were isolated from approximately half of all intra-abdominal specimens received from patients with gangrenous and perforated appendicitis, and subsequently also from normal faecal specimens. The organism was originally detected on Bacteroides-bile-aesculin (BBE) agar, and grew slowly on non-selective anaerobic media containing blood. It was stimulated by bile and differed from other known genera by being urease- and catalase-positive, and by reducing nitrate. It did not reduce sulphate. Other anaerobic Gram-negative rods showed no homology by DNA dot-blot hybridization. The thermal melting profile of chromosomal DNA showed 39-40 mol% G + C. The whole-cell fatty acid methyl ester profile included cyclic and branched long-chain acids, and differed from those of all other anaerobes that have been tested. beta-Lactamase was not detected. The name Bilophila wadsworthia gen. nov., sp. nov. is proposed for this organism. 10.1099/00221287-135-12-3405
Examination of the esterified fatty acids from mouse erythrocyte and synaptosomal membrane phospholipids and their distribution between the various phospholipid types. Wing D R,Harvey D J,La Droitte P,Robinson K,Belcher S Journal of chromatography Esterified fatty acids from mouse erythrocyte and synaptosomal membranes were characterised by fused-silica capillary gas-liquid chromatography and gas chromatography-mass spectrometry. Structural information was obtained from the mass spectra of a number of derivatives including trimethylsilyl (TMS), methyl and picolinyl esters together with the TMS ethers of glycols derived from the unsaturated acids. In addition to previously characterised acids, small concentrations of several acids previously unreported from these membranes were identified. These included branched chain acids and several unsaturated acids. 10.1016/s0021-9673(00)91051-3
Characterization of cerebroside (monoglycosylceramide) from the sea anemone, Metridium senile. Identification of the major long-chain base as an unusual dienic base with a methyl branch at a double bond. Karlsson K A,Leffler H,Samuelsson B E Biochimica et biophysica acta 1. Cerebroside of the sea anemone, Metridium senile, has been isolated (0.6 mg/g dry tissue weight) and structurally characterized. 2. The structure was shown by mass spectrometry, NMR spectroscopy and degradative studies as beta-glucopyranosylceramide. The major fatty acids were 16 : 0 and 20 : 0 D-2-hydroxy fatty acids. The major base was a novel base, D-erythro-1,3-dihydroxy-2-amino-9-methyl-trans-4, trans-8-octadecadiene. 3. Some unusual fatty acids of marine origin are suggested to originate in this long-chain base by metabolic conversion. 4. The implication of the methyl branch position of the base on our current view of sphingolipid function in the plasma membrane is discussed. 10.1016/0005-2760(79)90087-0
Nonomuraea jabiensis sp. nov., isolated from arid soil. Camas Mustafa,Sazak Anil,Spröer Cathrin,Klenk Hans-Peter,Cetin Demet,Guven Kiymet,Sahin Nevzat International journal of systematic and evolutionary microbiology A novel actinomycete, strain A4036(T), was isolated from a soil sample collected from the Jabi district in Abuja, Nigeria. The taxonomic position of strain A4036(T) was established using a combination of genotypic and phenotypic analyses. The organism formed extensively branched substrate and aerial hyphae that generated spiral chains of spores with warty surfaces. The cell wall contained meso-diaminopimelic acid and the cell-wall sugars were glucose, madurose, mannose and ribose. The predominant menaquinone was MK-9(H(4)). The polar lipids were diphosphatidylglycerol, phosphatidylethanolamine, phosphatidylinositol, phosphatidylmethylethanolamine, phosphatidylinositol mannoside, hydroxy-phosphatidylethanolamine, hydroxy-phosphatidylmethylethanolamine, two unidentified phospholipids and four unknown glucosamine-containing phospholipids. The major cellular fatty acids were iso-C(16 : 0) 2-OH, iso-C(16 : 0) and 10-methyl C(17 : 0). On the basis of 16S rRNA gene sequence similarity studies, strain A4036(T) grouped in the genus Nonomuraea, being most closely related to Nonomuraea angiospora IFO 13155(T) (99.05 %), Nonomuraea candida HMC10(T) (98.78 %), Nonomuraea kuesteri GW 14-1925(T) (98.49 %), Nonomuraea endophytica YIM 65601(T) (98.42 %), Nonomuraea maheshkhaliensis 16-5-14(T) (98.40 %), Nonomuraea turkmeniaca DSM 43926(T) (98.38 %), Nonomuraea helvata IFO 14681(T) (98.29 %), Nonomuraea rubra DSM 43768(T) (98.10 %) and Nonomuraea salmonea DSM 43678(T) (98.06 %). Levels of 16S rRNA gene sequence similarity to the type strains of other species of the genus Nonomuraea were <98 %. Despite the high 16S rRNA gene sequence similarities, DNA-DNA relatedness values and phenotypic data demonstrated that strain A4036(T) was clearly distinguished from all closely related species of the genus Nonomuraea. Thus, this isolate is considered to represent a novel species of the genus Nonomuraea, for which the name Nonomuraea jabiensis sp. nov. is proposed. The type strain is A4036(T) (= DSM 45507(T) = KCTC 19870(T)). 10.1099/ijs.0.039362-0
Metabolic imaging with beta-methyl-p-[(123)I]-iodophenyl-pentadecanoic acid identifies ischemic memory after demand ischemia. Dilsizian Vasken,Bateman Timothy M,Bergmann Steven R,Des Prez Roger,Magram Martin Y,Goodbody Anne E,Babich John W,Udelson James E Circulation BACKGROUND:After myocardial ischemia, prolonged suppression of fatty acid metabolism may persist despite restoration of blood flow, which is called metabolic stunning. We hypothesized that a branched-chain fatty acid, beta-methyl-p-[(123)I]-iodophenyl-pentadecanoic acid (BMIPP), might identify the presence of myocardial ischemia late after demand ischemia at rest up to 30 hours later. METHODS AND RESULTS:In 32 patients with exercise-induced ischemia on thallium SPECT, BMIPP was injected at rest within 30 hours of ischemia. SPECT images were acquired beginning 10 minutes after injection (early) and again 30 minutes after injection (delayed). Thallium and BMIPP SPECT data were read separately by 3 observers blinded to other imaging and clinical data. Agreement between BMIPP and thallium data for the presence of an abnormality on the patient level was 91% (95% CI, 75 to 98) for the early BMIPP data and 94% (95% CI, 79 to 99) for the delayed BMIPP data. Agreement between delayed BMIPP and thallium was 95% among 21 patients studied on the same day, a mean of 6.2+/-1.4 hours after exercise-induced ischemia, and 91% among the 11 patients studied on the next calendar day, a mean of 24.9+/-2.6 hours after ischemia (P=NS). The magnitude of resting BMIPP metabolic defect by semiquantitative visual analysis was correlated to the magnitude of exercise-induced thallium perfusion defect (r=0.6, P<0.001 for early BMIPP; r=0.5, P=0.005 for delayed BMIPP). CONCLUSIONS:Metabolic imaging with BMIPP identifies patients with recent exercise-induced myocardial ischemia. These findings support the concept that BMIPP imaging can successfully demonstrate the metabolic imprint of a stress-induced ischemic episode, also known as ischemic memory. 10.1161/CIRCULATIONAHA.104.530428
Transcriptome signature of liver tissue with divergent mutton odour and flavour using RNA deep sequencing. Gunawan Asep,Jakaria ,Listyarini Kasita,Furqon Ahmad,Sumantri Cece,Akter Syeda Hasina,Uddin Muhammad Jasim Gene Mutton consumption is less popular in many Asian countries including Indonesia, whose consumers often complain about the unpleasant flavour and odour of the meat. The main causes of mutton odour are the two compounds of branched chain fatty acid (BCFA): methylnonanoic (MNA), phenol, 3-methyl (MP), 4-methylnonanoic (MNA) and 4-ethyloctanoic (EOA) present in all the adipose tissue; and the 3-methylindole (MI) or skatole and indole, which are originated from pastoral diets. It is crucial to understand the genetic mechanism of mutton odour and flavour (MOF) to select sheep for lower BCFA and indole thus reduce the unpleasant flavour of meat. The aim of the present study was to investigate transcriptome profiling in liver tissue with divergent MOF using RNA deep sequencing. Liver tissues from higher (n = 3) and lower (n = 3) MOF sheep were analysed using Illumina HiSeq 2500. The total number of reads produced for each liver sample ranged from 21.37 to 25.37 million. Approximately 103 genes were differentially expressed (DEGs) with significance level of p-adjusted value <0.05. Among them, 60 genes were up-regulated, and 43 were down-regulated (p < 0.01, FC > 1.5) in higher MOF group. Differentially regulated genes in high MOF liver samples were enriched in biological processes such as cellular response to chemical stimulus and endogenous stimulus; cellular components such as such as basement membrane and extracellular matrix; and molecular functions such as haeme binding and oxidoreductase activity. Among the DEGs, metabolic phase I related genes belonging to the cytochrome P450 CYP2A6 were dominantly expressed. Additionally, phase II conjugation genes including UDP glucuronosyltransferases UGT2B18, sulfotransferase SULT1C1, and glutathione S-transferase GSTM1 were identified. The dominant candidate genes for SOF could be cytochrome P450, sodium-channel protein, transmembrane protein, glutathione transferase, UDP glucuronosyltransferases and sulfotransferase. Pathway analysis identified steroid hormone biosynthesis and chemical carcinogenesis by cytochrome P450 pathways which may play important roles in MOF-related molecules metabolism. This work highlighted potential genes and gene-networks that may affect meat off flavour and odour in sheep. 10.1016/j.gene.2018.06.086
Marmoricola aurantiacus gen. nov., sp. nov., a coccoid member of the family Nocardioidaceae isolated from a marble statue. Urzì C,Salamone P,Schumann P,Stackebrandt E International journal of systematic and evolutionary microbiology A Gram-positive, aerobic bacterium with coccoid cells occurring singly, in pairs and in clusters was isolated from the surface of a marble statue. The peptidoglycan contain LL-diaminopimelic acid as diagnostic diamino acid and a single glycine residue as interpeptide bridge (type A3 gamma). The major menaquinone is MK-8(H4). The cellular fatty acid pattern consists of straight chain saturated and monounsaturated components and 10-methyl octadecanoic (tuberculostearic) acid as the only branched chain fatty acid. Phosphatidylinositol, phosphatidylglycerol and diphosphatidylglycerol occur as characteristic polar lipids. The DNA G + C composition is 72 mol%. According to its phylogenetic position and 16S rDNA signature nucleotides, the organism is a member of the family Nocardioidaceae. The combination of chemotaxonomic characteristics is unique within this family and supports the description of a new genus and new species, Marmoricola aurantiacus. The type strain is strain BC 361T (= DSM 12652T). 10.1099/00207713-50-2-529
Fish oil supplemented for 9 months does not improve glycaemic control or insulin sensitivity in subjects with impaired glucose regulation: a parallel randomised controlled trial. Clark Louise F,Thivierge M C,Kidd Claire A,McGeoch Susan C,Abraham Prakash,Pearson Donald W M,Horgan Graham W,Holtrop Grietje,Thies Frank,Lobley Gerald E The British journal of nutrition The effects of fish oil (FO) supplementation on glycaemic control are unclear, and positive effects may occur only when the phospholipid content of tissue membranes exceeds 14% as n-3 PUFA. Subjects (n 36, thirty-three completed) were paired based on metabolic parameters and allocated into a parallel double-blind randomised trial with one of each pair offered daily either 6 g of FO (3·9 g n-3 PUFA) or 6 g of maize oil (MO) for 9 months. Hyperinsulinaemic-euglycaemic-euaminoacidaemic (HIEGEAA) clamps (with [6,6 2H2 glucose]) were performed at the start and end of the intervention. Endogenous glucose production (EGP) and whole-body protein turnover (WBPT) were each measured after an overnight fast. The primary outcome involved the effect of oil type on insulin sensitivity related to glycaemic control. The secondary outcome involved the effect of oil type on WBPT. Subjects on FO (n 16) had increased erythrocyte n-3 PUFA concentrations >14%, whereas subjects on MO (n 17) had unaltered n-3 PUFA concentrations at 9%. Type of oil had no effect on fasting EGP, insulin sensitivity or total glucose disposal during the HIEGEAA clamp. In contrast, under insulin-stimulated conditions, total protein disposal (P=0·007) and endogenous WBPT (P=0·001) were both increased with FO. In an associated pilot study (n 4, three completed), although n-3 PUFA in erythrocyte membranes increased to >14% with the FO supplement, the enrichment in muscle membranes remained lower (8%; P<0·001). In conclusion, long-term supplementation with FO, at amounts near the safety limits set by regulatory authorities in Europe and the USA, did not alter glycaemic control but did have an impact on WBPT. 10.1017/S0007114515004274
Ladderane lipid distribution in four genera of anammox bacteria. Rattray Jayne E,van de Vossenberg Jack,Hopmans Ellen C,Kartal Boran,van Niftrik Laura,Rijpstra W Irene C,Strous Marc,Jetten Mike S M,Schouten Stefan,Sinninghe Damsté Jaap S Archives of microbiology Intact ladderane phospholipids and core lipids were studied in four species of anaerobic ammonium oxidizing (anammox) bacteria, each representing one of the four known genera. Each species of anammox bacteria contained C18 and C20 ladderane fatty acids with either 3 or 5 linearly condensed cyclobutane rings and a ladderane monoether containing a C20 alkyl moiety with 3 cyclobutane rings. The presence of ladderane lipids in all four anammox species is consistent with their putative physiological role to provide a dense membrane around the anammoxosome, the postulated site of anammox catabolism. In contrast to the core lipids, large variations were observed in the distribution of ladderane phospholipids, i.e. different combinations of hydrophobic tail (ladderane, straight chain and methyl branched fatty acid) types attached to the glycerol backbone sn-1 position, in combination with different types of polar headgroup (phosphocholine, phosphoethanolamine or phosphoglycerol) attached to the sn-3 position. Intact ladderane lipids made up a high percentage of the lipid content in the cells of "Candidatus Kuenenia stuttgartiensis", suggesting that ladderane lipids are also present in membranes other than the anammoxosome. Finally, all four investigated species contained a C27 hopanoid ketone and bacteriohopanetetrol, which, indicates that hopanoids are anaerobically synthesised by anammox bacteria. 10.1007/s00203-008-0364-8
Identification of six species in the new genus Cronobacter (Enterobacter sakazakii) from culture using gas chromatographic analysis of fatty acid methyl esters. Whittaker Paul Journal of AOAC International Capillary GC with flame ionization detection (FID) was used to determine the cellular fatty acid (CFA) profiles of six species in the new genus Cronobacter (Enterobacter sakazakii). The six different species are C. sakazakii, C. malonaticus, C. dublinensis, C. muytjensii, C. turicensis, and C. genomospecies. For GC-FID analysis, whole cell fatty acid methyl esters (FAMEs) from cells cultured on brain heart infusion (BHI) agar at 35 degrees C for 24 h were obtained by saponification, methylation, and extraction into hexane-methyl tert-butyl ether. A data set for 57 strains of Cronobacter species was prepared using fatty acid profiles from two or three replicates prepared on different days. Major fatty acids of the Cronobacter strains evaluated in this study were straight-chain C12:0, C14:0, C16:0, and unsaturated C18:1, omega7c, summed C16:1 omega7c/C16:1 omega6c, and summed C14:0 3-OH/iso-C16:1, and C17:0 omega cyclo 7-8. The CFA profiles for the Cronobacter species are similar, but there are several fatty acids-C12:0, C14:0, C16:0, C18:1 omega7c, and summed C16:1 omega7c/ C16:1 omega6c--that differ significantly among these six species. Analysis of FAMEs from Cronobacter strains grown on BHI agar by a rapid GC-FID method is a sensitive procedure for the identification of these organisms, and this analytical method provides a procedure for the differentiation of strains from closely related Cronobacter species. 10.5740/jaoacint.10-451
Ester hydroxy derivatives of methyl oleate: tribological, oxidation and low temperature properties. Sharma Brajendra K,Doll Kenneth M,Erhan Sevim Z Bioresource technology Five branched oleochemicals were prepared from commercially available methyl oleate and common organic acids; and their lubricant properties were determined. These branched oleochemicals are characterized as 9(10)-hydroxy-10(9)-ester derivatives of methyl oleate. These derivatives show improved low temperature properties, over olefinic oleochemicals, as determined by pour point and cloud point measurements. The derivatization also increased thermo-oxidative stability, measured using both pressurized differential scanning calorimetry (PDSC) and thin film micro oxidation (TFMO) methods. Branched oleochemicals were used as additives both in soybean oil and in polyalphaolefin. Their lubrication enhancement was evaluated by both four-ball and ball-on-disk wear determinations. These derivatives have good anti-wear and friction-reducing properties at relatively low concentrations, under all test loads. Their surface tensions were also determined and a trend was observed. The materials with larger side chain branches had lower surface tension than those containing smaller side chain branches. An exception to this trend was found when studying the compound with the carbonyl containing levulinic acid side chain, which had the highest surface tension of the branched oleochemicals studied. Overall, the data indicate that some of these derivatives have significant potential as a lubricating oil or fuel additives. 10.1016/j.biortech.2007.12.057
Identification and quantification of lipids from rabbit Harderian glands by gas chromatography/mass spectrometry. Harvey D J Biomedical chromatography : BMC Lipids from hydrolysed extracts of Harderian glands from the rabbit were examined as trimethylsilyl, acetonide, nicotinate and picolinyl esters and shown to consist mainly of acylated glycerol ethers and acylated hydroxy-glycerol ethers. Constituents amounting to 98.8% of the recovered secretion were identified. Fatty acids were mainly normal, saturated compounds with chain lengths from 12 to 24 carbon atoms; n-16:0 and n-18:0 accounted for about 40% of the identified acids. Small concentrations of iso-17:0 and unsaturated acids with 18-carbon chains were also identified. Fatty alcohols were again mainly normal-unsaturated compounds; the chains varied from C18 to C25 with 20:0-OH and 22:0-OH being the most abundant. Three types of 1-alkyl glycerols were found. The major constituents had normal, saturated chains with from 14 to 23 carbon atoms with the even carbon chains predominating. These were accompanied by hydroxylated derivatives of the 16- and 18-carbon glycerol ethers with hydroxy groups in the 10, 11 and 12 positions. Branched-chain glycerol ethers were of low concentration and contained predominantly iso chains. Many of these compounds have not been reported before in this secretion. Low concentrations of the previously reported hydroxy acids with n-C14, -C15 and -C16 chains were also found. Nicotinate derivatives were applied to the structural determination of glycerol ethers for the first time and shown to reveal the position of methyl branch points in an analogous manner to that previously shown for mono- and di-hydric alcohols. Acids were identified as picolinyl esters. 10.1002/bmc.1130050402
Polyketide origin of pheromones of Carpophilus davidsoni and C. mutilatus (Coleoptera: Nitidulidae). Bartelt R J,Weisleder D Bioorganic & medicinal chemistry Biosynthesis of pheromones from Carpophilus davidsoni Dobson and C. mutilatus Erichson was investigated by feeding the beetles diets containing isotopically substituted (13C and deuterium) fatty acids and then analyzing the resulting labeled pheromone components. (2E,4E,6E,8E)-7-Ethyl-3,5-dimethyl-2,4,6,8-undecate traene, (2E,4E,6E,8E)-3,5,7-trimethyl-2,4,6,8-undecatetraen e and (2E,4E,6E)-5-ethyl-3-methyl-2,4,6-nonatriene from C. davidsoni and (3E,5E,7E)-5-ethyl-7-methyl-3,5,7-undecatriene from C. mutilatus were abundant enough to be analyzed by both NMR spectroscopy and MS. Eleven additional minor analogues were analyzed only by MS. Each hydrocarbon can be assembled from just three different acyl units: The initial unit can be acetate, propionate or butyrate. Propionate is the second unit in all of the analogues encountered so far, extending the chain by two carbons and producing a methyl branch. Subsequent chain-extending units can be either propionate or butyrate, leading to additional methyl or ethyl branches, respectively. The final acyl unit is either propionate or butyrate and it loses its carboxyl carbon during hydrocarbon biosynthesis. A hydrocarbon with four total units is a triene and one with five is a tetraene. Assembly is proposed to be as in usual fatty acid anabolism, except that other precursor units are used in addition to acetate and that the double-bond reduction step of each chain-elongation cycle does not occur, leaving the conjugated, unsaturated system. Seven of the analyzed hydrocarbons were not previously known to occur in C. davidsoni; two of these are novel: (2E,4E,6E,8E)-5,7-diethyl-3-methyl-2,4,6,8-undecate traene and (2E,4E,6E)-3,5-dimethyl-2,4,6-octatriene.
