Identification of methyl-branched fatty acids from the triacylglycerols of subcutaneous adipose tissue of lambs

A concentrate of branched chain fatty acids (as methyl esters) was prepared from the triacylglycerols of subcutaneous adipose tissue lipids of lambs receiving a carbohydrate-rich (cereal) diet. This was accomplished by procedures which allowed the removal of unsaturated components by peroxidation and straight chain saturated components by urea-adduct formation. The concentrate was analyzed by high resolution gas chromatography in combination with mass spectrometry and was shown to consist of a complex mixture of saturated methyl-substituted fatty acids. Methyl substitution occurred on even-numbered carbon atoms (relative to the carboxyl group) and the chain lengths of the acids ranged from 10 to 18 carbon atoms. Acids with one methyl substituent in the fatty acyl chain were most abundant; di-, tri- and tetramethyl-substituted acids were also present. The biosynthesis of these methyl-substituted acids is discussed briefly.     

Recent Advances in the Chemistry and Biochemistry of Methyl Branched Fatty Acids

The main aspects of recent research on the occurrence, isolation, structure, biogenesis and metabolism of the methyl branched fatty acids have been reviewed. For the purpose of this work the fatty acids were classified in the following 5 groups: 1. Iso- or anteiso-acids; 2. Branched chain acids with one methyl branching in the middle of the chain; 3. Multiple branched acids with methyl branching on alternate carbon atoms; 4. Multiple branched acids with isoprenoid structure; 5. Mycolic acids. The literature has been covered up to 1969.     

Components of royal jelly: I. Identification of the organic acids

This present work characterizes the fatty acid constituents of the lipid fraction of royal jelly. Among the organic acids found after fractionation by thin layer chromatography of the corresponding methyl esters, the following compounds were identified by combined GC-MS: saturated and unsaturated linear fatty acids, saturated and unsaturated linear and branched dicarboxylic acids, mono-and dihydroxy acids. The most common characteristic of the organic acids was that most contained 8 or 10 carbon atoms, whether saturated or unsaturated, linear or branched.     

Location of methyl branchings in fatty acids: Fatty acids in uropygial secretion of Shanghai Duck by GC-MS of 4,4-dimethyloxazoline derivatives

2-Substituted 4,4-dimethyloxazolines (DMOX) have been found to be a useful alternative to the commonly used methyl esters for the localization of unsaturated bounds and other substituents in the fatty chain by mass spectrometry. The powerful directed fragmentation coupled with good gas chromatographic ability enables the structure elucidation of modified fatty acids in complex mixtures. Continuing our previous study, 76 out of a total of 86 fatty acids obtained from the preen gland wax of shanghai duck now have been identified by gas chromatography-mass spectrometry (GC-MS) of their oxazoline derivatives. The identification was based on the interpretation of the mass spectra and comparison with the spectra and equivalent chain lengths (ECL) of the corresponding methyl esters. Main components of this lipid mixture are straight chain fatty acids (8.22%), and 2-, 4-or 6-monomethyl branched acids (53.69%), amounting to 61.91% of the total acid fraction. In addition, a large number of dimethyl-substituted fatty acids (31.4%) also have been found. Typical mass spectra, which are easily recognizable and highly specific for fatty acids substituted at various positions, are presented and classified according to the structural feature of the chain. Chemical Modification in Mass Spectrometry 6. For preceding paper in this series, see Ref. 17.     

Chemical composition of the wax secreted by a scale insect (Ceroplastes pseudoceriferus Green)

The wax material in the secretion of a scale insect,Ceroplastes pseudoceriferus Green was analyzed chemically with special interest to the composition of higher fatty acids and higher alcohols. The wax consists of 34.2% fatty acids, 27.1% unsaponifiable matter and 29.5% resin acids. The fatty acids were found to be a complex mixture of 15 normal acids ranging from C₈ to C₃₂. Of these, octacosanoic, triacontanoic and dotriacontanoic acids comprise over 30% of the wax. Presence of relatively large amount of unsaturated fatty acids of the C₁₈ series (2.8% of the wax) is of particular interest. From the unsaponifiable fraction, only one saturated straight chain aleohol, bexacosanol, was detected (2.7% of the original wax). The other unsaponifiable matter was considered to be cyclic or branched carbon chain, and consisted of at least 12 to 20 compounds. The resin acid fraction was also found to be a complex mixture of at least 13 to 14 components.     

Produkte der Dimerisierung ungesättigter Fettsäuren VIII: Über die Zusammensetzung der Fraktion der “Intermediates” bei der Fettsäuredimerisierung

Products of Dimerisation Unsaturated Fatty Acids VIII: The Fraction of “Intermediates” Obtained by Dimerisation of Unsaturated Fatty Acids The fraction of “intermediates” which is obtained by dimerisation of unsaturated fatty acid contains straight chain saturated fatty acids with 20-24 carbon atoms as well as methyl branched isomers thereof. The production of these compounds is probably caused by the presence of small amounts of monounsaturated fatty acids with 20-24 carbon atoms in the starting material. The fraction of “intermediates” contains in addition monocarboxylic acids with 36 carbon atoms. These are probably formed after dimerisation by an intramolecular cyclisation reaction under participation of one carboxylic group, followed by hydrogenation of the produced carbonyl group. Finally the formed alcoholic group is eliminated as a water molecule, and the produced double bond is hydrogenated.     

The fatty acids of degras

Degras contains a complex mixture of lipids comprised of branched and normal chain fatty acids, hydroxy acids, sterols, sterol esters and long chain wax esters. There are no glycerides in degras. This paper is a report on the composition of the branched and normal chain fatty acids. Preparative techniques of thin-layer chromatography were used to isolate the fatty acids from the other lipid classes. Gas chromatography was used on three different stationary phase separations of the fatty acid methyl esters. Identifications of the composition were based on a combination of techniques and known standards. Authorized for publication on April 20, 1965, as paper No. 3003 in the journal series of The Pennsylvania Agricultural Experiment Station.     

New phospholipid fatty acids from the marine spongeCinachyrella alloclada uliczka

The fatty acid composition of phospholipids from the Senegalese spongeCinachyrella alloclada was examined. Two new fatty acids not hitherto found in nature, namely 10,13-octadecadienoic acid and 16-tricosenoic acid, were identified. 8-Hexadecenoic, 13-nonadecenoic and 5,9,13-trimethyltretradecanoic fatty acids were also found for the first time in sponges. The latter compound (1.4% of the total fatty acid mixture), an