Conformational stability and thermodynamic characterization of the lipoic acid bearing domain of human mitochondrial branched chain alpha-ketoacid dehydrogenase. Naik Mandar T,Huang Tai-Huang Protein science : a publication of the Protein Society The lipoic acid bearing domain (hbLBD) of human mitochondrial branched chain alpha-ketoacid dehydrogenase (BCKD) plays important role of substrate channeling in oxidative decarboxylation of the branched chain alpha-ketoacids. Recently hbLBD has been found to follow two-step folding mechanism without detectable presence of stable or kinetic intermediates. The present study describes the conformational stability underlying the folding of this small beta-barrel domain. Thermal denaturation in presence of urea and isothermal urea denaturation titrations are used to evaluate various thermodynamic parameters defining the equilibrium unfolding. The linear extrapolation model successfully describes the two-step; native state <-->denatured state unfolding transition of hbLBD. The average temperature of maximum stability of hbLBD is estimated as 295.6 +/- 0.9 K. Cold denaturation of hbLBD is also predicted and discussed. 10.1110/ps.04783104
Diet-induced milk fat depression is associated with alterations in ruminal biohydrogenation pathways and formation of novel fatty acid intermediates in lactating cows. Ventto Laura,Leskinen Heidi,Kairenius Piia,Stefański Tomasz,Bayat Ali R,Vilkki Johanna,Shingfield Kevin J The British journal of nutrition The biohydrogenation theory of milk fat depression (MFD) attributes decreases in milk fat in cows to the formation of specific fatty acids (FA) in the rumen. Trans-10, cis-12-CLA is the only biohydrogenation intermediate known to inhibit milk fat synthesis, but it is uncertain if increased ruminal synthesis is the sole explanation of MFD. Four lactating cows were used in a 4×4 Latin square with a 2×2 factorial arrangement of treatments and 35-d experimental periods to evaluate the effect of diets formulated to cause differences in ruminal lipid metabolism and milk fat synthesis on the flow of FA and dimethyl acetal at the omasum. Treatments comprised total mixed rations based on grass silage with a forage:concentrate ratio of 35:65 or 65:35 containing 0 or 50 g/kg sunflower oil (SO). Supplementing the high-concentrate diet with SO lowered milk fat synthesis from -20·2 to -31·9 % relative to other treatments. Decreases in milk fat were accompanied by alterations in ruminal biohydrogenation favouring the trans-10 pathway and an increase in the formation of specific intermediates including trans-4 to trans-10-18 : 1, trans-8, trans-10-CLA, trans-9, cis-11-CLA and trans-10, cis-15-18 : 2. Flow of trans-10, cis-12-CLA at the omasum was greater on high- than low-concentrate diets but unaffected by SO. In conclusion, ruminal trans-10, cis-12-CLA formation was not increased on a diet causing MFD suggesting that other biohydrogenation intermediates or additional mechanisms contribute to the regulation of fat synthesis in the bovine mammary gland. 10.1017/S0007114517000010
Subcellular localization and physiological role of alpha-methylacyl-CoA racemase. Ferdinandusse S,Denis S,IJlst L,Dacremont G,Waterham H R,Wanders R J Journal of lipid research alpha-Methylacyl-CoA racemase plays an important role in the beta-oxidation of branched-chain fatty acids and fatty acid derivatives because it catalyzes the conversion of several (2R)-methyl-branched-chain fatty acyl-CoAs to their (S)-stereoisomers. Only stereoisomers with the 2-methyl group in the (S)-configuration can be degraded via beta-oxidation. Patients with a deficiency of alpha-methylacyl-CoA racemase accumulate in their plasma pristanic acid and the bile acid intermediates di- and trihydroxycholestanoic acid, which are all substrates of the peroxisomal beta-oxidation system. Subcellular fractionation experiments, however, revealed that both in humans and rats alpha-methylacyl-CoA racemase is bimodally distributed to both the peroxisome and the mitochondrion. Our findings show that the peroxisomal and mitochondrial enzymes are produced from the same gene and that, as a consequence, the bimodal distribution pattern must be the result of differential targeting of the same gene product. In addition, we investigated the physiological role of the enzyme in the mitochondrion. Both in vitro studies with purified heterologously expressed protein and in vivo studies in fibroblasts of patients with an alpha-methylacyl-CoA racemase deficiency revealed that the mitochondrial enzyme plays a crucial role in the mitochondrial beta-oxidation of the breakdown products of pristanic acid byconverting (2R,6)-dimethylheptanoyl-CoA to its (S)-stereoisomer.
First total syntheses of (Z)-15-methyl-10-hexadecenoic acid and the (Z)-13-methyl-8-tetradecenoic acid. Carballeira Néstor M,Montano Nashbly,Padilla Luis F Chemistry and physics of lipids The first total syntheses for the (Z)-15-methyl-10-hexadecenoic acid and the (Z)-13-methyl-8-tetradecenoic acid were accomplished in seven steps and in 31-32% overall yields. The (trimethylsilyl)acetylene was the key reagent in both syntheses. It is proposed that the best synthetic strategy towards monounsaturated iso methyl-branched fatty acids with double bonds close to the omega end of the acyl chain is first acetylide coupling of (trimethylsilyl)acetylene to a long-chain bifunctional bromoalkane followed by a second acetylide coupling to a short-chain iso bromoalkane, since higher yields are thus obtained. Spectral data is also presented for the first time for these two unusual fatty acids with potential as biomarkers and as topoisomerase I inhibitors. 10.1016/j.chemphyslip.2006.10.003
Mathematical method for the prediction of retention times of fatty acid methyl esters in temperature-programmed capillary gas chromatography. Torres Alexandre G,Trugo Nádia M F,Trugo Luiz C Journal of agricultural and food chemistry An accurate method for identification of fatty acids in complex mixtures analyzed by temperature-programmed capillary gas chromatography is described. The method is based on a mathematical approach using regression curves obtained by plotting the relative retention times of fatty acid methyl esters (FAMEs) analyzed in isothermal and gradient temperature conditions. The method was applied to a complex biological sample (human milk), and it was possible to identify 64 fatty acids, including branched-chain and other fatty acids for which reference standards were not readily available. The identities of the majority of the peaks were confirmed by mass spectrometry. The relative residuals and the relative differences between estimated and measured relative retention times of individual FAMEs varied from 0.03 to 3.15% and from 0.0 to 2.9%, respectively. The method is useful for identification of fatty acids in routine analysis. 10.1021/jf011259j
[Investigations on the structure of the sphingolipids of the genus Bacteroides (author's transl)]. Fritsche D Zentralblatt fur Bakteriologie, Parasitenkunde, Infektionskrankheiten und Hygiene. Erste Abteilung Originale. Reihe A: Medizinische Mikrobiologie und Parasitologie In 1972 Fritsche and Thelen have described the difference between the structure of the komplex lipids of the genus Bacteroides and the genus Sphaerophorus. Further investigations of Fritsche demonstrated the possibility of grouping gramnegative anaerobes into the genus Bacteroides in spite of the fact, that one of the final products of metabolism of these strains is butyric acid. These strains are the so-called butyric acid producing Bacteroides. This paper describes the structure of the still unknown fatty acids of the komplex lipids of Bacteroides strains and confirms the heterogenity of the sphingosine bases of Bacteroides as a principle. Fife strains of Bacteroides - with and without production of butyric acid - were used for purification of their long chain bases, which were characterized by degradation. The unknown fatty acids were isolated from B. thetaiotaomicron and analyzed by Dr. Rosenfelder with the aid of mass spectrometry, O-methylation and dehydratisation. The experiments of Rosenfelder demonstrate, that the unknown fatty acids have the behaviour of 3-hydroxy fatty acids, the two main peaks are a hexadecanoic and a heptade-behaviour of 3-hydroxy fatty acids, the two main peaks are a hexadecanoic and a heptadecanoic acid. They have an identical behaviour with the 3-hydroxy-15-methyl-palmitic acid of Myxococcus fulvus. Therefore the genus Bacteroides differs from the genus Sphaerophorus by synthesis of 3-hydroxy fatty acids. The production of sphingolipids is a common characteristic of the genus Bacteroides, each of the five strains demonstrated a heterogeneous pattern of bases with sphingosines with 16 to 20, perhaps also 12 to 14 carbon atoms, sometimes predominantly the branched and n-heptadeca- and the octadeca-sphinganine can be identified. The possibility of the production of phyto-sphingosines is discussed.
Assessment of Fuel Quality Parameters and Selection of Bacteria Using PROMETHEE-GAIA Algorithm. Shunmugam Sumathy,Gayathri Manickam,Muralitharan Gangatharan Methods in molecular biology (Clifton, N.J.) Recently, biodiesel is gaining significant importance due to eco-friendly nature and development of large-scale production methodologies. Biodiesel is a mixture of mono-alkyl esters of fatty acids (FA). During transesterification, the long-chain FAs are combined with methanol to produce fatty acid methyl ester (FAME), the principle component of biodiesel. The biodiesel fuel properties are determined by structural components of FAs such as chain length, degree of unsaturation, and branching of the carbon chain. The fuel quality of biodiesel are evaluated by assessing the properties such as cetane number (CN), iodine value (IV), cold filter plugging point (CFPP), higher heating value (HHV), cloud point (CP), pour point (PP) etc., of FAME. The amount of lipid or fat produced may vary from organism to organism. A particular species may have high biomass with low lipid content and vice versa. So the selection of suitable species/genus by decision analysis software is much needed. Besides various multi-criteria decision analyses, Preference Ranking Organization Method for Enrichment of Evaluation (PROMETHEE) and Graphical Analysis for Interactive Aid (GAIA) analysis is considered as the most promising tool in selecting the prominent biodiesel producing strain. Here we describe the method of evaluating the fuel quality parameters for the produced FAME and selecting the prominent strain through PROMETHEE-GAIA algorithm. 10.1007/978-1-4939-9484-7_14
Location of functional groups in mycobacterial meromycolate chains; the recognition of new structural principles in mycolic acids. Watanabe Motoko,Aoyagi Yutaka,Mitome Hidemichi,Fujita Tsuyoshi,Naoki Hideo,Ridell Malin,Minnikin David E Microbiology (Reading, England) Mycobacterial alpha-, methoxy- and keto-mycolic acid methyl esters were separated by argentation chromatography into mycolates with no double bond, with one trans double bond or with one cis double bond. Meromycolic acids were prepared from each methyl mycolate fraction by pyrolysis, followed by silver oxide oxidation, and analysed by high-energy collision-induced dissociation/fast atom bombardment MS to reveal the exact locations of the functional groups within the meromycolate chain. The locations of cis and trans double bonds, cis and trans cyclopropane rings, methoxy and keto groups, and methyl branches within the meromycolate chain were determined from their characteristic fragment ion profiles, and the structures of the meromycolic acids, including those with three functional groups extracted from Mycobacterium tuberculosis H37Ra, Mycobacterium bovis BCG and Mycobacterium microti, were established. Meromycolic acids with one cis double bond were structurally closely related to those with one cis cyclopropane ring, whereas the meromycolic acids with one trans cyclopropane ring were closely related to the corresponding meromycolic acids with one cis cyclopropane ring. A close relationship between methoxy- and keto-meromycolic acids was also implied. The relationship between the meromycolic acids with a trans double bond and the other meromycolic acids was not clearly revealed, and they did not appear to be immediate substrates for trans cyclopropanation. 10.1099/00221287-148-6-1881
Mycolic acids of Mycobacterium aurum. Structure and biogenetic implications. Lanéelle M A,Lacave C,Daffé M,Lanéelle G European journal of biochemistry Mycobacterium aurum (type strain) was analyzed for its mycolate content. Three types of mycolates were identified: di-unsaturated, oxo and dicarboxy mycolates, each type being constituted by two subtypes. The acid released by pyrolysis was identified as docosanoic acid. By use of mass spectrometry and oxidation techniques, the structures of these six subtypes of mycolates were elucidated. They contain Z and E double bonds, the latter having an adjacent methyl branch. No cyclopropane ring was observed. All the methyl branches occurring in these mycolates derived from methionine, the methyl-branched chiral center adjacent to the double bond having an R configuration. The structures of the major di-unsaturated mycolates suggest that they cannot be the precursors of oxo mycolates. The amount of long-chain secondary alcohol (2-octadecanol) obtained from the whole cells was found to be much greater than that expected from hydrolysis of wax ester mycolate (ester of 2-octadecanol and dicarboxy-mycolic acid). Further investigations showed that 2-octadecanol was also present in triacylglycerols, esterifying the omega-carboxyl group of long-chain fatty acids structurally related to dicarboxy-mycolates. 10.1111/j.1432-1033.1988.tb14416.x
1-Alkyl-2,3-diacylglycerol synthesis in primary culture cells of guinea pig harderian gland. Park S H,Kano K,Seyama Y Journal of biochemistry Using a primary culture system of guinea pig Harderian gland cells, we investigated the metabolism of a unique lipid: 1-alkyl-2,3-diacylglycerol containing methyl-branched fatty acids. The cells were obtained by collagenase digestion, and cells with lipid-droplets were collected by two-step centrifugation. We cultured these cells, and examined their lipid and fatty acid compositions. The de novo synthesis of lipids in these cells was studied as to the incorporation of [1(2)-14C]acetate and [U-14C]glucose. The major lipid proved to be 1-alkyl-2,3-diacylglycerol, as in tissue, and it contained a large amount of methylbranched fatty acids specific to this gland. The incorporation of [14C]acetate and [14C]glucose into 1-alkyl-2,3-diacylglycerol in the cultured cells amounted to 79.7 and 88.2% of the total incorporation into the lipid fraction, respectively. The incorporation of [14C]acetate into fatty acids in the cultured cells was detected for the chain lengths of C14 to C25. The activities of glycerol-3-phosphate dehydrogenase in the cultured cells and Harderian gland were lower than that in adipose tissue. These results confirm that cultured cells reflect the lipid metabolism originating in the Harderian gland and show that this culture system can serve as one part of the armamentarium for further study of this unique lipid metabolism. 10.1093/oxfordjournals.jbchem.a124205
Lipid composition in the classification of Rhodococcus equi. Barton M D,Goodfellow M,Minnikin D E Zentralblatt fur Bakteriologie : international journal of medical microbiology The fatty acid, menaquinone and polar lipid composition of representatives of Rhodococcus equi and related taxa were determined. All of the R. equi strains had major proportions of straight chain saturated, monounsaturated and 10-methyl branched fatty acids, dihydrogenated menaquinones with eight isoprene units as the predominant isoprenologue, and characteristic polar lipid patterns that contained diphosphatidylglycerol, phosphatidylethanolamine, phosphatidylinositol, phosphatidylinositol mannosides and glycolipids including a "cord factor"-like compound that was most pronounced in fresh isolates. The mycolic acids of these strains fell within the range C24 to C48, had 0 to 4 double bonds and released major amounts of C14:0 esters on pyrolysis. These lipid data provide further evidence that R. equi strains form a distinct taxospecies within the genus Rhodococcus. The remaining strains also gave lipid profiles consistent with their assignment to the genus Rhodococcus. These organisms included strains identified as R. sputi. 10.1016/s0934-8840(89)80002-7
Effects of resistant potato starch on odor emission from feces in Swine production units. Willig Stephanie,Lösel Dorothea,Claus Rolf Journal of agricultural and food chemistry Odor emission from swine facilities is determined by microbial breakdown of amino acids or carbohydrates in the pig colon. It was the aim to influence apoptosis and thus amino acid availability for odor formation by feeding resistant starch (300 g kg(-1) feed) over the whole fattening period to 40 pigs. Concentrations of 12 key components (indoles, volatile fatty acids, methanethiol) were measured in feces and headspace over the slurry duct and compared to 40 normally fed controls in a separate compartment. Concentrations of substances resulting from amino acids were reduced in feces by 70% (indoles) and 8% (branched chain fatty acids) and in the headspace by 72% and 20%. Resistant starch only led to minor increases of straight chain fatty acid concentration. Maximal reduction occurred for 3-methyl-1H-indole (skatole) which is the main determinant of malodor so that the results point to promising strategies for reducing pig odor emission. 10.1021/jf048658+
Diversity and specificity of lipid patterns in basal soil food web resources. Kühn Jakob,Schweitzer Kathlin,Ruess Liliane PloS one Soil food webs are important drivers for key ecological functions in terrestrial systems such as carbon and nutrient cycling. However, soil food web models generally lack quantitative data, mainly due to the shortage in high-throughput methods to describe energy flows. In marine environments, multivariate optimization models (Quantitative Fatty Acid Signature Analysis) and Bayesian approaches (source-tracking algorithm) were established to predict the proportion of predator diets using lipids as tracers. A premise for the application of such models to soil systems is to acquire the fatty acid pattern of a broad range of resources and to reveal potential overlap in their signatures. We present a comprehensive comparison of lipid pattern across widespread taxa of plants (leaves and roots, n = 48), algae (n = 59), fungi (n = 60), and bacteria (n = 62) as basal food web resources. Lipid profiles from microorganisms and algae were assessed from laboratory cultures, whereas plant tissue was derived from an arable field. A lipid library was constructed and multivariate data analyses (hierarchical clustering, nMDS) was used to assess the extent of separation in lipid pattern by species or resource type. The performance of the lipid library was tested by leave-one-prey-out (LOPO) analysis, giving the distinctiveness of the resource (prey) groups. Fungi and plant leaves were correctly assigned based on their lipid pattern with more than 98%, while plant roots and bacteria achieved 88 and 85%, respectively. However, algae were only correctly classified by 60%, pointing to a bias in the herbivore food chain. Fatty acids most important for separation of algae and plant leaves were of the omega 3 type, i.e. 16:3ω3 and 18:3ω3. In plant roots 18:1ω9 was most important, whereas bacteria were distinguished predominantly by methyl-branched fatty acids. Overall, the lipid pattern of major soil food web resources are sufficiently differentiated to allow for qualitative (biomarker) analyses as well as quantitative modelling, yet with precaution in the case of algae. 10.1371/journal.pone.0221102
Analysis of beta-hydroxy-beta-methyl butyrate in plasma by gas chromatography and mass spectrometry. Nissen S,Van Koevering M,Webb D Analytical biochemistry A method for measuring the branched chain hydroxy acid beta-hydroxy-beta-methyl butyrate (HMB, a product of leucine catabolism) has been described. A [2H6]HMB internal standard was added to plasma and standards, and samples were extracted with diethyl ether, backextracted into neutral phosphate, dried, and derivatized for gas chromatography and mass spectrometry. The natural HMB was monitored at 175 amu and the deuterated HMB was monitored at 181 amu. Standard curves were linear to at least 25 microns and were quantitatively recovered from plasma. Basal concentrations of plasma HMB were from 1 to 2 microM in sheep and increased three- to fourfold when leucine's alpha-ketoacid (alpha-ketoisocaproate, KIC) was fed to lambs. This method can also be adapted to quantitate KIC and other branched chain ketoacids in plasma during the same run. 10.1016/0003-2697(90)90522-b
Cellular fatty acids of Alcaligenes and Pseudomonas species isolated from clinical specimens. Dees S B,Moss C W Journal of clinical microbiology The cellular fatty acid composition of 25 clinical isolates of Alcaligenes and Pseudomonas was determined by gas-liquid chromatography (GLC). The GLC fatty acid profiles of three species of Pseudomonas were markedly different from those of Alcaligenes. The most significant differences were the presence and relative amounts of hydroxy, branched-chain, and cyclopropane fatty acids. One of the major fatty acids in A. faecalis was a 17-carbon cyclopropane (17 delta) acid, whereas a 15-carbon branched-chain acid (13-methyl tetradecanoate) characterized isolates of P. putrefaciens. The determination of these fatty acids by GLC provides a rapid and specific means of distinguishing clinical isolates of Pseudomonas and Alcaligenes. 10.1128/jcm.1.5.414-419.1975
GC/MS determination of fatty acid picolinyl esters by direct curie-point pyrolysis of whole bacterial cells. Kurkiewicz Slawomir,Dzierzewicz Zofia,Wilczok Tadeusz,Dworzanski Jacek P Journal of the American Society for Mass Spectrometry A single-step method suitable for cellular fatty acid derivatization to picolinyl esters with the use of a pyrolyzer as a thermochemical micro-reactor was developed for whole bacterial cells. This reduced the preparation time from several hours to less than two minutes. In addition, the minimal bacterial mass required for analysis was reduced from several milligrams to micrograms. The profiling of cellular fatty acids of gram-positive and gram-negative bacteria was achieved using three derivatization methods: preparation of methyl esters, beta-picolinyl esters by Harvey's method and a new method based on pyrolytic derivatization to beta-picolinyl esters. It was shown that there are great similarities between profiles of bacterial fatty acids determined by the pyrolytic derivatization method and traditional preparation methods of picolinyl and methyl esters prior to GC analysis. Results obtained by application of the new technique have immense diagnostic value due to vast similarities between profiles of fatty acids derivatized to either picolinyl and methyl esters. Although the latter are referred to in the literature most often, mass spectra of picolinyl esters contain fragment ions that provide structural information about the chain branching, position of unsaturation, and other substituents. 10.1016/S1044-0305(02)00817-6
Nonomuraea muscovyensis sp. nov., isolated from soil. Ozdemir-Kocak Fadime,Isik Kamil,Veyisoglu Aysel,Tatar Demet,Sahin Nevzat International journal of systematic and evolutionary microbiology A novel actinomycete, strain FMN03(T), was isolated from a soil sample collected from Yuga Zapadnaya South-West Forest Park, Moscow, Russia. The isolate had chemical and morphological properties typical of members of the genus Nonomuraea and formed a distinct 16S rRNA gene subclade with the type strains Nonomuraea roseoviolacea subsp. carminata NBRC 15903(T) and Nonomuraea roseoviolacea subsp. roseoviolacea NBRC 14098(T). The organism formed extensively branched substrate and aerial hyphae, which generated spiral chains of spores with smooth surfaces. The cell wall contained meso-diaminopimelic acid and the whole cell sugars were glucose, galactose and trace amounts of madurose, mannose and xylose. The polar lipids were phosphatidylethanolamine, hydroxyphosphatidylethanolamine, four unidentified phospholipids, four unidentified glycolipids and one unidentified lipid. The predominant menaquinone was MK-9(H4). The major fatty acids were iso-C16 : 0 2-OH, C17 : 0 10-methyl, C17 : 1 cis9 and iso-C16 : 0. Analyses of its morphological, physiological and biochemical characteristics, together with DNA-DNA relatedness data, confirmed that strain FMN03(T) is a representative of a novel species of the genus Nonomuraea, which is distinct from closely related reference strains. Strain FMN03(T) ( = DSM 45913(T) = KCTC 29233(T)) is proposed as the type strain of a novel species, for which the name Nonomuraea muscovyensis sp. nov. is proposed. 10.1099/ijs.0.061291-0
Kinetic flux profiling elucidates two independent acetyl-CoA biosynthetic pathways in Plasmodium falciparum. Cobbold Simon A,Vaughan Ashley M,Lewis Ian A,Painter Heather J,Camargo Nelly,Perlman David H,Fishbaugher Matthew,Healer Julie,Cowman Alan F,Kappe Stefan H I,Llinás Manuel The Journal of biological chemistry The malaria parasite Plasmodium falciparum depends on glucose to meet its energy requirements during blood-stage development. Although glycolysis is one of the best understood pathways in the parasite, it is unclear if glucose metabolism appreciably contributes to the acetyl-CoA pools required for tricarboxylic acid metabolism (TCA) cycle and fatty acid biosynthesis. P. falciparum possesses a pyruvate dehydrogenase (PDH) complex that is localized to the apicoplast, a specialized quadruple membrane organelle, suggesting that separate acetyl-CoA pools are likely. Herein, we analyze PDH-deficient parasites using rapid stable-isotope labeling and show that PDH does not appreciably contribute to acetyl-CoA synthesis, tricarboxylic acid metabolism, or fatty acid synthesis in blood stage parasites. Rather, we find that acetyl-CoA demands are supplied through a "PDH-like" enzyme and provide evidence that the branched-chain keto acid dehydrogenase (BCKDH) complex is performing this function. We also show that acetyl-CoA synthetase can be a significant contributor to acetyl-CoA biosynthesis. Interestingly, the PDH-like pathway contributes glucose-derived acetyl-CoA to the TCA cycle in a stage-independent process, whereas anapleurotic carbon enters the TCA cycle via a stage-dependent phosphoenolpyruvate carboxylase/phosphoenolpyruvate carboxykinase process that decreases as the parasite matures. Although PDH-deficient parasites have no blood-stage growth defect, they are unable to progress beyond the oocyst phase of the parasite mosquito stage. 10.1074/jbc.M113.503557
Bailinhaonella thermotolerans gen. nov., sp. nov., a new member of the order Streptosporangiales. Feng Yu-Zhou,Yang Ling-Ling,Gao Sheng,Ji Yang,Yin Min,Zhao Yu-Rong,Chunyu Wei-Xun,Li Ping,Zhi Xiao-Yang,Tang Shu-Kun International journal of systematic and evolutionary microbiology A Gram-positive, aerobic, non-motile actinobacterium, designated YIM 75507, that was isolated from a soil sample collected from a dry-hot valley, was subjected to a polyphasic taxonomic study. The isolate formed branched hyphae and no fragmentation was found. Clustered spore chains were borne from aerial mycelium. The cell-wall peptidoglycan contained glutamic acid, alanine and meso-diaminopimelic acid. Whole-cell sugars were galactose, mannose, glucosamine, glucose and ribose. The major menaquinones were MK-9(H6), MK-9(H8) and MK-10(H6). The polar phospholipids contained phosphatidylmethylethanolamine, phosphatidylethanolamine and ninhydrin-positive phosphoglycolipid. Major fatty acids were iso-C16 : 0 and 10-methyl-C17 : 0. Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain YIM 75507 formed a stable and distinct lineage clustered with the genus Sinosporangium in the family Streptosporangiaceae. The draft genome sequence of strain YIM 75507 exhibited low average nucleotide identity to the closest related strain, Sinosporangium album CPCC 201354 (83.97 %), well below the 95-96 % species circumscription threshold. The G+C content of the genomic DNA was 73.8 mol%. On the basis of morphological, chemotaxonomic and phylogenetic evidence, strain YIM 75507 is assigned to a novel species of a new genus, for which the name Bailinhaonella thermotolerans gen. nov., sp. nov. is proposed. The type strain of Bailinhaonella thermotolerans is YIM 75507 (=KCTC 49229=CGMCC 4.7547). 10.1099/ijsem.0.003379
New 17-methyl-13-octadecenoic and 3,16-docosadienoic acids from the sponge Polymastia penicillus. Denis Claire,Wielgosz-Collin Gaëtane,Bretéché Anne,Ruiz Nicolas,Rabesaotra Vony,Boury-Esnault Nicole,Kornprobst Jean-Michel,Barnathan Gilles Lipids The phospholipid fatty acid composition of the North-East Atlantic sponge Polymastia penicillus (South Brittany, France) was investigated. Sixty fatty acids (FA) were identified as methyl esters (FAME) and N-acyl pyrrolidides (NAP) by gas chromatography-mass spectrometry (GC/MS), including eight Delta5,9 unsaturated FA and three long-chain 2-hydroxylated FA. The major phospholipid FA were palmitic (14.3% of the total FA mixture), vaccenic (12.7%), 15(Z)-docosenoic (13.4%) and 5(Z),9(Z)-hexacosadienoic (13.3%) acids. In addition to the iso- and anteiso-branched saturated FA, several unusual short-chain branched saturated FA were identified. In addition to the known Delta5,9 FA, and interestingly regarding their identification by GC-MS as N-acyl pyrrolidides, was the co-occurrence of unusual FA possessing a Delta3, Delta4 and Delta5 double bond such as iso-4-pentadecenoic, iso-5-heptadecenoic, anteiso-5-heptadecenoic and two new compounds, not hitherto found in nature, namely 17-methyl-13-octadecenoic (0.8%) and 3,16-docosadienoic (1.1%) acids. 10.1007/s11745-009-3291-9
Screening of bacterial associates of marine sponges for single cell oil and PUFA. Patnayak S,Sree A Letters in applied microbiology AIM:To screen bacterial associates from marine sponges for single cell oil (SCO)/polyunsaturated fatty acid (PUFA) production. METHODS AND RESULTS:Using Sudan black 'B' staining technique the bacterial associates were screened for cellular lipid accumulation, effect of culture media, incubation period and C : N ratio. Extraction of the bacterial lipids was carried out by Floch's method and fatty acid methyl esters were analysed by GC and GC/MS. Four bacterial associates of 50 isolated from eight marine sponges tested positive for lipid accumulation. Two bacterial associates, viz. Bacillus subtilis (RRL-8) from Aurora globostellata and Pseudomonas spp. (RRL-28) from Heteronema erecta were found to produce total lipids 16.9 and 31.7%, respectively, of their dry biomass. CONCLUSIONS:Increase in C:N ratio significantly improved lipid production to 33.4 and 42.7%. Both the isolates produced gamma-linolenic acid (18:3 omega6; 4.5 and 1.12% respectively), whereas B. subtilis showed 3.8% of eicosapentaenoic acid (20:5 omega3) along with branched chain fatty acids. SIGNIFICANCE AND IMPACT OF THE STUDY:This is the first report of oleaginous bacterial associates from marine sponges. 10.1111/j.1472-765X.2005.01671.x
Mechanism of the stimulation of branched chain oxoacid oxidation in liver by carnitine. May M E,Aftring R P,Buse M G The Journal of biological chemistry The oxidation of 4-methyl-2-oxopentanoate (alpha-ketoisocaproate) by rat liver mitochondria was shown to be independent of exogenous coenzyme A and exogenous NAD+. Carnitine stimulated the oxidation of 4-methyl-2-oxopentanoate in rat liver homogenates and mitochondria; octanoate, DL-octanoylcarnitine, 4-pentenoate, and 3-methylbutyrate (isovalerate) were inhibitory, and 2-bromopalmitate had no effect. Addition of carnitine was found to increase the export from the mitochondria of acylcarnitines derived from 4-methyl-2-oxopentanoate in the presence of absence of 4-pentenoate but not in the presence of octanoylcarnitine. It is concluded that the branched chain oxoacid dehydrogenase is localized on the inner surface of the inner mitochondrial membrane and that it is regulated in part by the intramitochondrial levels of branched chain fatty acyl-CoA esters and/or free CoA.
Meganema perideroedes gen. nov., sp. nov., a filamentous alphaproteobacterium from activated sludge. Thomsen Trine R,Blackall Linda L,de Muro Marilena Aquino,Nielsen Jeppe L,Nielsen Per H International journal of systematic and evolutionary microbiology An industrial wastewater treatment plant at Grindsted, Denmark, has suffered from bulking problems for several years caused by filamentous bacteria. Five strains were isolated from the sludge by micromanipulation. Phylogenetic analysis of the 16S rRNA gene sequences showed that the strains formed a monophyletic cluster in the Alphaproteobacteria, and they were phenotypically different from their closest relatives and from all hitherto known filamentous bacteria described (closest relative Brevundimonas vesicularis ATCC 11426(T), 89.8 % sequence similarity). In pure culture, the cells (1.5-2.0 microm) in filaments are Gram-negative and contain polyphosphate and polyhydroxyalkanoates. The optimum temperature for growth is 30 degrees C and the strains grow in 2 % NaCl and are oxidase- and catalase-positive. Ubiquinone 10 is the major quinone. The major fatty acid (C(18 : 1)omega7c) and smaller amounts of unsaturated fatty acids, 3-hydroxy fatty acids with a chain length of 16 and 18 carbon atoms and small amounts of 10-methyl-branched fatty acids with 18 carbon atoms (C(19 : 0) 10-methyl) affiliated the strains with the Methylobacterium/Xanthobacter group in the Alphaproteobacteria. The G+C content of the DNA is 42.9 mol% (for strain Gr1(T)). The two most dissimilar isolates by 16S rRNA gene comparison (Gr1(T) and Gr10; 97.7 % identical) showed 71.5 % DNA-DNA relatedness. Oligonucleotide probes specific for the pure cultures were designed for fluorescence in situ hybridization and demonstrated that two filamentous morphotypes were present in the Grindsted wastewater treatment plant. It is proposed that the isolates represent a new genus and species, Meganema perideroedes gen. nov., sp. nov. The type strain of Meganema perideroedes is strain Gr1(T) (=DSM 15528(T)=ATCC BAA-740(T)). 10.1099/ijs.0.02916-0
Structural studies of the major glycolipid from Saccharopolyspora genus. Gamian A,Mordarska H,Ekiel I,Ulrich J,Szponar B,Defaye J Carbohydrate research A major glycolipid was isolated from the well characterized Saccharopolyspora species, S. hirsuta, S. rectivirgula, S. erythraea and one not completely identified strain (Saccharopolyspora sp.). On the basis of sugar and methylation analysis, specific enzymatic and chemical degradations of the carbohydrate moiety, its FAB mass spectrometry and NMR spectroscopy characterizations, the carbohydrate part was shown to be the glycerol linked dimannoside alpha-D-Manp-(1-->3)-alpha-D-Manp-(1-->1/3)Gro. The internal mannose residue is esterified at C-6 by one fatty acid residue, whereas another fatty acyl chain substitutes the primary methylene position of glycerol. The main fatty acyl residues are anteiso-branched heptadecanoic acid and the iso-branched fatty acids iso-17:0, iso-16:0, and iso-18:0, with the former species being predominant. The major glycolipid has potential value for taxonomic and diagnostic purposes, especially in the specific diagnosis of farmer's lung disease.
Characterization of CDC group DF-3 by cellular fatty acid analysis. Wallace P L,Hollis D G,Weaver R E,Moss C W Journal of clinical microbiology Fourteen strains of Centers for Disease Control group DF-3 bacteria were examined for cellular fatty acid composition to evaluate their chemical relatedness to known bacterial species and groups. The fatty acids were liberated from whole cells by base hydrolysis, methylated, and analyzed by capillary gas-liquid chromatography. All group DF-3 strains possessed a distinct fatty acid profile which was characterized by large amounts (24%) of 12-methyltetradecanoate (a-C15:0), moderate amounts of saturated iso-branched-chain acids (i-C14:0 and i-C15:0), and small to moderate amounts of both branched- and straight-chain hydroxy acids (3-OH C15:0, i-3-OH C16:0, 3-OH C16:0, and i-3-OH C17:0). This fatty acid profile was unique as compared with the profiles of other bacteria we have previously tested but was most similar to the profiles of Capnocytophaga species. 10.1128/jcm.27.4.735-737.1989
A rapid micro technique for differentiating between iso, anteiso and other mono methyl branched fatty chains. Nicolaides N,Fu H C Lipids
Essential nutrient supplementation prevents heritable metabolic disease in multigenerational intrauterine growth-restricted rats. Goodspeed Danielle,Seferovic Maxim D,Holland William,Mcknight Robert A,Summers Scott A,Branch D Ware,Lane Robert H,Aagaard Kjersti M FASEB journal : official publication of the Federation of American Societies for Experimental Biology Intrauterine growth restriction (IUGR) confers heritable alterations in DNA methylation, rendering risk of adult metabolic syndrome (MetS). Because CpG methylation is coupled to intake of essential nutrients along the one-carbon pathway, we reasoned that essential nutrient supplementation (ENS) may abrogate IUGR-conferred multigenerational MetS. Pregnant Sprague-Dawley rats underwent bilateral uterine artery ligation causing IUGR in F1. Among the F2 generation, IUGR lineage rats were underweight at birth (6.7 vs. 8.0 g, P < 0.0001) and obese by adulthood (p160: 613 vs. 510 g; P < 0.0001). Dual energy X-ray absorptiometry studies revealed increased central fat mass (Δ+40 g), accompanied by dyslipidemic (>30% elevated, P < 0.05) serum triglycerides (139 mg/dl), very-LDLs (27.8 mg/dl), and fatty acids (632 µM). Hyperglycemic-euglycemic clamp studies and glucose tolerance testing revealed insulin resistance. Conversely, IUGR lineage ENS-fed rats did not manifest MetS, with significantly lower body weight (p160: 410 g), >5-fold less central fat mass, normal hepatic glucose efflux, and >70% reduced circulating triglycerides and very-LDLs compared with IUGR control-fed F2 offspring (P < 0.01). Moreover, increased methylation of the IGF-1 P2 transcriptional start site among IUGR lineage F2 offspring was reversed in ENS (P < 0.04). This is an initial demonstration that supplementation along the one-carbon pathway abrogates adult morbidity and associated epigenomic modifications of IGF-1 in a rodent model of multigenerational MetS. 10.1096/fj.14-259614
Deficiency in mycolipenate- and mycosanoate-derived acyltrehaloses enhances early interactions of Mycobacterium tuberculosis with host cells. Rousseau Cécile,Neyrolles Olivier,Bordat Yann,Giroux Stéphanie,Sirakova Tatiana D,Prevost Marie-Christine,Kolattukudy Pappachan E,Gicquel Brigitte,Jackson Mary Cellular microbiology Lipids that are uniquely found in the cell envelope of pathogenic mycobacteria, such as those containing multiple methyl-branched long-chain fatty acids, have long been thought to play a role in host-pathogen interactions. The recent construction by Dubey et al. (2002) Mol Microbiol 45: 1451-1459, of a Mycobacterium tuberculosis mutant that is deficient in the synthesis of the di- and tri-methylbranched fatty acids, mycolipenates and mycosanoates, found in some forms of diacyltrehaloses (DAT) and polyacyltrehaloses (PAT) provided the opportunity to assess the contribution of these complex lipids to pathogenesis directly. We provide evidence that DAT/PAT deficiency affects the surface global composition of the mycobacterial cell envelope improving the efficiency with which M. tuberculosis binds to and enters phagocytic and non-phagocytic host cells. Interestingly, this property did not affect the overall replication and persistence of the tubercle bacillus in the lungs, spleen and liver of mice infected via the respiratory or intravenous route. 10.1046/j.1462-5822.2003.00289.x
Actinomadura amylolytica sp. nov. and Actinomadura cellulosilytica sp. nov., isolated from geothermally heated soil. Jiao Jian-Yu,Liu Lan,Zhou En-Min,Wei Da-Qiao,Ming Hong,Xian Wen-Dong,Yuan Chang-Guo,Zhong Jing-Mei,Li Wen-Jun Antonie van Leeuwenhoek Two aerobic, Gram-positive actinomycetes, designated YIM 77502(T) and YIM 77510(T), were isolated from geothermally heated soil of Tengchong county, Yunnan province, south-west China. The taxonomic position of strains YIM 77502(T) and YIM 77510(T) were investigated by a polyphasic approach. Phylogenetic analyses based on 16S rRNA gene sequences showed that strains YIM 77502(T) and YIM 77510(T) belong to the genus Actinomadura. Both strains form extensively-branched substrate and aerial mycelia which differentiated into short spore chains. The cell wall of the two strains contained meso-diaminopimelic acid, while the whole-cell sugars detected were glucose, madurose, mannose and rhamnose. The polar lipid profile of strain YIM 77502(T) was found to consist of diphosphatidylglycerol, phosphatidylinositol mannoside, phosphatidylinositol, two unidentified phospholipids and an unidentified polar lipid, while strain YIM 77510(T) consisted of diphosphatidylglycerol, phosphatidylinositol mannoside and phosphatidylinositol. The respiratory quinones of strains YIM 77502(T) and YIM 77510(T) were MK-9(H6) and MK-9(H8). The major fatty acids (>10 %) of strain YIM 77502(T) were C17:0, iso-C16:0, C17:010-methyl and iso-C18:0, and those of strain YIM 77510(T) were iso-C16:0, C17:010-methyl and iso-C18:0. The G+C contents of strains YIM 77502(T) and YIM 77510(T) were determined to be 71.3 and 70.2 mol%, respectively. The DNA-DNA hybridization values of strains YIM 77502(T), YIM 77510(T) and their closest phylogenetic neighbours Actinomadura echinospora BCRC 12547(T) and Actinomadura umbrina KCTC 9343(T) were less than 70 %. Based on the morphological and physiological properties, and phylogenetic analyses, strains YIM 77502(T) and YIM 77510(T) are considered to represent two novel species of the genus Actinomadura, for which the names Actinomadura amylolytica sp. nov. (type strain YIM 77502(T) = DSM 45822(T) = CCTCC AA 2012024(T)) and Actinomadura cellulosilytica sp. nov. (type strain YIM 77510(T) = DSM 45823(T) = CCTCC AA 2012023(T)) are proposed. 10.1007/s10482-015-0465-8
19F-nuclear magnetic resonance study of glycerolipid fatty acyl chain order in Acholeplasma laidlawii B membranes. McDonough B,Macdonald P M,Sykes B D,McElhaney R N The Yale journal of biology and medicine The technique of 19F-nuclear magnetic resonance (19F-NMR) spectroscopy offers a number of advantages for studies of lipid fatty acyl chain orientation and dynamics in biomembranes. However, the geminal difluoromethylene fatty acid probes usually employed in such studies appreciably perturb the organization of lipid bilayers. We have thus synthesized a series of specifically monofluorinated palmitic acids and carried out biophysical, biochemical, and physiological studies establishing their suitability as relatively non-perturbing probes of lipid hydrocarbon chain organization. These 19F-NMR probes were then used to determine the fatty acyl chain order profiles of Acholeplasma laidlawii B membranes highly enriched in a variety of different exogenous fatty acids, particularly those containing a methyl branch or a trans-double bond.
Methamphetamine downregulates striatal glutamate receptors via diverse epigenetic mechanisms. Jayanthi Subramaniam,McCoy Michael T,Chen Billy,Britt Jonathan P,Kourrich Saїd,Yau Hau-Jie,Ladenheim Bruce,Krasnova Irina N,Bonci Antonello,Cadet Jean Lud Biological psychiatry BACKGROUND:Chronic methamphetamine (METH) exposure causes neuroadaptations at glutamatergic synapses. METHODS:To identify the METH-induced epigenetic underpinnings of these neuroadaptations, we injected increasing METH doses to rats for 2 weeks and measured striatal glutamate receptor expression. We then quantified the effects of METH exposure on histone acetylation. We also measured METH-induced changes in DNA methylation and DNA hydroxymethylation. RESULTS:Chronic METH decreased transcript and protein expression of GluA1 and GluA2 alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid receptor (AMPAR) and GluN1 N-methyl-D-aspartate receptor subunits. These changes were associated with altered electrophysiological glutamatergic responses in striatal neurons. Chromatin immunoprecipitation-polymerase chain reaction revealed that METH decreased enrichment of acetylated histone H4 on GluA1, GluA2, and GluN1 promoters. Methamphetamine exposure also increased repressor element-1 silencing transcription factor (REST) corepressor 1, methylated CpG binding protein 2, and histone deacetylase 2 enrichment, but not of sirtuin 1 or sirtuin 2, onto GluA1 and GluA2 gene sequences. Moreover, METH caused interactions of REST corepressor 1 and methylated CpG binding protein 2 with histone deacetylase 2 and of REST with histone deacetylase 1. Surprisingly, methylated DNA immunoprecipitation and hydroxymethylated DNA immunoprecipitation-polymerase chain reaction revealed METH-induced decreased enrichment of 5-methylcytosine and 5-hydroxymethylcytosine at GluA1 and GluA2 promoter sequences. Importantly, the histone deacetylase inhibitor, valproic acid, blocked METH-induced decreased expression of AMPAR and N-methyl-D-aspartate receptor subunits. Finally, valproic acid also attenuated METH-induced decrease H4K16Ac recruitment on AMPAR gene sequences. CONCLUSIONS:These observations suggest that histone H4 hypoacetylation may be the main determinant of METH-induced decreased striatal glutamate receptor expression. 10.1016/j.biopsych.2013.09.034
Highly stereocontrolled total synthesis of β-D-mannosyl phosphomycoketide: a natural product from Mycobacterium tuberculosis. Li Nan-Sheng,Scharf Louise,Adams Erin J,Piccirilli Joseph A The Journal of organic chemistry β-D-mannosyl phosphomycoketide (C32-MPM), a naturally occurring glycolipid found in the cell walls of Mycobacterium tuberculosis, acts as a potent antigen to activate T-cells upon presentation by CD1c protein. The lipid portion of C32-MPM contains a C32-mycoketide, consisting of a saturated oligoisoprenoid chain with five chiral methyl branches. Here we develop several stereocontrolled approaches to assemble the oligoisoprenoid chain with high stereopurity (>96%) using Julia-Kocienski olefinations followed by diimide reduction. By careful choice of olefination sites, we could derive all chirality from a single commercial compound, methyl (2S)-3-hydroxy-2-methylpropionate (>99% ee). Our approach is the first highly stereocontrolled method to prepare C32-MPM molecule with >96% stereopurity from a single >99% ee starting material. We anticipate that our methods will facilitate the highly stereocontrolled synthesis of a variety of other natural products containing chiral oligoisoprenoid-like chains, including vitamins, phytol, insect pheromones, and archaeal lipids. 10.1021/jo4006602
Glucosylceramide having a novel tri-unsaturated long-chain base from the spermatozoa of the starfish, Asterias amurensis. Irie A,Kubo H,Hoshi M Journal of biochemistry Glucosylceramide (Glc beta 1-1Cer) was isolated from the spermatozoa of the starfish, Asterias amurensis. The long-chain bases of the glycolipid consisted of dihydroxy (d18:2, d18:3, d19:3, and d22:2), and trihydroxy (t22:1) types. Long-chain aldehydes derived from them were analyzed mainly by proton nuclear-magnetic resonance to determine the detailed structures. Two of the tri-unsaturated bases were identified as (4E,8E,10E)-2-amino-4,8,10-octadecatriene-1,3-di ol (d18:3) and (4E,8E,10E)-2-amino-9-methyl-4,8,10-octadecatriene+ ++-1,3-diol (d19:3), which is a novel base. Both d22:2 and t22:1 had a cis double bond at the C9 or C13 position. All fatty acids were 2-hydroxylated (C14-C25): Most of them were saturated and unbranched. About 10% was mono-unsaturated and unbranched (C22-C25), while saturated but branched (iso- and anteiso-types) C15-C18 acids were found as minor components. The main fatty acids, which summed up to more than 93% of the fatty acids in the glucosylceramide, were n-14h:0, n-15h:0, n-16h:0, n-17h:0, n-18h:0, and n-24h:1. 10.1093/oxfordjournals.jbchem.a123089
Inter-correlated gut microbiota and SCFAs changes upon antibiotics exposure links with rapid body-mass gain in weaned piglet model. Che Lianqiang,Hu Qi,Wang Ru,Zhang Du,Liu Cong,Zhang Yihe,Xin Guizhong,Fang Zhengfeng,Lin Yan,Xu Shengyu,Feng Bin,Chen Daiwen,Wu De,Gao Fei The Journal of nutritional biochemistry The risk of overweight or obesity in association with early exposure of antibiotics remains an important public issue for health-care of children. Low-dose antibiotics (LDA) have been widely used to enhance growth rate of pigs, providing a good animal model to study the underlying mechanism. In present study, 28 female piglets, weaned at 21 d, were randomly classified into two groups, receiving either a control diet or a diet supplemented with LDA for 4 weeks. The total bacterial load and intestinal microbiota were determined by qPCR and 16S rRNA amplicon sequencing. UPLC-QTRAP-MS/MS and RNA-seq were further used to determine the colonic SCFAs and transcriptomes. Results showed that LDA significantly increased growth rate and food intake. The F/B index, Methanosphaera species, and the pathway of "carbohydrate metabolism" were improved by LDA exposure, indicating the better carbohydrate degradation and energy utilization. Furthermore, correlation analysis indicated the microbial community contributing to SCFAs production was enriched upon LDA exposure, associating with increased concentrations of short-chain and branched-chain fatty acids (caproate, 2-methyl butyrate and 4-methyl valerate). A multivariate linear fitting model analysis highlighted that caproate was positively correlated with two genera (Faecalibacterium and Allisonella) and four differentially expressed genes (ZNF134, TBX5, NEU4 and SEMA6D), which were all significantly increased upon LDA exposure. Collectively, our study indicates that the growth-promoting effect of LDA exposure in early life is associated with the shifts of colonic microbiota to increase utilization of carbohydrates and energy, enhanced SCFAs production and colonic functions. 10.1016/j.jnutbio.2019.108246
Preparation, Structural Analysis, and Intestinal Probiotic Properties of a Novel Oligosaccharide from Enzymatic Degradation of Polysaccharide. Journal of agricultural and food chemistry polysaccharide (HSP) has attracted more and more interest due to its potential health benefits. Despite being an excellent source for the preparation of oligosaccharides, there are currently no relevant research reports on HSP. In the present study, a novel oligosaccharide (HSO) with a molecular weight of 1791 Da and a degree of polymerization of 11 was prepared through enzymatic degradation of crude HSP (cHSP). Methylation and NMR analyses revealed that the main chain of HSO was (1 → 4)-α-d-glucose with two O-6-linked branched chains. Morphological observations indicated that HSO exhibited smooth surface with lamellar and filamentary structure, and the glycan size ranged from 0.03 to 0.20 μm. Notably, HSO significantly promoted the proliferation of , , and , thereby making positive alterations in intestinal microbiota composition. Moreover, HSO markedly increased the content of short-chain fatty acids during fermentation. Metabolomics analysis illustrated the important metabolic pathways primarily involving glucose metabolism, amino acid metabolism, and fatty acid metabolism. 10.1021/acs.jafc.3c05666
Chemical characterization of clinical isolates which are similar to CDC group DF-3 bacteria. Daneshvar M I,Hollis D G,Moss C W Journal of clinical microbiology Six clinical isolates, taken from blood or wounds, that had biochemical characteristics most similar to Centers for Disease Control group DF-3 bacteria were examined for cellular fatty acid composition and isoprenoid quinone content to evaluate their chemical relatedness to known bacterial species and groups. The fatty acids were liberated from whole cells by base hydrolysis, methylated, and analyzed by capillary gas-liquid chromatography. The isoprenoid quinones were extracted from lyophilized whole cells and analyzed by reverse-phase high-performance liquid chromatography. All six strains, which were designated group DF-3-like, possessed a distinct fatty acid profile that was characterized by large amounts (greater than 20%) of 13-methyltetradecanoate (i-C15:0) and 12-methyltetradecanoate (a-C15:0), moderate amounts of saturated branched-chain 13-carbon acids (i-C13:0 and a-C13:0) and hexadecanoate (n-C16:0), and small to moderate amounts of both branched- and straight-chain hydroxy acids (i-3-OH-C15:0, 3-OH-C16:0, i-3-OH-C17:0, and 2-OH-C17:0). This fatty acid profile was unique compared with the profiles of group DF-3 and other bacteria we have previously tested and is useful for the rapid identification of group DF-3-like isolates. The isoprenoid quinone content of four group DF-3-like strains was similar, with ubiquinone-9 (Q-9) and Q-10 as their major quinones, while the other two group DF-3-like strains contained Q-7 as their major quinones, with smaller amounts of Q-8 and Q-9. 10.1128/jcm.29.10.2351-2353.1991
Fatty acid composition of gliding bacteria: oral isolates of Capnocytophaga compared with Sporocytophaga. Holt S C,Forcier G,Takacs B J Infection and immunity The extractable and bound lipids and cellular fatty acids of the gram-negative gliding bacteria, Capnocytophaga sputigena, C. gingivalis, and C. ochracea were compared to the non-host-related gliding bacterium Sporocytophaga myxococcoides. The extractable lipids represented between 17 and 28% of the cell dry weight, whereas only 2 to 4% of the lipids were in the bound fraction. The methyl esters of the cellular fatty acids were mainly aC15:0, which accounted for 69 to 73% of the total extractable fatty acids; S. myxococcoides had a similar distribution of branched-chain fatty acids; however, aC17:0 was the predominant fatty acid in this free-living gliding organism. 10.1128/iai.26.1.298-304.1979
Lipid metabolites of carbon tetrachloride. Gordis E The Journal of clinical investigation 5 min after intravenous injection into rats of (14)C- or (36)Cl-carbon tetrachloride, liver lipids were found labeled. Most of the radioactivity was found in the phospholipid fraction. The metabolites were shown to comprise a heterogeneous group of branched long-chain chlorinated fatty acids, probably containing the trichloromethyl side chain. Surviving liver slices also formed these metabolites. In a simple chemical system which generates trichloromethyl free radicals, carbon tetrachloride added to methyl oleate to form esters which behaved like the metabolites during counter-current distribution and urea adduction. The evidence strongly suggests the formation of these metabolites by free radical attack on unsaturated lipids. The relation of these observations to current theories of carbon tetrachloride intoxication is discussed. 10.1172/JCI105969
Antimicrobial effect of simple lipids with different branches at the methyl end group. Larsson K,Norén B,Odham G Antimicrobial agents and chemotherapy Various fatty acids of branched nature possess fungistatic and bacteriostatic properties. Some of these, particularly those of iso-configuration, strongly enhance the effect of conventional antimicrobial agents that act inside the cell membrane. A relation between this biological effect and the collapse properties of the corresponding monomolecular surface film on water has been observed. In this work, a series of fatty acids with a slightly smaller end group than iso-propyl, the omega-cyclopropane fatty acids, as well as one possessing a somewhat larger end group, the neo-branched fatty acids, have been examined. The omega-cyclopropane fatty acids were found to be more fungistatic than the iso-acids studied earlier. Furthermore, both cyclopropane and neo-fatty acids of short chain lengths exhibited synergistic effects in combination with tetramethylthiuramdisulfide. 10.1128/AAC.8.6.742
Phospholipid fatty acids and sterols of two Cinachyrella sponges from the Saudi Arabian Red Sea: comparison with Cinachyrella species from other origins. Barnathan Gilles,Genin Emilie,Velosaotsy Nambinina E,Kornprobst Jean-Michel,Al-Lihaibi Sultan,Al-Sofyani Abdulmohsin,Nongonierma Rita Comparative biochemistry and physiology. Part B, Biochemistry & molecular biology Phospholipid class compositions, fatty acids and sterols of the sponges Cinachyrella alloclada and C. kükenthali from the Saudi Arabian Red Sea were studied and compared with previous results for other Cinachyrella spp. collected in Senegal (East Atlantic) and New Caledonia (West Pacific). More than 50 fatty acids were identified as methyl esters and N-acyl pyrrolidides in each phospholipid mixture by GC/MS. Six fatty acids not hitherto found in nature were identified, namely 17-methyltetracosanoic in C. kükenthali and 18-methyltetracosanoic, 18-methylpentacosanoic, 18-methylhexacosanoic, 18,24-dimethyl-hexacosanoic and 6-bromo-5,9-nonacosadienoic acids in C. alloclada. Approximately 20 Delta 5,9 unsaturated fatty acids were found, including three 6-brominated acids. The presence of bacteria was evidenced by the relatively high proportions of phosphatidylglycerol and high levels of branched short-chain fatty acids. A total of 20 free 3beta-hydroxysterols were found by GC/MS, including clerosterol in relatively high amounts and gorgosterol in low amounts. The latter sterol has not been reported to date in a sponge. Comparisons with Cinachyrella species from other geographical areas show marked differences for both phospholipid fatty acid and sterol compositions.
Chemical characterization of lipopolysaccharides from Legionella feeleii, Legionella hackeliae and Legionella jordanis. Sonesson A,Jantzen E,Tangen T,Zähringer U Microbiology (Reading, England) Lipopolysaccharides (LPS) from Legionella feeleii serogroup 1, L. hackeliae serogroup 1 and L. jordanis were subjected to chemical analysis. All three LPS contained D-mannose, D-glucose, D-glucosamine, L-glycero-D-manno-heptose, 2-keto-3-deoxyoctonic acid and glycerol. In addition the LPS of L. feeleii was characterized by L-quinovose (tentatively identified) and L-fucosamine, L. hackeliae LPS by D-quinovosamine, D-galactosamine and D-galacturonic acid, and L. jordanis LPS by D-quinovosamine. Phosphorylated sugars were detected in all three LPS. The backbone sugar of the lipid A part was in each case 2,3-diamino-2,3-dideoxy-D-glucose substituted with a complex pattern of fatty acid, including 20-22 different amide-linked (non-branched and methyl-branched) 3-hydroxy fatty acids of chain-length ranging from 12 to 23 carbon atoms. The fatty acid patterns included also ester-linked nonhydroxylated entities and the uncommon 27-oxo-octacosanoic acid and 29-oxotriacontanoic acid. The LPS of L. hackeliae and L. jordanis also contained heptacosane-1,27-dioic and nonacosane-1,29-dioic acid, and their 2-hydroxy analogues were characteristic of L. jordanis LPS. SDS-PAGE patterns of the three LPS were distinctly different. Both L. feeleii and L. jordanis produced smooth-form LPS with characteristic ladder patterns, whereas L. hackeliae LPS were of more rough-type character. 10.1099/00221287-140-10-2663
Analysis of mycolic acids from a group of corynebacteria by capillary gas chromatography and mass spectrometry. Gailly C,Sandra P,Verzele M,Cocito C European journal of biochemistry The cell wall of leprosy-derived corynebacteria (a group of 'diphtheroids' isolated from human leprosy lesions and patients' blood) was previously shown to contain, in addition to peptidoglycan and arabinogalactan, mycolic acids. These alpha-branched beta-hydroxy fatty acids were attributed to the corynomycolic group, according to their RF in monodimensional thin-layer chromatography. In the present work, mycolic acids from leprosy-derived and reference corynebacteria have been fractionated by monodimensional and bidimensional thin-layer chromatography and by gas chromatography. Pyrolyzed mycolic acids have been analyzed on conventional packed columns, whereas intact methyl esters of mycolic acids with free and silylated beta-hydroxyl group have been analyzed on capillary columns, and their structure has been established by mass spectrometry. In all leprosy-derived corynebacteria, some 20 components containing 24-36 carbon atoms and 0-4 double bonds were obtained. The three major groups had 32, 34 and 36 carbons, and the frequency of unsaturated versus saturated chains increased proportionally to the molecular weight. For comparison, the main components of a reference corynebacterium. Corynebacterium diphtheriae PW8, had 30 and 32 carbons, and their hydrocarbon chains were essentially saturated. This work confirms the relative chemical homogeneity of different leprosy-derived corynebacteria and describes some peculiar traits in the chemical structure of this group of organisms. In addition, it shows the complexity of the mycolic acid fraction of corynebacterial cell wall and suggests that the mycolic acid pattern is a sort of fingerprint of each bacterial strain grown under standard conditions. Finally, the fractionation of intact corynomycolic acid methyl esters with free or silylated beta-hydroxyl group by capillary gas chromatography proved to be the best analytical procedure at present available for resolving this complex mixture of corynomycolate isomers. Structural determination of silylated samples by mass spectrometry is preferred because they have more diagnostic fragments. 10.1111/j.1432-1033.1982.tb06654.x
Occurrence of 7-methyl-7-hexadecenoic acid, the corresponding alcohol, 7-methyl-6-hexadecenoic acid, and 5-methyl-4hexadecenoic acid in sperm whale oils. Pascal J C,Ackman R G Lipids Two sperm whale oils from the northern hemisphere and two from the southern hemisphere were fractionated. Triglyceride and wax esters were examined for fatty acids and alcohols with monoethylenic unsaturation bearing a methyl branch on an ethylenic carbon. The 7-methyl-7-hexadecenoic acid (0.37-1.37%) was accompanied by the corresponding alcohol (0.28-0.72%), but these materials were not accompanied by shorter chain homologues. The 7-methyl-6-hexadecenoic acid was relatively less important (0.23-0.68%), but was accompanied by 5-methyl-4-hexadecenoic acid (0.10-0.39%), and a partially identified C13 compound. Chromatographic properties on silver nitrate impregnated silicic acid TLC and on three GLC liquid phases are reported.
Use of fatty acid profiles to identify food-borne bacterial pathogens and aerobic endospore-forming bacilli. Whittaker Paul,Fry Fred S,Curtis Sherill K,Al-Khaldi Sufian F,Mossoba Magdi M,Yurawecz M Pete,Dunkel Virginia C Journal of agricultural and food chemistry Capillary gas chromatography (GC) with flame ionization detection was used to determine the cellular fatty acid profiles of various food-borne microbial pathogens and to compare the fatty acid profiles of spores and vegetative cells of the same endospore-forming bacilli. Fifteen bacteria, representing eight genera (Staphylococcus, Listeria, Bacillus, Yersinia, Salmonella, Shigella, Escherichia, and Vibrio) and 11 species were used to compare the extracted fatty acid methyl esters (FAMEs). Endospore-forming bacilli were processed to obtain pure spores and whole cell FAMEs for GC analysis. A data set for each bacterial agent was prepared using fatty acid profiles from five replicates prepared on different days. The results showed that these fatty acid intensity profiles were unique for each of the 11 species and that they could be used as a fingerprint for the organisms. The cellular fatty acid profiles for Bacillus anthracis and Bacillus cereus show that there are two branched chain fatty acids, iso 17:1 omega10c and 17:1 anteiso, which are unique in these species. Iso 17:1 omega10c is present in B. cereus vegetative cells and spores but is not observed in B. anthracis. The 17:1 anteiso fatty acid is present in B. anthracis cells but not in B. cereus cells. Fatty acids 16:0 2OH and 17:0 iso 3OH are present in B. anthracis and B. cereus spores but not in the vegetative cells. In summary, analysis of FAMEs from bacteria and spores can provide a sensitive procedure for the identification of food-borne pathogens. 10.1021/jf040458a
Comparison of the effects of acid and base hydrolyses on hydroxy and cyclopropane fatty acids in bacteria. Lambert M A,Moss C W Journal of clinical microbiology The cellular fatty acid compositions of Legionella oakridgensis, Brucella suis, Pseudomonas aeruginosa, and Francisella tularensis were compared after base hydrolysis (saponification), acid hydrolysis, and acid methanolysis procedures were used to release the fatty acids. The branched-chain, unsaturated, saturated, and ester-linked hydroxy acids were released as effectively with saponification at 100 degrees C for 30 min as with acid hydrolysis or acid methanolysis at 85 degrees C for 16 h. Although the amide-linked hydroxy acids were released more effectively by acid hydrolysis or acid methanolysis, these methods degraded the cyclopropane fatty acids, producing a number of new peaks or artifacts in the chromatograms. Cyclopropane fatty acids were not degraded by saponification, and at least 50% of the hydroxy acids were released when the cells were saponified with 15% NaOH in 50% aqueous methanol. Thus, the results show that saponification for 30 min at 100 degrees C with 15% NaOH, followed by methylation is an excellent method for routine fatty acid analysis of bacteria and for screening cultures whose identity and fatty acid composition are unknown. 10.1128/jcm.18.6.1370-1377.1983
Occurrence of cis-9,10-methylenehexadecanoic and cis-9, 10-methyleneoctadecanoic acids in the lipids of immature and mature Fundulus heteroclitus (L.), and in roe. Cosper C I,Ackman R G Comparative biochemistry and physiology. B, Comparative biochemistry Analysis of saturated fatty acids in the mummichog Fundulus heteroclitus (L.) by argentation chromatography and open-tubular gas-liquid chromatography detected cyclopropanoid fatty acids as well as all of the anticipated saturated fatty acids, including a variety of branched-chain saturated fatty acids previously found in fish. Cyclopropanoid fatty acids were identified in juveniles, male and female bodies, and roe. When the levels of these acids in eviscerated male and female bodies were compared with roe, roe had the highest concentration, followed by female and then male fish. Whole immature mummichog had almost twice the proportion of cyclopropanoid fatty acids found in whole mature male fish. The cyclic acids probably originate indirectly in the diet of the mummichog. This consists mainly of invertebrates probably consuming bacteria associated with plant detritus. The Atlantic silversides Menidia menidia collected from the same habitat had lower proportions of odd-chain methyl-branched fatty acids, and lower proportions of cyclopropanoid fatty acids, indicating differences in sources of dietary fatty acids.
Softness and fatty acid composition of subcutaneous adipose tissue, and methylmalonic acid concentrations in the plasma of intensively reared lambs. Berthelot V,Normand J,Bas P,Kristensen N B. Small ruminant research : the journal of the International Goat Association The aim of the present work was to study the relationships between lamb growth performance, soft adipose tissue and fatty acid composition of subcutaneous adipose tissue of intensively reared lambs, and to determine if the occurrence of soft fat, and of odd numbered (Odd FA) and methyl-branched-chain fatty acids in subcutaneous adipose tissue was related to plasma concentrations of methylmalonic acid (MMA). For this purpose, a sensitive gas chromatography assay to measure low plasma concentrations of MMA was developed and validated. In all, 49 male lambs were reared from 23.6 to 41.0kg. They were fed ad libitum with hay and pelleted concentrates containing either cereals (80%, C) or sugar beet pulp (70%, BP). Plasma concentrations of MMA were measured 12 days before slaughter. Softness score and fatty acid compositions of caudal adipose tissue were determined after slaughter. At the end of the trial, 75% of the carcasses had soft adipose tissue. The occurrence of soft fat appears to be related to high metabolisable energy intake per kg body weight. Soft fat was characterised by a higher water content, a lower proportion of saturated even-numbered fatty acids and higher proportions of Odd FA and methyl-branched-chain fatty acids in caudal adipose tissue, compared to firm fat. Despite high proportions of Odd FA and branched-chain fatty acids in caudal adipose tissue, plasma concentrations of MMA were low (2.02+/-1.98&mgr;mol/l). No clear relationships between MMA concentrations and soft fat or the proportions of branched-chain fatty acids other than the Iso and Anteiso acids was observed. It was concluded that the present study does not support the hypothesis that the liver's capacity to metabolise MMA was exceeded. 10.1016/s0921-4488(01)00190-0
Regulation of enzymatic activity involved in sex pheromone production in the housefly, Musca domestica. Blomquist G J,Tillman J A,Reed J R,Gu P,Vanderwel D,Choi S,Reitz R C Insect biochemistry and molecular biology Ovarian produced ecdysteroids regulate sex pheromone production in the female housefly, inducing the synthesis of (Z)-9-tricosene (Z9-23:Hy), cis-9,10-epoxytricosane, (Z)-14-tricosen-10-one and methylalkanes. Experiments were performed to gain a detailed understanding of the processes affected by 20-hydroxyecdysone (20-HE) that result in sex pheromone production as the female becomes reproductively mature. A novel microsomal fatty acid synthetase (FAS) is present in the epidermal tissue and plays a role in producing the methyl-branched fatty acid precursors to the methylalkanes. This FAS is released from the microsomes in the presence of 3 M KCl. A major enzyme activity influenced by 20-HE is the fatty acyl-CoA elongation system. A shift in the chain length specificity of the products of the elongation system causes the change in the chain lengths of the alkenes produced to switch from C27 and longer in the previtellogenic female to C23 in the mature female. Data is presented indicating that it is the condensation activity of the elongation system that is affected. Z9-23:Hy arises from a 24 carbon acyl group which is reduced to an aldehyde, and then converted to the hydrocarbon. Data is presented demonstrating that it is the fatty acyl-CoA derivative and not the free fatty acid that is the substrate. There does not appear to be a chain length specificity which regulates the conversion of fatty acyl-CoAs to hydrocarbons as both 24 and 28 carbon fatty acyl-CoAs are converted to hydrocarbon by both males and females of all ages. 10.1016/0965-1748(95)00015-n
Smaragdicoccus niigatensis gen. nov., sp. nov., a novel member of the suborder Corynebacterineae. Adachi Kyoko,Katsuta Atsuko,Matsuda Satoru,Peng Xue,Misawa Norihiko,Shizuri Yoshikazu,Kroppenstedt Reiner M,Yokota Akira,Kasai Hiroaki International journal of systematic and evolutionary microbiology A polyphasic taxonomic approach was applied to determine the taxonomic position of a hydrocarbon-degrading actinomycete, strain Hou_blueT, which was isolated from soil samples collected from an oil spring in Niigata, Japan. The results of 16S rRNA and gyrB gene sequence comparisons indicated that strain Hou_blueT represented a novel lineage in the suborder Corynebacterineae. Colonies were malachite green-like in colour on 1/10 trypticase soy agar and the cell morphology was coccoid in all growth phases. The cell-wall diamino acid and sugar indicated chemotype IV and variation A1gamma. The sugars of the peptidoglycan were glycolated. The polar lipids were composed of diphosphatidylglycerol, phosphatidylethanolamine, phosphatidylinositol, phosphatidylinositol mannoside and some unspecified glycolipids. The organism contained two novel cyclic forms of menaquinone, smaragdiquinone A-8(H4, omega-cycl) and smaragdiquinone B-8(H4, dicycl). The major fatty acids were cis-9-18 : 1 (34.46 %) and 16 : 0 (25.1 %). Small amounts of 10-methyl-branched fatty acids were also present (10-methyl-17 : 0, 0.17 %), but not tuberculostearic acid (10-methyl-18 : 0), which has been shown to be present in all nocardiae. Gas-chromatographic analysis of the mycolic acid revealed a carbon-chain length of C43-C49. The DNA G+C content was 63.7 mol%. On the basis of phenotypic and phylogenetic distinctness, the organism is proposed to represent a novel genus and species, Smaragdicoccus niigatensis gen. nov., sp. nov., with the type strain Hou_blueT (=MBIC 06267T=DSM 44881T). 10.1099/ijs.0.64254-0
Nocardioides mesophilus sp. nov., isolated from soil. Dastager Syed G,Lee Jae-Chan,Pandey Ashok,Kim Chang-Jin International journal of systematic and evolutionary microbiology A short coccoid- to rod-shaped, motile, mesophilic actinobacterium, strain MSL-22(T), was isolated from soil on Bigeum Island, Korea. A polyphasic study was undertaken to establish the taxonomic position of this strain. Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain MSL-22(T) formed an evolutionary lineage within the radiation of the genus Nocardioides. In particular, it formed a monophyletic lineage with Nocardioides jensenii KCTC 9134(T) with which it shared the highest sequence similarity of about 97.3%. However, DNA-DNA relatedness demonstrated that strain MSL-22(T) was distinct from its closest phylogenetic neighbours. The cell-wall peptidoglycan of strain MSL-22(T) contained LL-diaminopimelic acid. The predominant menaquinone was MK-8(H₄). Strain MSL-22(T) had a cellular fatty acid profile containing straight-chain, branched, unsaturated and 10-methyl fatty acids, with iso-C₁₆:₀ as the major fatty acid. The DNA G+C content of the strain was 68.7 mol%. On the basis of phenotypic and phylogenetic evidence, the strain is separate from previously described members of the genus Nocardioides and represents a novel species in this genus, for which the name Nocardioides mesophilus sp. nov. is proposed. The type strain is MSL-22(T) (=DSM 19432(T)=KCTC 19310(T)). 10.1099/ijs.0.019059-0
Distinctness of spore and vegetative cellular fatty acid profiles of some aerobic endospore-forming bacilli. Song Y,Yang R,Guo Z,Zhang M,Wang X,Zhou F Journal of microbiological methods A gas chromatographic analysis method was employed to determine the cellular fatty acid (CFA) profiles of spores and vegetative cells of some aerobic endospore-forming bacilli. The harvests of experimental strains were processed to obtain pure spores and acquire whole cell fatty acid methyl esters for the subsequent gas chromatographic analysis, and the corresponding vegetative cells were set as control. Evaluation of reproducibility of spore CFA components revealed that, provided under standardized experimental procedure, spore CFA composition was stable enough for research purposes. Fatty acids recovered in spores in greater quantities were saturated branched-chain acids containing 15 and 17 carbon atoms, similar to the vegetative cells. Commonly, the proportions of saturated branched-chain acids in spores were greater than in vegetative cells. The dendrograms obtained by cluster analysis provided some meaningful taxonomic information of the experimental strains. The fatty acids analysis of spores seems to be a promising supplementary tool for the chemotaxonomic research of aerobic endospore-forming bacilli. 10.1016/s0167-7012(99)00123-2
n-Hexyl laurate and fourteen related fatty acid esters: new secretory compounds from the julid millipede, Anaulaciulus sp. Shimizu Nobuhiro,Kuwahara Yasumasa,Yakumaru Ryota,Tanabe Tsutomu Journal of chemical ecology A total of fifteen saturated fatty acid esters were newly identified from the secretions of an unidentified Anaulaciulus sp. (Julida: Julidae). The fatty acid components of the esters were composed of normal chain acids (from C(10) to C(14)) and of branched chain acids (from iso-C(12) to iso-C(15) and anteiso-C(15)). The alcohol moieties were all composed of normal chain alcohols varying from n-butanol to n-octanol. The most abundant component found in the total esters was n-hexyl laurate (64.7%). Novel compounds identified from the millipede secretion extracts include six branched iso- and anteiso-fatty esters, an odd-numbered C(11)-fatty acid ester, a C(13)-fatty acid ester, and a C(7)-alcohol ester, all of which were previously undescribed natural products. In addition, a characteristic mixture of benzoquinones, such as 2-methyl-1,4-benzoquinone, 2-methoxy-3-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, 2-methoxy-6-methyl-1,4-benzoquinone, and 2,3-dimethoxy-5-methyl-1,4-benzoquinone were identified from the secretions, together with trace amounts of 1,4-benzoquinone. 10.1007/s10886-012-0063-4
Actinoplanes teichomyceticus ATCC 31121 as a cell factory for producing teicoplanin. Taurino Carlo,Frattini Luca,Marcone Giorgia Letizia,Gastaldo Luciano,Marinelli Flavia Microbial cell factories BACKGROUND:Teicoplanin is a glycopeptide antibiotic used clinically in Europe and in Japan for the treatment of multi-resistant Gram-positive infections. It is produced by fermenting Actinoplanes teichomyceticus. The pharmaceutically active principle is teicoplanin A2, a complex of compounds designated T-A2-1-A2-5 differing in the length and branching of the fatty acid moiety linked to the glucosamine residue on the heptapeptide scaffold. According to European and Japanese Pharmacopoeia, components of the drug must be reproduced in fixed amounts to be authorized for clinical use. RESULTS:We report our studies on optimizing the fermentation process to produce teicoplanin A2 in A. teichomyceticus ATCC 31121. Robustness of the process was assessed on scales from a miniaturized deep-well microtiter system to flasks and 3-L bioreactor fermenters. The production of individual factors T-A2-1-A2-5 was modulated by adding suitable precursors to the cultivation medium. Specific production of T-A2-1, characterized by a linear C10:1 acyl moiety, is enhanced by adding methyl linoleate, trilinoleate, and crude oils such as corn and cottonseed oils. Accumulation of T-A2-3, characterized by a linear C10:0 acyl chain, is stimulated by adding methyl oleate, trioleate, and oils such as olive and lard oils. Percentages of T-A2-2, T-A2-4, and, T-A2-5 bearing the iso-C10:0, anteiso-C11:0, and iso-C11:0 acyl moieties, respectively, are significantly increased by adding precursor amino acids L-valine, L-isoleucine, and L-leucine. Along with the stimulatory effect on specific complex components, fatty acid esters, oils, and amino acids (with the exception of L-valine) inhibit total antibiotic productivity overall. By adding industrial oils to medium containing L-valine the total production is comparable, giving unusual complex compositions. CONCLUSIONS:Since the cost and the quality of teicoplanin production depend mainly on the fermentation process, we developed a robust and scalable fermentation process by using an industrial medium in which a complex composition can be modulated by the combined addition of suitable precursors. This work was performed in the wild-type strain ATCC 31121, which has a clear genetic background. This is important for starting a rational improvement program and also helps to better control teicoplanin production during process and strain development. 10.1186/1475-2859-10-82
Palmitic acid is the major fatty acid responsible for significant anti-N-methyl-N'-nitro-N-nitroguanidine (MNNG) activity in yogurt. Nadathur S R,Carney J R,Gould S J,Bakalinsky A T Mutation research We describe here the isolation and identification of palmitic acid as being responsible for significant anti-N-methyl-N'-nitro-N-nitroguanidine (MNNG) activity in yogurt. The Ames test (Salmonella typhimurium TA100) was used to direct fractionation of activity. Yogurt was freeze-dried and extracted with acetone to yield a crude extract. The crude extract was purified by normal phase silica gel, Sephadex LH-20, and reversed phase medium pressure liquid chromatographies. The major compound in the active medium pressure liquid chromatographic fractions was determined to be palmitic acid on GC and high pressure liquid chromatography (HPLC) systems, and by nuclear magnetic resonance (NMR) analysis. Other saturated straight chain and methyl branched fatty acids were detected by GC/MS and were later shown to possess anti-MNNG activity. Of the straight chain fatty acids, palmitic acid had the highest anti-MNNG activity. All omega - 1 methyl branched fatty acids tested were more active than their straight chain counterparts. A trace amount of isopalmitic acid (14-methyl pentadecanoic acid), a minor milk lipid, was detected in one of the active fractions, and was later shown to be five times more active than palmitic acid. Isopalmitic acid also inhibited mutagenesis induced 4-nitroquinoline-N-oxide (4NQO), and 7, 12-dimethyl benz[a]anthracene (DMBA), and was found to inhibit the metabolic activation of DMBA. 10.1016/s0165-1161(96)90265-4
[Analysis of fatty acids from lipopolysaccharides of Bacteroides thetaiotaomicron and Bacteroides fragilis]. Rokosz A,Meisel-Mikołajczyk F,Kot K,Mieszała M,Szponar B,Gamian A Medycyna doswiadczalna i mikrobiologia The aim of this study was to determine and to compare fatty acids occurring in lipopolysaccharides (LPS) isolated from B. thetaiotaomicron and B. fragilis strains of different origin. Lipopolysaccharides of three B. thetaiotaomicron strains and four B. fragilis strains were isolated by phenol-water extraction according to the procedure of Westphal and Jann (1965). Water-phase LPS fractions were then treated with nucleases and purified by ultracentrifugation as described by Gmeiner (1975). Fatty acid methyl esters, obtained by methanolysis of LPS, were analysed in gas-liquid chromatography combined with mass spectrometry (GLC-MS). Trimethylsilylated hydroxyl groups of fatty acid methyl esters were identified with GLC-MS using a method of selective ion monitoring (SIM). Lipopolysaccharides of B. thetaiotaomicron and B. fragilis strains contained long-chain (15-18 carbon atoms) fatty acids. The broad spectrum of simple long-chain and branched-chain fatty acids as well as 3-hydroxy fatty acids were detected. The main fatty acid of analyzed bacterial species was 3-hydroxy-hexadecanoic acid (3OH C16:0). Several 3-hydroxy fatty acids were detected in LPS of examined strains. Fatty acids occurring in LPS of B. thetaiotaomicron and B. fragilis strains appeared to be qualitatively similar. Quantitative differences in fatty acids composition of lipopolysaccharides isolated from strains of different origin were observed.
Negative energy balance affects imprint stability in oocytes recovered from postpartum dairy cows. O'Doherty Alan M,O'Gorman Aoife,al Naib Abdullah,Brennan Lorraine,Daly Edward,Duffy Pat,Fair Trudee Genomics Ovarian follicle development in post-partum, high-producing dairy cows, occurs in a compromised endogenous metabolic environment (referred to as negative energy balance, NEB). Key events that occur during oocyte/follicle growth, such as the vital process of genomic imprinting, may be detrimentally affected by this altered ovarian environment. Imprinting is crucial for placental function and regulation of fetal growth, therefore failure to establish and maintain imprints during oocyte growth may contribute to early embryonic loss. Using ovum pick-up (OPU), oocytes and follicular fluid samples were recovered from cows between days 20 and 115 post-calving, encompassing the NEB period. In a complimentary study, cumulus oocyte complexes were in vitro matured under high non-esterified fatty acid (NEFA) concentrations and in the presence of the methyl-donor S-adenosylmethionine (SAM). Pyrosequencing revealed the loss of methylation at several imprinted loci in the OPU derived oocytes. The loss of DNA methylation was observed at the PLAGL1 locus in oocytes, following in vitro maturation (IVM) in the presence of elevated NEFAs and SAM. Finally, metabolomic analysis of postpartum follicular fluid samples revealed significant differences in several branched chain amino acids, with fatty acid profiles bearing similarities to those characteristic of lactating dairy cows. These results provide the first evidence that (1) the postpartum ovarian environment may affect maternal imprint acquisition and (2) elevated NEFAs during IVM can lead to the loss of imprinted gene methylation in bovine oocytes. 10.1016/j.ygeno.2014.07.006
Localization of methyl-branched ceramide [EOS] species within the long-periodicity phase in stratum corneum lipid model membranes: A neutron diffraction study. Eichner Adina,Sonnenberger Stefan,Dobner Bodo,Hauß Thomas,Schroeter Annett,Neubert Reinhard H H Biochimica et biophysica acta The outermost layer of the mammalian skin, the stratum corneum (SC), is a very thin structure and realizes simultaneously the main barrier properties. The penetration barrier for xenobiotica is mostly represented by a complex lipid matrix. There is great interest in the subject of getting information about the arrangement of the lipids, which are mainly ceramides (CER), free fatty acids (FFA) and cholesterol (CHOL). SC lipid model membranes containing synthetically derived lipids in a non-physiological ratio were investigated. To compare the study to a former experiment, a methyl-branched ceramide [EOS] species in presence of the ultra-long chain CER[AP], CHOL and behenic acid (23/10/33/33, wt%) was applied. The membrane structure was studied using the very versatile technique of neutron diffraction. We were able to identify a long-periodicity phase (LPP) with a size of 114Å or 118Å with CER[EOS]-br in a ratio of >60wt% of the ceramides. Furthermore, we figured out two additional coexisting short-periodicity phases (SPP) with repeat distances of 48Å and 45Å, respectively. Partial deuterations of CER[EOS]-br and CER[AP] enabled the localization of the molecules within the multiphase system. CER[EOS]-d3 was present in the LPP, but absent in both SPP. CER[AP]-d3 was determined in both short phases but not localized within the LPP. Besides, we revealed influences of humidity and time with respect to the long-periodicity phase. 10.1016/j.bbamem.2016.09.002
Net Absorption and Metabolism of β-Hydroxy- β-Methyl Butyrate during Late Gestation in a Pig Model. Hu Liang,Kristensen Niels Bastian,Krogh Uffe,Theil Peter Kappel Nutrients The leucine metabolite, β-hydroxy-β-methyl butyrate (HMB), is widely used in human nutrition and animal production as a nutritional supplement. Although the HMB usage during late gestation has been demonstrated to have a positive effect on fetal development, knowledge on net absorption and metabolism of HMB and impact of HMB on branched chain amino acids (BCAAs) metabolism is lacking. To address this, we conducted a study using pigs during the perinatal period as a model organism. Eight-second parity sows were fitted with indwelling catheters in the femoral artery and in the portal, hepatic, femoral, and mesenteric veins. Eight hourly sets of blood samples were taken starting 30 min before the morning meal on day -10 and day -3 relative to parturition. Four control (CON) sows were fed a standard lactation diet from day -15 and throughout the experiment, and 4 HMB sows were fed the control diet supplemented with 15 mg Ca(HMB)/kg body weight mixed in one third of the morning meal from day -10 until parturition. Blood gases, plasma metabolites, milk compositions, and apparent total tract digestibility of nutrients were measured. Arterial plasma concentrations of HMB ( < 0.001), Cys ( < 0.001), and Lys ( < 0.10) were increased in HMB supplemented sows, while arterial plasma triglycerides concentration was decreased ( < 0.05). The net portal recovery of Ala and Asp were increased in HMB sows ( < 0.05). Sows fed HMB had increased hepatic vein flow and net hepatic fluxes of Met, Asn, and Gln ( < 0.05). In contrast, the femoral extraction rates of Ala and Ser were decreased by dietary HMB supplementation ( < 0.05). Dietary HMB treatment and sampling time relative to feeding had an interaction on arterial concentrations, net portal fluxes, and femoral extraction rates of BCAAs. The net portal recovery of HMB was 88%, while 14% of supplemented HMB was excreted through urine and 4% through feces. Moreover, the gastrointestinal tract metabolized 8% while the liver metabolized 12%. Finally, 26% of the daily intake of HMB was secreted via colostrum at the day of farrowing. This study demonstrated that dietary HMB supplementation increased net uptake of amino acids and increased fatty acid oxidation through improving blood flow and insulin sensitivity during the late gestation. Most importantly, oral HMB administration could maintain a stable postprandial absorption and altered metabolism in BCAAs. Net portal flux of HMB at 5.5 to 6.5 h after feeding approached zero, indicating that HMB ideally should be administrated two or three times, daily. 10.3390/nu12020561
Actinomadura deserti sp. nov., isolated from desert soil. Cao Chengliang,Xu Tangyu,Liu Jinjuan,Cai Xiaorui,Sun Yong,Qin Sheng,Jiang Jihong,Huang Ying International journal of systematic and evolutionary microbiology A Gram-positive, strictly aerobic actinobacterium, designated BMP B8004, was isolated from desert soil collected in Xinjiang Province, Northwest China. It produced an extensively branched non-fragmenting substrate mycelium, and very scanty aerial mycelium that formed a short hooked chain of arthrospores with a smooth surface. Optimum growth occurred at 28 °C, pH 7.0 and 0 % (w/v) NaCl. Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain BMP B8004 formed a distinct phyletic lineage within the genus Actinomadura. It shared the highest 16S rRNA gene sequence similarity to Actinomadura apis IM17-1 (99.2 %) and Actinomadura rifamycini NBRC 14183 (98.6 %). However, it could be distinguished from the two closest strains based on the low levels of DNA-DNA relatedness (52.7±0.7 and 45±1.8 %, respectively). Chemotaxonomic characteristics, including the main phospholipids, diphosphatidylglycerol, phosphatidylglycerol, phosphatidylinositol and phosphatidylinositol mannosides, the major menaquinones MK-9(H6) and MK-9(H8), the predominant fatty acids iso-C16 : 0, C16 : 0, C18 : 0 10-methyl and C18 : 1ω9c, were also consistent with the properties of the genus Actinomadura. The DNA G+C content of strain BMP B8004 was 71.9 mol%. Based on phenotypic and genotypic features, strain BMP B8004 is considered to represent a novel species of the genus Actinomadura, for which the name Actinomadura deserti sp. nov. is proposed. The type strain is BMP B8004 (=CGMCC 4.7432=KCTC 39998). 10.1099/ijsem.0.002922
Prediction and manipulation of the stereochemistry of enoylreduction in modular polyketide synthases. Kwan David H,Sun Yuhui,Schulz Frank,Hong Hui,Popovic Bojana,Sim-Stark Joalice C C,Haydock Stephen F,Leadlay Peter F Chemistry & biology When an enoylreductase enzyme of a modular polyketide synthase reduces a propionate extender unit that has been newly added to the growing polyketide chain, the resulting methyl branch may have either S or R configuration. We have uncovered a correlation between the presence or absence of a unique tyrosine residue in the ER active site and the chirality of the methyl branch that is introduced. When this position in the active site is occupied by a tyrosine residue, the methyl branch has S configuration, otherwise it has R configuration. In a model PKS in vivo, a mutation (Tyr to Val) in an erythromycin PKS-derived ER caused a switch in the methyl branch configuration in the product from S to R. In contrast, alteration (Val to Tyr) at this position in a rapamycin-derived PKS ER was insufficient to achieve a switch from R to S, showing that additional residues also participate in stereocontrol of enoylreduction. 10.1016/j.chembiol.2008.09.012
Systematic study of the 3-hydroxy fatty acid composition of mycobacteria. Alugupalli S,Portaels F,Larsson L Journal of bacteriology Twenty-seven strains belonging to 12 Mycobacterium species were studied for 3-hydroxy fatty acid composition. Mycobacterial cells were subjected to both mild and strong acid methanolysis, after which the liberated hydroxy fatty acids were purified and analyzed by gas chromatography-mass spectrometry as methyl ester trimethylsilyl ether derivatives. Altogether, 21 3-hydroxy fatty acids containing 14 to 28 carbon atoms were detected; 10 were straight chain, 6 were 2-methyl branched chain, and 5 were 2,4,6-trimethyl branched chain. The mycobacterial strains were classified in groups according to 3-hydroxy fatty acid patterns. 10.1128/jb.176.10.2962-2969.1994
Evaluating the Role of Drone-Produced Chemical Signals in Mediating Social Interactions in Honey Bees (Apis mellifera). Villar Gabriel,Wolfson Megan D,Hefetz Abraham,Grozinger Christina M Journal of chemical ecology Pheromones play a critical role in shaping societies of social insects, including honey bees, Apis mellifera. While diverse functions have been ascribed to queen- and worker-produced compounds, few studies have explored the identity and function of male-produced (drone) compounds. However, several lines of evidence suggest that drones engage in a variety of social interactions inside and outside of the colony. Here we elucidate the chemical composition of extracts of the drone mandibular gland, and test the hypothesis that compounds produced in these glands, or a synthetic blend consisting of the six main compounds, mediate drone social interactions in and out of the colony. Drone mandibular glands primarily produce a blend of saturated, unsaturated and methyl branched fatty acids ranging in chain length from nonanoic to docosanoic acids, and both gland extracts and synthetic blends of these chemicals serve to attract drones outside of the hive, but do not attract workers inside the hive. These studies shed light on the role drones and drone-produced chemicals have on mediating social interactions with other drones and highlight their potential importance in communicating with other castes. 10.1007/s10886-017-0912-2
Unusual cholesterol esters in the sebum of young children. Stewart M E,Downing D T The Journal of investigative dermatology Cholesterol esters (CE) having fatty acids of more than 18 carbons are a prominent feature of fetal skin surface lipid (vernix caseosa), but are a minor component of adult lipid. The difference may be related to the fact that fetal sebaceous glands generally synthesize little lipid. If so, it would be expected that prepuberal children, who also have very inactive glands, would secrete CE with a large proportion of very-long-chain fatty acids. To test this conjecture, skin surface CE from young children were isolated and analyzed. Sebum was extracted from the hair of 38 children, aged six to nine. To obtain a measure of sebaceous lipogenesis, the class composition of the lipid was determined by quantitative thin-layer chromatography and the ratio of wax esters/[cholesterol + cholesterol esters] (WE/[CH + CE]) was calculated. CE were then isolated from the lipid and hydrolyzed. The freed fatty acids were converted to fatty acid methyl esters (FAME) and analyzed by capillary gas chromatography to determine the proportion with more than 18 carbons. FAME from five of the subjects were then separated into saturated and monounsaturated fractions and analyzed again by gas chromatography to identify chain types. Ratios of WE/[CH + CE] ranged from 0.08 to 2.8 in the subjects. The proportion of CE FAME with more than 18 carbons ranged from 15 to 72%, with the highest proportion being found in the children with the lowest WE/[CH + CE]. The saturated FAME were mostly iso- or anteiso-branched, whereas the monounsaturated FAME were mostly straight-chain extension products of 16: 1 delta 9 or 18: 1 delta 9. 10.1111/1523-1747.ep12505597
Identification of meibomian gland lipids by gas chromatography-mass spectrometry: application to the meibomian lipids of the mouse. Harvey D J,Tiffany J M Journal of chromatography Methods are described for the structural determination of the constituent alcohols, steroids and fatty acids from meibomian gland esters. The compounds, obtained from hydrolysed extracts, were separated and quantified as trimethylsilyl and methyl ester-trimethylsilyl derivatives by fused-silica capillary column gas chromatography. Structural information relating to the position of chain branching and the position of double bonds in the aliphatic chains of the acids and alcohols was obtained from the mass spectra of a number of other derivatives. Thus pyrrolidide-trimethylsilyl and picolinyl ester-trimethylsilyl derivatives provided information on both branching and unsaturation. The double-bond position in unsaturated fatty acids was also examined by use of trimethylsilyl derivatives of the derived glycols. The positions of chain branching of the alcohols were determined by the spectra of their acetate and nicotinate derivatives and by their gas-liquid chromatographic retention times. In meibomian gland lipids from the mouse, cholesterol was the major constituent; alcohols from the n-, iso-, anteiso- and unsaturated series were present with iso-C26 and anteiso-C27 being the most abundant. Mono-unsaturated fatty acids belonged mainly to the omega 9 series and saturated acids belonged to the iso-, anteiso- and n-series. Several 1,2-diols were also identified. The most abundant of these had iso-C16 and iso-C20 chains. GC-MS studies on the intact wax esters showed them to be composed of the branched-chain alcohols and both branched-chain and unsaturated acids. 10.1016/s0021-9673(01)89187-1
Fatty acids bound to Fasciola hepatica 12 kDa fatty acid-binding protein, a candidate vaccine, differ from fatty acids in extracts of adult flukes. Carballeira Néstor M,Cruz Heidyleen,Hillyer George V Lipids The FA composition of Fasciola hepatica 12 kDA purified native FA-binding protein (nFh12), a candidate vaccine against fascioliasis, is described. The FA chain lengths ranged between 12 and 24 carbons. The principal FA were 16:0, 18:1n-9, 18:0, 20:4n-6, and 20:1n-9. The acids 16:0, 18:1n-9, and 18:0 comprised over half the FA that were bound to the whole FA-binding protein. Small amounts (1.0-2.8%) of iso-anteiso methyl-branched FA also were characterized. Forty-one different FA were identified in extracts of the adult flukes, with the three most abundant FA also being 16:0, 18:1n-9, and 18:0. A similar proportion of saturated vs. unsaturated FA was observed between the whole extract from F. hepatica and the nFh12 protein. However, the n-3/n-6 ratio of PUFA was significantly different, being 1.2 in the whole extract vs. 9.6 in the nFh12 protein complex. The nFh12 protein binds more n-5, n-6, and n-7 PUFA and less n-3 and n-9 PUFA than the whole extract. In addition, cholesterol (56%), sitosterol (36%), and fucosterol (8%) also were bound to the nFh12 protein complex.
Structural determination of cerebrosides isolated from Asterias amurensis starfish eggs using high-energy collision-induced dissociation of sodium-adducted molecules. Park Taeseong,Park Young Seung,Rho Jung-Rae,Kim Young Hwan Rapid communications in mass spectrometry : RCM Six cerebrosides were isolated from the eggs of the starfish Asterias amurensis using solvent extraction, silica gel column chromatography, and reversed-phase high-performance liquid chromatography. This study demonstrated that the structures of cerebrosides could be completely characterized, based on their sodium-adducted molecules, using fast atom bombardment (FAB) tandem mass spectrometry. The high-energy collision-induced dissociation of the sodium-adducted molecule, [M + Na](+), of each cerebroside molecular species generated abundant ions, providing information on the compositions of the 2-hydroxy fatty acids and long-chain sphingoid bases, as well as the sugar moiety polar head group. Each homologous ion series along the fatty acid and aliphatic chain of the sphingoid base was useful for locating the double-bond positions of both chains and the methyl branching position of the long-chain base. The N-fatty acyl portions were primarily long-chain saturated or monoenoic acids (C16 to C24) with an α-hydroxy group. The sphingoid long-chain base portions were aliphatic chains (C18 or C22) with two or three degrees of unsaturation and with or without methyl branching. 10.1002/rcm.4896
Metabolic signatures and risk of type 2 diabetes in a Chinese population: an untargeted metabolomics study using both LC-MS and GC-MS. Lu Yonghai,Wang Yeli,Ong Choon-Nam,Subramaniam Tavintharan,Choi Hyung Won,Yuan Jian-Min,Koh Woon-Puay,Pan An Diabetologia AIMS/HYPOTHESIS:Metabolomics has provided new insight into diabetes risk assessment. In this study we characterised the human serum metabolic profiles of participants in the Singapore Chinese Health Study cohort to identify metabolic signatures associated with an increased risk of type 2 diabetes. METHODS:In this nested case-control study, baseline serum metabolite profiles were measured using LC-MS and GC-MS during a 6-year follow-up of 197 individuals with type 2 diabetes but without a history of cardiovascular disease or cancer before diabetes diagnosis, and 197 healthy controls matched by age, sex and date of blood collection. RESULTS:A total of 51 differential metabolites were identified between cases and controls. Of these, 35 were significantly associated with diabetes risk in the multivariate analysis after false discovery rate adjustment, such as increased branched-chain amino acids (leucine, isoleucine and valine), non-esterified fatty acids (palmitic acid, stearic acid, oleic acid and linoleic acid) and lysophosphatidylinositol (LPI) species (16:1, 18:1, 18:2, 20:3, 20:4 and 22:6). A combination of six metabolites including proline, glycerol, aminomalonic acid, LPI (16:1), 3-carboxy-4-methyl-5-propyl-2-furanpropionic acid and urea showed the potential to predict type 2 diabetes in at-risk individuals with high baseline HbA1c levels (≥6.5% [47.5 mmol/mol]) with an AUC of 0.935. Combined lysophosphatidylglycerol (LPG) (12:0) and LPI (16:1) also showed the potential to predict type 2 diabetes in individuals with normal baseline HbA1c levels (<6.5% [47.5 mmol/mol]; AUC = 0.781). CONCLUSIONS/INTERPRETATION:Our findings show that branched-chain amino acids and NEFA are potent predictors of diabetes development in Chinese adults. Our results also indicate the potential of lysophospholipids for predicting diabetes. 10.1007/s00125-016-4069-2
Determination of the structure of the fatty acid chain in a cyclic lipopeptide using GC-MS. Yang Shi-Zhong,Wei Dong-Zhi,Mu Bo-Zhong Journal of biochemical and biophysical methods A GC-EIMS method to determine the structure of the fatty acid chains in cyclic lipopeptides is described. The structure of the fatty acid chains can be determined by the characteristic peaks of the MS spectrogram according to the fact that the alpha cleavage predominates the MS of a fatty acid with amino and hydroxy groups, while the McLafferty rearrangement predominates the MS of one without amino or hydroxy group. The characteristics of the strongest peaks of 103 and 102 in MS spectrograms due to alpha cleavage represent the beta-hydroxy-fatty acid and the beta-amino fatty acid, respectively; the strongest peak of 117 due to alpha cleavage and the relatively weak peak of 88 due to McLafferty rearrangement indicate the beta-hydroxy-fatty acid with a branched methyl group at its alpha position. The strongest peak of 74 due to McLafferty suggests the fatty acid without hydroxy or amino group. The ratio of relative intensity (I(43)/I(57)) characterizes the branches of alkyl chains. The greater I(43)/I(57) corresponds to an iso alkyl, and the smaller I(43)/I(57) corresponds to an anteiso alkyl. This method can be used to determine the full structure of the fatty acid chains in lipopeptides. 10.1016/j.jbbm.2007.01.005
Mutation in the putative ketoacyl-ACP reductase CaKR1 induces loss of pungency in Capsicum. Koeda Sota,Sato Kosuke,Saito Hiroki,Nagano Atsushi J,Yasugi Masaki,Kudoh Hiroshi,Tanaka Yoshiyuki TAG. Theoretical and applied genetics. Theoretische und angewandte Genetik KEY MESSAGE:A putative ketoacyl-ACP reductase (CaKR1) that was not previously known to be associated with pungency of Capsicum was identified from map-based cloning and functional characterization. The pungency of chili pepper fruits is due to the presence of capsaicinoids, which are synthesized through the convergence of the phenylpropanoid and branched-chain fatty acid pathways. The extensive, global use of pungent and non-pungent peppers underlines the importance of understanding the genetic mechanism underlying capsaicinoid biosynthesis for breeding pepper cultivars. Although Capsicum is one of the earliest domesticated plant genera, the only reported genetic causes of its loss of pungency are mutations in acyltransferase (Pun1) and putative aminotransferase (pAMT). In this study, a single recessive gene responsible for the non-pungency of pepper No.3341 (C. chinense) was identified on chromosome 10 using an F population derived from a cross between Habanero and No.3341. Five candidate genes were identified in the target region, within a distance of 220 kb. A candidate gene, a putative ketoacyl-ACP reductase (CaKR1), of No.3341 had an insertion of a 4.5-kb transposable element (TE) sequence in the first intron, resulting in the production of a truncated transcript missing the region coding the catalytic domain. Virus-induced gene silencing of CaKR1 in pungent peppers resulted in the decreased accumulation of capsaicinoids, a phenotype consistent with No.3341. Moreover, GC-MS analysis of 8-methyl-6-nonenoic acid, which is predicted to be synthesized during the elongation cycle of branched-chain fatty acid biosynthesis, revealed that its deficiency in No.3341. Genetic, genomic, transcriptional, silencing, and biochemical precursor analyses performed in combination provide a solid ground for the conclusion that CaKR1 is involved in capsaicinoid biosynthesis and that its disruption results in a loss of pungency. 10.1007/s00122-018-3195-2
The role of wax and sterol ester fatty acids in chronic blepharitis. Dougherty J M,Osgood J K,McCulley J P Investigative ophthalmology & visual science The authors analyzed the long-chain fatty acids derived from the wax and sterol ester fractions of meibomian secretions from patients with chronic blepharitis and normal individuals. Meibomian secretions were partitioned into separate lipid classes by thin-layer chromatography (TLC). Wax and sterol esters were eluted and transesterified. The liberated fatty acid methyl esters (FAME) were analyzed by gas liquid chromatography. Equivalent chain lengths (ECL) were determined for the 58 peaks found. Thirty-three peaks were positively identified by standards. Peaks were quantified by area normalization. Percentage compositions were computed for each individual and tabulated by group; each fatty acid was analyzed by analysis of variance, and each clinical group was compared with normal subjects. The authors found increases in the series of monounsaturated fatty acids from patient wax/sterol esters compared with normal subjects (P less than 0.05). The authors also found differences in some members of the series of normal, straight, and branched saturated moieties. These differences between normal groups and the blepharitic groups represent a biologically significant pattern that may relate to the disease process. Discriminant analysis provided a 73% probability of correct classification into clinical groups based strictly on FAME analysis (P less than 0.05).
Androgenic control of 1-alkyl-2,3-diacylglycerol in the harderian gland of the golden hamster, Mesocricetus auratus. Seyama Y,Hida A,Hayashi S,Buzzell G R Journal of biochemistry Harderian glands of golden hamsters produce a copious lipid secretion, most of which is in the form of 1-alkyl-2,3-diacylglycerol (ADG). Sexual differences are seen in the composition of golden hamster ADG and in the morphology of secretory lipid droplet. ADGs from females contained abundant iso- and anteiso-branched chain alkyl groups and fatty acids [Seyama, Y., Otsuka, H., Ohashi, K., Vivien-Roels, B., and Pevet, P. (1995) J. Biochem. 117, 661-670]. Female hamsters were either untreated or given subcutaneous testosterone pellets. Treatment of females with testosterone led to the disappearance of such branched chain alkyl groups and fatty acids. Intact males had ADGs with entirely saturated straight chain alkyl groups and fatty acids. Castration led to the appearance of iso- and anteiso-branched chain alkyl groups and fatty acids. These observations suggested that the production of branched chain fatty acids in the Harderian gland of golden hamster is inhibited by testosterone at the step of isovaleryl-CoA dehydrogenase and 2-methyl branched-chain acyl-CoA dehydrogenase 10.1093/oxfordjournals.jbchem.a021310
The esg locus of Myxococcus xanthus encodes the E1 alpha and E1 beta subunits of a branched-chain keto acid dehydrogenase. Toal D R,Clifton S W,Roe B A,Downard J Molecular microbiology The esg locus of Myxococcus xanthus appears to control the production of a signal that must be transmitted between cells for the completion of multicellular development. DNA sequence analysis suggested that the esg locus encodes the E1 decarboxylase (composed of E1 alpha and E1 beta subunits) of a branched-chain keto acid dehydrogenase (BCKAD) that is involved in branched-chain amino acid (BCAA) metabolism. The properties of an esg::Tn5 insertion mutant supported this conclusion. These properties include: (i) the growth yield of the mutant was reduced with increasing concentrations of the BCAAs in the medium while the growth yield of wild-type cells increased, (ii) mutant extracts were deficient in BCKAD activity, and (iii) growth of the mutant in media with short branched-chain fatty acids related to the expected products of the BCKAD helped to correct the mutant defects in growth, pigmentation and development. The esg BCKAD appears to be involved in the synthesis of long branched-chain fatty acids since the mutant contained reduced levels of this class of compounds. Our results are consistent with a model in which the esg-encoded enzyme is involved in the synthesis of branched-chain fatty acids during vegetative growth, and these compounds are used later in cell-cell signalling during development.
Apibacter mensalis sp. nov.: a rare member of the bumblebee gut microbiota. Praet Jessy,Aerts Maarten,Brandt Evie De,Meeus Ivan,Smagghe Guy,Vandamme Peter International journal of systematic and evolutionary microbiology Isolates LMG 28357T (=R-53146T) and LMG 28623 were obtained from gut samples of Bombus lapidarius bumblebees caught in Ghent, Belgium. They had identical 16S rRNA gene sequences which were 95.7 % identical to that of Apibacter adventoris wkB301T, a member of the family Flavobacteriaceae. Both isolates had highly similar matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) MS and randomly amplified polymorphic DNA (RAPD) profiles. A draft genome sequence was obtained for strain LMG 28357T (Gold ID Gp0108260); its DNA G+C content was 30.4%, which is within the range reported for members of the family Flavobacteriaceae (27 to 56 mol%) and which is similar to that of the type strain of A. adventoris (29.0 mol%). Whole-cell fatty acid methyl ester analysis of strain LMG 28357T revealed many branched-chain fatty acids, a typical characteristic of bacteria of the family Flavobacteriaceae and a profile that was similar to that reported for A. adventoris wkB301T. MK6 was the major respiratory quinone, again conforming to bacteria of the family Flavobacteriaceae. The isolates LMG 28357T and LMG 28623 could be distinguished from A. adventoris strains through their oxidase activity. On the basis of phylogenetic, genotypic and phenotypic data, we propose to classify both isolates as representatives of a novel species of the genus Apibacter, Apibacter mensalis sp. nov., with LMG 28357T (=DSM 100903T=R-53146T) as the type strain. 10.1099/ijsem.0.000921
Effect of systemic hyperinsulinemia on amino acid flux across human legs in postabsorptive state. Arfvidsson B,Zachrisson H,Möller-Loswick A C,Hyltander A,Sandström R,Lundholm K The American journal of physiology The effect of physiological hyperinsulinemia (approximately 110 mU/l) on leg tissue protein balance was investigated in eight weight-stable healthy individuals. A primed constant infusion of L-[U-14C]tyrosine was used to measure the disposal and release of tyrosine across the leg before and during 2 h of euglycemic clamp studies. The leg exchange of 3-methyl-L-histidine (3-MH) and all amino acids in blood were measured before and during insulinization, including the muscle tissue content of amino acids. Hyperinsulinemia decreased whole body tyrosine flux from 52 +/- 2 to 35 +/- 1 mumol/min (P less than 0.0001), whereas neither disposal (53 +/- 9 vs. 45 +/- 9 nmol.min-1.100 g-1) nor release of tyrosine across the leg (76 +/- 11 vs. 66 +/- 10 nmol X min-1 X 100 g-1) was significantly influenced. The arterial concentration and the leg exchange of 3-MH were not significantly affected by 2 h of hyperinsulinemia, but the sum of all amino acids declined significantly. The net leg balance of tyrosine was not affected at all by hyperinsulinemia, whereas the balance of the branched-chain amino acids and methionine were switched from efflux toward influx. Phenylalanine efflux from the leg only showed a trend to a significant effect by insulin. The muscle tissue concentration of six individual amino acids decreased significantly during hyperinsulinemia, particularly the branched-chain amino acids. The leg exchange of glucose, free fatty acids, and glycerol immediately changed significantly, as expected in response to insulinization.(ABSTRACT TRUNCATED AT 250 WORDS) 10.1152/ajpendo.1991.260.1.E46
Pseudomonas maltophilia: identification of the hydrocarbons, glycerides, and glycolipoproteins of cellular lipids. Tornabene T G,Peterson S L Canadian journal of microbiology The nature of quantity of the free lipids of Pseudomonas maltophilia have been examined. Lipid components identified as phosphatidyl ethanolamine, phosphatidyl glycerol, diphosphatidyl glycerol, phosphatidylamino acid derivatives and phosphatidic acid accounted for about one-half of the total lipids and are generally typical of gram-negative bacteria. The remaining lipids were identified as a complex family of aliphatic hydrocarbon isomers (C22--C32) and a mixture of glycolipoproteins. These components are generally atypical lipids of bacteria. The glycolipoproteins were composed of a broad range of amino acids, ketodeoxyotulonic acid, mannose, glucose, 4-aminopentose, glucosamine, phosphates, and a relatively large quantity of fatty acids, principally OH-13:0. The total esterified fatty acids consist of cyclopropane, iso- and anteiso-branched and normal saturated and unsaturated chains in the range from C14 to C20. Amide bound fatty acids consist of OH 11:0, OH-12:0, OH-13:0, and methyl-branched OH-13 in addition to methyl-branched and normal saturated and unsaturated chains.
Elimination of n-butylated hydroxytoluene methylation during fatty acid analysis by gas chromatography. Zang L Y,Kalbach H L,Brown B,Jackson L L,van Kuijk F J Journal of chromatography. B, Biomedical applications An improved method for fatty acids analysis with optimum recovery of highly polyunsaturated fatty acids methyl esters in biological systems is presented. The method is based on transesterification of phospholipid and triacylglycerols to fatty acid methyl esters using a commercially available reagent, Methyl-Prep II. Without proper precautions, as much as 50% of n-butylated hydroxytoluene (BHT) added to prevent oxidation of polyunsaturated fatty acids, could be methylated during the transesterification step. Methylated BHT elutes close to 14:0 (myristic acid) and no longer functions as an antioxidant, but the modified conditions virtually eliminate the methylation of BHT. Sample extraction and methylation was completed in 30 min at room temperature. A chelator (diethylenetriamine-pentaacetic acid; DTPA) is also added to prevent peroxidation of metal catalyzed free radical chain reactions. The standard deviations of the major fatty acids from multiple human plasma samples prepared on different days were less than 5%. The recovery of arachidonic acid, 20:4, from plasma was improved using the new method, and the recovery for docosahexaenoic acid, 22:6, spiked to human plasma was found to be 99%.
Composition of the saturated and monounsaturated fatty acids of Mycobacterium phlei. Campbell I M,Naworal J Journal of lipid research Combined gas-liquid chromatography-mass spectrometry has been used to identify unusual fatty acids of Mycobacterium phlei. In addition to many normal saturated and monounsaturated fatty acids, series of iso, anteiso, 10-methyl, and (n-8)-methyl substituted fatty acids have been found and identified. These mid-chain branched acids may arise by methylation of monounsaturated acids followed (if necessary) by chain elongation.
Fatty acids of vegetative cells and spores of Bacillus licheniformis. Martin J H Journal of dairy science Lipids were extracted from vegetative cells and spores of Bacillus licheniformis. Vegetative cells were grown in nutrient broth and spores on nutrient agar. Total lipid approximated 2.89% of the dry weight of vegetative cells and 2.09% of the dry weight of spores. The fatty acids were prepared as methyl esters and analyzed by gas chromatography and mass spectrometry. There were six fatty acids in concentrations greater than 5% of the total lipid in both spores and vegetative cells, but only palmitic acid was common to both. Fatty acids from vegetative cells in quantities of 5% or more of the total lipid material were lauric, myristic, palmitic, palmitoleic, and linoleic acids. Fatty acids from spores in concentrations greater than 5% of the total lipid were isopentadecylic, palmitic, Carbon-17 iso, and three other long or branched chain fatty acids which were not identified. Spores contained more long and branched chain fatty acids with odd numbers of carbon atoms than did vegetative cells. 10.3168/jds.s0022-0302(76)84444-x
Isonicotinic acid hydrazide induced changes and inhibition in mycolic acid synthesis in Nocardia and related taxa. Tomiyasu I,Yano I Archives of microbiology The mycolic acid compositions of Nocardia rubra and related bacteria grown in media containing different concentrations of antituberculous isonicotinic acid hydrazide (INH) were determined in detail by gas chromatography-mass spectrometry. On the basis of molecular species composition, average carbon numbers of mycolic acids were calculated. In Nocardia rubra, N. lutea and Rhodococcus rhodochrous IFO-13161, the ratio of mycolic to non-mycolic fatty acids and the average carbon numbers of mycolic acids were decreased at the INH concentrations of higher than 1 microgram/ml, paralleling with the significant inhibition of growth. In above three species the synthesis of longer chain mycolic acids (longer than C44 or C46 ) was inhibited more significantly than shorter homologues such as C38 or C40 . In contrast, neither growth inhibition nor change in corynomycolic acid composition was observed in Corynebacteria xerosis and Rhodococcus rhodochrous IFO-13165 at the concentration region of INH up to 100 micrograms/ml. The direct mass fragmentographic analysis of the trimethylsilylated (TMS) derivatives of mycolic acid methyl esters, monitoring [M-15] ions of individual molecular species, revealed that the chain shortening of total mycolic acid molecule by INH occurred more greatly in more highly unsaturated subclasses than in less unsaturated subclasses. Furthermore, mass fragmentographic analysis, monitoring fragment ions (A) and (B), due to straight chain and branched chain alkyl units, respectively, demonstrated the inhibition of mycolic acids was not attributed to the shortening of alpha-alkyl chain, but to the inhibition of chain elongation of C28 to C32 straight chain meromycolic acids. It was also indicated the amounts of trehalose mono- and di- mycolate (cord factor) decreased significantly with the addition of INH (1 to 20 micrograms/ml) in the above strains. From the results obtained above, INH appeared to inhibit the synthesis of mycolic acids longer than C44 or C46 specifically by inhibiting chain elongation or desaturation of precursor long chain fatty acids longer than C28 or C30.
Effect of the photoperiod in modulating the androgenic control of 1-alkyl-2,3-diacylglycerol composition in the harderian gland of the golden hamster, Mesocricetus auratus. Buzzell G R,Hida A,Fu S,Seyama Y The Journal of experimental zoology The golden hamster Harderian gland produces a lipid secretion consisting mainly of 1-alkyl-2,3-diacylglycerol. We investigated the composition of alkyl and acyl groups in male and female hamster Harderian alkyldiacylglycerol, in animals kept in long and short photoperiods. Female hamsters in long days have alkyl groups with long saturated straight chains (C18:0 and C20:0) and methyl-branched chains (even and odd chain length iso-branched and odd chain length anteiso-branched chains). Acyl groups in females in long days are mostly long straight chains (C16:0) and methyl-branched chains. In females, short photoperiods led to reductions in the proportions of methyl-branched chains and changes in the proportions of straight chain alkyl and acyl groups; these changes were prevented by pinealectomy. Male hamsters with intact gonads, maintained in long days, had no methyl-branched chain alkyl or acyl groups; saturated straight chains were generally shorter than those of females and the odd chain length saturated C15:0 acyl group was common. Short photoperiods did not significantly alter the composition of male alkyldiacylglycerol. Castrated male hamsters in long days showed a distinctively female phenotype, with long straight chains and methyl-branched alkyl and acyl groups. Castrated males in short days showed a mixture of male and female characteristics: shorter straight chain alkyl and acyl groups, a total absence of methyl-branched alkyl groups, and the presence of methyl-branched acyl groups. These results and those of other studies suggest that testosterone controls the enzymes isovaleryl acyl-CoA dehydrogenase and 2-methyl branched-chain acyl-CoA dehydrogenase; in the absence of these enzymes, the primers for the synthesis of methyl-branched chain fatty acids are produced. Our results indicate that this control is modulated by short photoperiods (perhaps due to reduced prolactin levels). It is also suggested that characteristics of male-type alkyldiacylglycerol are better adapted to conditions of autumn and winter than are those of female-type alkyldiacylglycerol.
Derepression of bkd by the FadR loss dictates elevated production of BCFAs and isoleucine starvation. Sun Yijuan,Meng Qiu,Zhang Yongting,Gao Haichun Biochimica et biophysica acta. Molecular and cell biology of lipids In many γ-proteobacteria, FadR is recognized as a global transcriptional regulator: in addition to being the most prominent regulator for FA biosynthesis and degradation, the protein also mediates expression of many genes in diverse biological processes. In Shewanella oneidensis, a bacterium renowned for its respiratory versatility, FadR directly controls only a few genes. However, the FadR loss substantially increases BCFA contents and impairs growth. In this study, we showed that FadR is required to activate a number of important FA biosynthesis genes, including fabA, fabB, and fabH1. Although most of these genes are controlled by FadR in a direct manner, they are not critically responsible for the phenotypes resulting from the FadR depletion. Subsequent investigations identified BKD encoded by the bkd operon as the critical factor for enhanced BCFA production. In the absence of FadR, the bkd operon is derepressed, resulting in elevated conversion of 3MOP to 3-methylbutanoyl-CoA, one of the direct substrates for BCFA synthesis. We further showed that the growth defect of the fadR mutant is due to BCAA shortage, a scenario also attributable to excessive BKD: 3MOP, the common substrate for both BCFA and BCAA, is disproportionately used for BCFA synthesis, leading to reduced production of BCAA. Collectively, our findings reveal that the S. oneidensis FadR regulon is surely larger than previously proposed and a new mechanism by which FadR impacts bacterial physiology. 10.1016/j.bbalip.2019.158577
BgFas1: A fatty acid synthase gene required for both hydrocarbon and cuticular fatty acid biosynthesis in the German cockroach, Blattella germanica (L.). Pei Xiao-Jin,Chen Nan,Bai Yu,Qiao Jian-Wen,Li Sheng,Fan Yong-Liang,Liu Tong-Xian Insect biochemistry and molecular biology Insect cuticular hydrocarbons (CHCs), the evolutionary products of aquatic hexapod ancestors expanding to terrestrial environment, are deposited on the surface of insect integument and originally functioned primarily as waterproofing agents. CHCs are derived from the conserved fatty acid synthesis pathway in insects. However, the pivotal fatty acid synthase (FAS) involved in hydrocarbon (HC) biosynthesis remains unknown in many insect orders including the primitive Blattodea. Here, we investigated functional FAS genes that modulate cuticular lipid biogenesis in the German cockroach, Blattella germanica (L.). Based on our full-length transcriptomic data and the available genomic data, seven FAS genes (BgFas1-7) were identified from B. germanica. Tissue-specific expression analysis revealed that BgFas1, BgFas3, BgFas4 and BgFas7 were highly expressed in the integument, whereas BgFas2 was dominantly expressed in the fat body. BgFas5/6 mRNA was almost negligible in the tested tissues. Systemic RNAi screen was performed against BgFas1-7, we found that only RNAi knockdown of BgFas1 caused a dramatic reduction of methyl-branched HCs (mbHCs) and a slight decrease of straight-chain HCs (scHCs) for both internal and external HCs. Significant reduction of cuticular free fatty acids (cFFAs) was also detected within BgFas1-repressed cockroaches, while repression of CYP4G19 resulted in dramatic increase of cFFAs. Moreover, we found that BgFas1 mRNA levels were correlated with insect molting cycles, and could be induced by long-term mild dryness treatment. Furthermore, desiccation assay revealed that BgFas1 suppression accelerated water loss and led to early death of cockroaches under desiccation. Our results indicate that BgFas1 is necessary for both HC and cFFA biosynthesis in B. germanica. In addition, our study also confirms that cuticular lipids, particularly mbCHCs, are critical for desiccation resistance in B. germanica. 10.1016/j.ibmb.2019.103203
Mechanism of activation of branched-chain alpha-keto acid dehydrogenase complex by exercise. Xu M,Nagasaki M,Obayashi M,Sato Y,Tamura T,Shimomura Y Biochemical and biophysical research communications Branched-chain alpha-keto acid dehydrogenase (BCKDH) complex catalyzes the committed step of branched-chain amino acid catabolism, and its activity is regulated by the phosphorylation-dephosphorylation cycle. BCKDH kinase is responsible for inactivation of the complex by phosphorylation. In the present study, we examined acute exercise on the activity state of the complex as well as the amounts of bound and free forms of the kinase in rat liver and skeletal muscle. Acute exercise activated the complex in association with a decrease in the bound form of kinase in both liver and muscle. The free form of kinase in both tissues was slightly increased but the total amount of the kinase was not affected by acute exercise. The protein amount ratio of bound kinase to E1beta component of the complex was much higher in muscle than in the liver of rats, reflecting the low activity state of the complex in muscle. These results suggest that the amount of the bound kinase plays an important role in regulation of the activity state of the complex. We propose that the alteration in the amount of bound BCKDH kinase is a short-term regulatory mechanism for determining the activity of BCKDH complex. 10.1006/bbrc.2001.5647
Dietary sources of branched-chain fatty acids and their biosynthesis, distribution, and nutritional properties. Food chemistry Branched-chain fatty acids (BCFAs) consist of a wide variety of fatty acids with alkyl branching of methyl group. The most common BCFAs are the types with one methyl group (mmBCFA) on the penultimate carbon (iBCFA) or the antepenultimate carbon (aiBCFA). Long-chain mmBCFAs are widely existing in animal fats, milks and are mostly derived from bacteria in the diet or animal digestive system. Recent studies show that BCFAs benefit human intestinal health and immune homeostasis, but the connection between their content, distribution in the human and their nutritional functions are not well established. In this paper, we reviewed BCFAs from various dietary sources focused on their molecular species. The BCFAs biosynthesis in bacteria, Caenorhabditis elegans, mammals and their distribution in human tissues are summarized. This paper also discusses the nutritional properties of BCFAs including influences on intestinal health, immunoregulatory effects, anti-carcinoma, and anti-obesity activities, by highlighting the most recent research progress. 10.1016/j.foodchem.2023.137158
Factors affecting levels of volatile 4-alkyl branched-chain fatty acids in sheep milk from 2 contrasting farming systems in New Zealand. Teng Fei,Reis Mariza G,Broadhurst Marita,Lagutin Kirill,Samuelsson Linda,Ma Ying,Stevens David,Day Li Journal of dairy science Knowledge of factors influencing the levels of 4-alkyl branched-chain fatty acid (vBCFA), and consequently the "sheepy flavor" intensity of New Zealand sheep milk, is currently limited. In this study, we investigated the effects of 2 contrasting farming systems (fully housed/mid-lactation or pasture-grazed/late lactation) on the levels of vBCFA in sheep milk on a commercial farm in the North Island of New Zealand. Fully housed/mid-lactation ewes were housed 24 h/d and fed a total mixed ration. Pasture-grazed/late-lactation ewes were grazed 24 h/d and offered approximately 40% supplements because of poor pasture growth resulting from dry and hot climatic conditions. Any effects of genetics, age, lactation stage, feed composition, lambing date, or the environment in the housing barn or outdoors were confounded. The results obtained in this study were descriptive rather than definitive, because of the limitations of the experimental design. Levels of 4-methyloctanoic acid and 4-methylnonanoic acid in milk from fully housed/mid-lactation ewes increased during the trial period, but remained low in milk from pasture-grazed/late-lactation ewes. Levels of 4-ethyloctanoic acid in milk from the 2 groups of ewes were comparable throughout the trial. Increases in levels of 4-methyloctanoic acid and 4-methylnonanoic acid in sheep milk were associated with lactation stage and the proportion of lucerne silage fed to ewes. The level of free-form 4-ethyloctanoic acid was positively correlated with the proportion of soy meal in the diet and negatively correlated with the proportion of barley. Milk from fully housed/mid-lactation ewes had a higher flavor values than milk from pasture-grazed/late-lactation ewes because of its higher total amounts of vBCFA. 10.3168/jds.2019-17192
Low molecular weight branched-chain and n-chain fatty acids in caprine and bovine colostrum. Attaie R,Richter R L,Reine A H Journal of dairy science Colostrum from French-Alpine and Anglo-Nubian goats and Holstein cows was collected and analyzed for both total and FFA of 12 and fewer carbon atoms. Short-chain VFA were separated from long-chain fatty acids using simultaneous distillation extraction. The n-butyl esters of fatty acids were quantified by gas chromatography, and their identity was confirmed by gas chromatography-mass spectrometry. The concentration of decanoic acid was 33 and 83% less in Holstein colostrum than in colostrum from Alpine and Nubian goats, respectively. Colostrum from Nubian goats had twice as much decanoic acid as colostrum from Alpine goats. The FFA in colostrum that differed between species but not between goat breeds were octanoic and decanoic acids. These respective fatty acids were approximately two and three times greater in colostrum from goats than in colostrum from Holsteins. The quantity of decanoic acid was different between goat breeds and between animal species. The ratio of total fatty acid concentration to free-state concentration for hexanoic acid appeared to be useful for differentiating between Nubian and Alpine goat colostrum as well as between Nubian and Holstein colostrums. 10.3168/jds.S0022-0302(93)77323-3
Biosynthesis of branched-chain fatty acids by preparations from bovine adipose tissue [proceedings]. Wahle K W,Paterson S M,Garton G A Biochemical Society transactions 10.1042/bst0061157
Branched chain fatty acids reduce the incidence of necrotizing enterocolitis and alter gastrointestinal microbial ecology in a neonatal rat model. Ran-Ressler Rinat R,Khailova Ludmila,Arganbright Kelly M,Adkins-Rieck Camille K,Jouni Zeina E,Koren Omry,Ley Ruth E,Brenna J Thomas,Dvorak Bohuslav PloS one INTRODUCTION:Branched chain fatty acids (BCFA) are found in the normal term human newborn's gut, deposited as major components of vernix caseosa ingested during late fetal life. We tested the hypothesis that premature infants' lack of exposure to gastrointestinal (GI) BCFA is associated with their microbiota and risk for necrotizing enterocolitis (NEC) using a neonatal rat model. METHODS:Pups were collected one day before scheduled birth. The pups were exposed to asphyxia and cold stress to induce NEC. Pups were assigned to one of three experimental treatments. DF (dam-fed); Control, hand-fed rat milk substitute; BCFA, hand-fed rat milk substitute with 20%w/w BCFA. Total fat was equivalent (11%wt) for both the Control and BCFA groups. Cecal microbiota were characterized by 16S rRNA gene pyrosequencing, and intestinal injury, ileal cytokine and mucin gene expression, interleukin-10 (IL-10) peptide immunohistochemistry, and BCFA uptake in ileum phospholipids, serum and liver were assessed. RESULTS:NEC incidence was reduced by over 50% in the BCFA group compared to the Control group as assessed in ileal tissue; microbiota differed among all groups. BCFA-fed pups harbored greater levels of BCFA-associated Bacillus subtilis and Pseudomonas aeruginosa compared to Controls. Bacillus subtilis levels were five-fold greater in healthy pups compared to pups with NEC. BCFA were selectively incorporated into ileal phospholipids, serum and liver tissue. IL-10 expression increased three-fold in the BCFA group versus Controls and no other inflammatory or mucosal mRNA markers changed. CONCLUSION:At constant dietary fat level, BCFA reduce NEC incidence and alter microbiota composition. BCFA are also incorporated into pup ileum where they are associated with enhanced IL-10 and may exert other specific effects. 10.1371/journal.pone.0029032
The first naturally occurring alpha-methoxylated branched-chain fatty acids from the phospholipids of Amphimedon complanata. Carballeira N M,Alicea J Lipids The phospholipid fatty acid composition of the sponge Amphimedon complanata was reinvestigated, and the 2-methoxy-13-methyltetradecanoic acid, 2-methoxy-14-methylpentadecanoic acid, and 2-methoxy-13-methylpentadecanoic acid were identified for the first time in nature. Structure characterization was accomplished by means of gas chromatographic retention times and gas chromatography-mass spectrometry. These acids could have originated from bacteria in symbiosis with the sponge.
Fatty acids of the genus Bacillus: an example of branched-chain preference. Kaneda T Bacteriological reviews 10.1128/br.41.2.391-418.1977
The origin and function of some methyl groups in branched-chain fatty acids, plant sterols and quinones. Lederer E The Biochemical journal 10.1042/bj0930449
Oxidation of branched-chain fatty acids in rat liver homogenates. Björkhem I,Danielsson H European journal of biochemistry 10.1111/j.1432-1033.1970.tb00313.x
The saturated methyl branched fatty acids of adult human skin surface lipid. Nicolaides N,Apon J M Biomedical mass spectrometry 10.1002/bms.1200040604
Dataset describing the amino acid catabolism of . Data in brief The dataset depicts the catabolism of branched-chain amino acids by in the presence of thiosulfate under different culture conditions. The results reveal that the strain can degrade all three branched-chain amino acids resulting in the production of their corresponding branched-chain fatty acids and branched-chain alcohols with the fatty acids always being the dominant product. The highest amounts of 2-methyl-1-butanol from isoleucine were at pH 6.5, liquid-gas ratio of 0.98, and at 20 mM thiosulfate concentration. A kinetic experiment of the branched-chain amino acids was done in the presence of thiosulfate as are data on selected enzyme activities related to alcohols and aldehydes. Finally, an NMR study using C1 methyl-1-butyrate during the degradation of leucine in the presence of thiosulfate was done to prove that the C1-methyl-1-butanol was indeed from its corresponding fatty acid. 10.1016/j.dib.2023.110017
Modulation of fatty acid composition and growth in Sporosarcina species in response to temperatures and exogenous branched-chain amino acids. Tsuda Kentaro,Nagano Hideaki,Ando Akinori,Shima Jun,Ogawa Jun Applied microbiology and biotechnology Psychrotolerant endospore-forming Sporosarcina species have been predominantly isolated from minced fish meat (surimi), which is stored under refrigeration after heat treatment. To develop a better method for preserving surimi-based food products, we studied the growth and fatty acid compositions of the isolated strain S92h as well as Sporosarcina koreensis and Sporosarcina aquimarina at cold and moderate temperatures. The growth rates of strain S92h and S. koreensis were the fastest and slowest at cold temperatures, respectively, although these strains grew at a similar rate at moderate temperatures. In all three strains, the proportions of anteiso-C and unsaturated fatty acids (UFAs) were significantly higher at cold temperatures than at moderate temperatures. Furthermore, supplementation with valine, leucine, and isoleucine resulted in proportional increases in iso-C, iso-C, and anteiso-C, respectively, among the fatty acid compositions of these strains. The proportions of the UFAs were also altered by the supplementation. At cold temperatures, the growth rates of strain S92h and S. koreensis, but not of S. aquimarina, were affected by supplementation with leucine. Supplementation with isoleucine enhanced the growth of S. koreensis at cold temperatures but not that of the other strains. Valine did not affect the growth of any strain. These results indicate that anteiso-C and UFAs both play important roles in the cold tolerance of the genus Sporosarcina and that these bacteria modulate their fatty acid compositions in response to the growth environment. 10.1007/s00253-017-8227-3
Fatty acid composition of tissue lipids of rats given dietary branched-chain fatty acids [proceedings]. Smith A,Lough A K,Earl C R The Proceedings of the Nutrition Society
Branched-chain fatty acids in the neonatal gut and estimated dietary intake in infancy and adulthood. Ran-Ressler Rinat R,Glahn Raymond P,Bae SangEun,Brenna J Thomas Nestle Nutrition Institute workshop series Branched-chain fatty acids (BCFA) are primarily saturated fatty acids (FA) with a methyl branch, usually near the terminal methyl group. BCFA are abundant in bacteria, skin, and vernix caseosa but have seldom been studied with respect to human nutrition. They are constituents of the term newborn infant gut lumen, being swallowed as vernix particulate components of amniotic fluid in the last trimester of normal pregnancy. We recently showed that BCFA protect against necrotizing enterocolitis (NEC) in the rat pup model. Dietary BCFA at levels similar to those found in human vernix reduced NEC incidence by more than 50%, increased the abundance of BCFA-containing bacteria, and increased the expression of ileal anti-inflammatory IL-10. The few published reports of BCFA in human milk enable an estimate that breastfed infants consume 19 mg BCFA per 100 ml milk. Dietary BCFA consumption from milk fat and other ruminant products, the main sources of dietary BCFA, is more than 400 mg BCFA per day in adult Americans. This estimate exceeds by severalfold the average dietary intake of bioactive FA, such as docosahexaenoic acid. BCFA are bioactive, abundant but neglected components of the human food supply. 10.1159/000351396
Towards enantioselective ultrahigh performance liquid chromatography-mass spectrometry-based metabolomics of branched-chain fatty acids and anteiso-fatty acids under reversed-phase conditions using sub-2-μm amylose- and cellulose-derived chiral stationary phases. Geibel Christian,Zhang Li,Serafimov Kristian,Gross Harald,Lämmerhofer Michael Chirality Branched-chain fatty acids (BCFAs) are mostly saturated fatty acids with one or more methyl, seldom ethyl, branches in the alkyl chain. They are derived from branched-chain amino acids, ruminant-derived food, or biosynthetic side products of acetyl-CoA carboxylase. They possess iso- (branching at penultimate carbon) and anteiso-fatty acid structure (branching at antepenultimate carbon) or are branched at any other position of the carbon chain. Except for iso-fatty acids, BCFAs are chiral. They are commonly analyzed by GC-MS, while there is a lack of enantioselective LC-MS methods. In this work, we present a methodology for targeted enantioselective UHPLC-ESI-MS/MS metabolomics of BCFAs. It makes use of precolumn derivatization with 1-naphthylamine and reversed-phase elution conditions. A homologous series of short BCFA analytes with distinct chain lengths (having up to eight carbon atoms), branching type (methyl or ethyl), and position of branching (2, 3, and 4, anteiso and iso) has been systematically studied on six commercially available polysaccharide UHPLC columns. Chiralpak IB-U exhibited the highest and broadest enantioselectivity while IH-U maintained enantioselectivity also for BCFAs with chirality distant from the carboxylic function (i.e., with other branching than in 2-position). The method was used to assign the absolute configuration of a 4-methylhexanoic acid side chain of a natural product from Streptomyces sp. SHP 22-7. The potential of the corresponding UHPLC-ESI-QTOF-MS/MS assay for analyzing stereoselectively BCFAs and other short organic acids by untargeted analysis in human urine was further elucidated in a preliminary proof-of-principle test. 10.1002/chir.23413
Profiling of branched chain and straight chain saturated fatty acids by ultra-high performance liquid chromatography-mass spectrometry. Journal of chromatography. A Branched chain fatty acids (BCFAs) are one of the important sub categories of fatty acids (FAs) which have unique functions in nature. They are commonly analyzed by GC-MS after derivatization to methyl esters (FAMEs). On the other hand, there is a lack of isomer-selective LC-MS methods which allow the distinction of different isomers with wide coverage of carbon chain length. In this work, a systematic retention and isomer selectivity study on seven commercially available UHPLC columns (six polysaccharide columns Chiralpak IA-U, IB-U, IC-U, ID-U, IG-U and IH-U; one Acquity UPLC CSH C18 column) was performed. Various experimental factors were evaluated including column temperatures, gradient profiles and flow rates to elucidate their effects on the separation ability of homologous series of BCFAs with distinct chain lengths, different branching types and branching positions. In general, IG-U outperformed the other columns in terms of isomer selectivity especially for the short and medium-chain BCFA isomers while RP C18 showed good potential in terms of selectivity for long-chain BCFA isomers. Furthermore, after the evaluation of the chromatographic retention pattern on the various columns and method optimization, we report a methodology for untargeted isomer-selective BCFA profiling without precolumn derivatization with UHPLC-ESI-MS/MS by quadrupole-time-of-flight instrument with SWATH acquisition. The best method provides selectivity for constitutional isomers of BCFAs covering distinct chain length (C5-C20) with different branching types (methyl or ethyl) and branching positions (2Me, 3Me, 4Me, 6Me, anteiso and iso-BCFAs) with an optimized LC condition on Acquity UPLC CSH C18 column. Finally, the optimized method was applied for the BCFAs profiling in lipid extracts of Staphylococcus aureus samples. Besides, pooled human platelets and pooled human plasma were evaluated as mammalian samples for presence of BCFAs as well. The new method showed strong potential for BCFA profiling in bacterial samples including different isomers anteiso and iso-BCFAs, which could be a useful tool for related subdisciplines in metabolomics and lipidomics in particular in combination with electron-activated dissociation MS. Compared to GC, the presented isomer selective LC methods can be also of great utility for preparative purposes. Equivalent (carbon) chain length numbers were calculated for RP18 and Chiralpak IG-U and compared to those of FAMEs obtained by GC. 10.1016/j.chroma.2023.464111
Effect of methyl-branched fatty acids on the structure of lipid bilayers. Poger David,Caron Bertrand,Mark Alan E The journal of physical chemistry. B Methyl-branched fatty acids are widespread in prokaryotic membranes. Although anteiso and iso branching (that is on the antepenultimate and penultimate carbons) and the presence of multiple methyl branches in the phytanoyl chain are known to modify the thermotropic behavior and enhance the fluidity of lipid bilayers, little is known about the effect of methyl branching on the structure of lipid bilayers. In this study, molecular dynamics simulations are used to examine systematically the impact of one or more methyl branches at different positions along the sn-1 palmitoyl chain on the structural properties of a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayer. It is found that methyl branching reduces lipid condensation, decreases the bilayer thickness, and lowers chain ordering. Branching also results in the formation of kinks at the branching point, thereby enhancing the fluidity of lipid bilayers. Furthermore, this effect varies in a methyl-position-dependent fashion. In the case of polymethylated chains, the simulations suggest that if the gap between the methyl groups is sufficient (two or three carbons), the effects of the methyl branches are additive and equivalent to the combined effect of the corresponding monomethyl-branched lipids. 10.1021/jp503910r
Nutritional Interventions to Improve Cachexia Outcomes in Cancer-A Systematic Review. Medicina (Kaunas, Lithuania) : The prevalence of cachexia has increased across all of the cancer types and accounts for up to 20% of cancer-related deaths. This paper is a systematic review of nutritional interventions aiming to improve cachexia outcomes in cancer, focusing on weight gain. : A search in Medline and Elsevier databases for articles up until the 23 January 2022, was conducted. : Out of 5732 screened records, 26 publications were included in the final analysis. Four randomized clinical trials showed a significant body weight (BW) increase in patients treated with eicosapentaenoic acid (EPA), β-hydroxy-beta-methyl butyrate (β-HMB), arginine, and glutamine or marine phospholipids (MPL). An upward BW trend was observed in patients treated with L-carnitine, an Ethanwell/Ethanzyme (EE) regimen enriched with ω-3 fatty acids, micronutrients, probiotics, fish oil, a leucine-rich supplement, or total parental nutrition (TPN) with a high dose of a branched-chain amino acid (BCAA). : Although clinical trials relating to large numbers of nutritional supplements present promising data, many trials provided negative results. Further studies investigating the underlying mechanisms of action of these nutritional supplements in cancer cachexia are needed. Early screening for cancer cachexia risk and nutritional intervention in cancer patients before aggravating weight loss may stabilize their weight, preventing cachexia syndrome. According to the GRADE methodology, no positive recommendation for these nutritional supplements may be expressed. 10.3390/medicina58070966
Profiling of branched-chain fatty acids nitroxide radical-directed dissociation integrated on an LC-MS/MS workflow. The Analyst Chain modifications on fatty acyls, such as methyl branching, are important to modulate the biochemical and biophysical properties of lipids. The current lipid analysis workflows which mainly rely on collisional-induced dissociation (CID) to obtain the structural information of lipids often fail in locating the chain modifications. Radical-directed dissociation (RDD) is a new type of tandem mass spectrometry (MS/MS) method capable of producing intrachain cleavages, thus allowing the detailed characterization of lipid structures. In this study, we have developed an RDD method induced by nitroxide radicals (NO˙) for the analysis of branched-chain fatty acids (BCFAs). Fatty acids (FAs) are first amidated by -benzylhydroxylamine; MS CID of the lithium adduct ion of the derivatized FAs uncages the nitroxide radical, which subsequently initiates RDD along the chain. The location of methyl branching can be determined characteristic 28 Da spacing due to cleavages on either side of the branching point, with enhanced fragmentation observed toward the carbonyl end. This nitroxide-RDD method has been integrated onto reversed-phase liquid chromatography and applied for the profiling of BCFAs from yak milk powder and pooled human plasma samples. Other than the more often encountered iso- and anteiso-BCFAs, we have identified FA n-5 17 : 0 as a minor component from human plasma, which has been rarely reported before. 10.1039/d2an00266c
Alpha-oxidation. Jansen Gerbert A,Wanders Ronald J A Biochimica et biophysica acta Phytanic acid (3,7,11,15-tetramethylhexadecanoic acid) is a branched chain fatty acid, which is a constituent of the human diet. The presence of the 3-methyl group of phytanic acid prevents degradation by beta-oxidation. Instead, the terminal carboxyl group is first removed by alpha-oxidation. The mechanism of the alpha-oxidation pathway and the enzymes involved are described in this review. 10.1016/j.bbamcr.2006.07.012
Sensitive LC-MS/MS method for the temporal profiling of bile acids, fatty acids and branched-chain alpha-keto acids in maternal plasma during pregnancy and cord blood plasma at delivery. Clinica chimica acta; international journal of clinical chemistry BACKGROUND AND AIMS:There are significant changes to the maternal inflammatory profile across pregnancy. Recent studies suggest that perturbations in maternal gut microbial and dietary-derived plasma metabolites over the course of pregnancy mediate inflammation through a complex interplay of immunomodulatory effects. Despite this body of evidence, there is currently no analytical method that is suitable for the simultaneous profiling of these metabolites within human plasma. MATERIALS AND METHODS:We developed a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the high-throughput analysis of these metabolites in human plasma without derivatization. Plasma samples were processed using liquid-liquid extraction method with varying proportions of methyl tert-butyl ether, methanol, and water in a 3:10:2.5 ratio to reduce matrix effects. RESULTS:LC-MS/MS detection was sufficiently sensitive to quantify these gut microbial and dietary-derived metabolites at physiological concentrations and linear calibration curves with r > 0.99 were obtained. Recovery was consistent across concentration levels. Stability experiments confirmed that up to 160 samples could be analyzed within a single batch. The method was validated and applied to analyse maternal plasma during the first and third trimester and cord blood plasma of 5 mothers. CONCLUSION:This study validated a straightforward and sensitive LC-MS/MS method for the simultaneous quantitation of gut microbial and dietary-derived metabolites in human plasma within 9 minutes without prior sample derivatization. 10.1016/j.cca.2023.117449
Supplementing branched-chain volatile fatty acids in dual-flow cultures varying in dietary forage and corn oil concentrations. II: Biohydrogenation and incorporation into bacterial lipids. Journal of dairy science To maintain membrane homeostasis, ruminal bacteria synthesize branched-chain fatty acids (BCFA) or their derivatives (vinyl ethers) that are recovered during methylation procedures as branched-chain aldehydes (BCALD). Many strains of cellulolytic bacteria require 1 or more branched-chain volatile fatty acid (BCVFA). Therefore, the objective of this study was to investigate BCVFA incorporation into bacterial lipids under different dietary conditions. The study was an incomplete block design with 8 continuous culture fermenters used in 4 periods with treatments (n = 4) arranged as a 2 × 2 × 2 factorial. The factors were high (HF) or low forage (LF, 67 or 33% forage, 33:67 alfalfa:orchardgrass), without or with supplemental corn oil (CO; 3% dry matter, 1.5% linoleic fatty acid), and without or with 2.15 mmol/d (5 mg/d C each of isovalerate, isobutyrate, and 2-methylbutyrate). After methylation of bacterial pellets collected from each fermenter's effluent, fatty acids and fatty aldehydes were separated before analysis by gas chromatography and isotope ratio mass spectrometry. Supplementation of BCVFA did not influence biohydrogenation extent. Label was only recovered in branched-chain lipids. Lower forage inclusion decreased BCFA in bacterial fatty acid profile from 9.45% with HF to 7.06% with LF and decreased BCALD in bacterial aldehyde profile from 55.4% with HF to 51.4% with LF. Supplemental CO tended to decrease iso even-chain BCFA and decreased iso even-chain BCALD in their bacterial lipid profiles. The main 18:1 isomer was cis-9 18:1, which increased (P < 0.01) by 25% from CO (data not shown). Dose recovery in bacterial lipids was 43.3% lower with LF than HF. Supplemental CO decreased recovery in the HF diet but increased recovery with LF (diet × CO interaction). Recovery from anteiso odd-chain BCFA and BCALD was the greatest; therefore, 2-methylbutyrate was the BCVFA primer most used for branched-chain lipid synthesis. Recovery in iso odd-chain fatty acids (isovalerate as primer) was greater than label recovery in iso even-chain fatty acids (isobutyrate as primer). Fatty aldehydes were less than 6% of total bacterial lipids, but 26.0% of C recovered in lipids were recovered in BCALD because greater than 50% of aldehydes were branched-chain. Because BCFA and BCALD are important in the function and growth of bacteria, especially cellulolytics, BCVFA supplementation can support the rumen microbial consortium, increasing fiber degradation and efficiency of microbial protein synthesis. 10.3168/jds.2022-23192
Production of 10-methyl branched fatty acids in yeast. Blitzblau Hannah G,Consiglio Andrew L,Teixeira Paulo,Crabtree Donald V,Chen Shuyan,Konzock Oliver,Chifamba Gamuchirai,Su Austin,Kamineni Annapurna,MacEwen Kyle,Hamilton Maureen,Tsakraklides Vasiliki,Nielsen Jens,Siewers Verena,Shaw A Joe Biotechnology for biofuels BACKGROUND:Despite the environmental value of biobased lubricants, they account for less than 2% of global lubricant use due to poor thermo-oxidative stability arising from the presence of unsaturated double bonds. Methyl branched fatty acids (BFAs), particularly those with branching near the acyl-chain mid-point, are a high-performance alternative to existing vegetable oils because of their low melting temperature and full saturation. RESULTS:We cloned and characterized two pathways to produce 10-methyl BFAs isolated from actinomycetes and γ-proteobacteria. In the two-step bfa pathway of actinomycetes, BfaB methylates Δ9 unsaturated fatty acids to form 10-methylene BFAs, and subsequently, BfaA reduces the double bond to produce a fully saturated 10-methyl branched fatty acid. A BfaA-B fusion enzyme increased the conversion efficiency of 10-methyl BFAs. The ten-methyl palmitate production (tmp) pathway of γ-proteobacteria produces a 10-methylene intermediate, but the TmpA putative reductase was not active in E. coli or yeast. Comparison of BfaB and TmpB activities revealed a range of substrate specificities from C14-C20 fatty acids unsaturated at the Δ9, Δ10 or Δ11 position. We demonstrated efficient production of 10-methylene and 10-methyl BFAs in S. cerevisiae by secretion of free fatty acids and in Y. lipolytica as triacylglycerides, which accumulated to levels more than 35% of total cellular fatty acids. CONCLUSIONS:We report here the characterization of a set of enzymes that can produce position-specific methylene and methyl branched fatty acids. Yeast expression of bfa enzymes can provide a platform for the large-scale production of branched fatty acids suitable for industrial and consumer applications. 10.1186/s13068-020-01863-0
Identification and quantification of dimethyl acetals from plasmalogenic lipids in lamb intramuscular fat under different derivatization procedures. Gómez-Cortés P,Rodríguez-Pino V,Marín A L Martínez,de la Fuente M A Journal of chromatography. B, Analytical technologies in the biomedical and life sciences Meat lipids are mostly comprised by triacylglycerols, but small amounts of plasmalogens are also present in intramuscular fat. The purpose of this study was to evaluate the effect of lipid derivatization on the presence of dimethyl acetal (DMA) molecules from plasmalogenic lipids in intramuscular fat samples. Three different methods of methylation were assayed. Acid-catalyzed methanolysis using HCl, the traditional procedure to derivatize meat lipids, was compared to two base-catalyzed methanolysis based on the ISO International standard procedure using either KOH and/or NaOCH which, apparently, are only able to methylate fatty acids from triacylglycerols. DMA compounds were isolated by thin layer chromatography and then identified by gas chromatography-mass spectrometry. The most prominent DMA molecules detected were 16:0 and 18:0, but also minor amounts of monounsaturated and branched-chain DMA were quantified. Acid methylation yielded the highest amounts of DMA. However, the present article demonstrates that ISO standard based methylation procedures could also generate DMA derivatives in considerable quantities, which is not usually considered and may interfere with the determination of fatty acid methyl esters (FAME) from triacylglycerides. The current research warns scientist about possible FAME misidentifying and overestimations in intramuscular fat analysis using basic methylation and the need to consider the presence of DMA in samples that contain plasmalogens. 10.1016/j.jchromb.2019.04.049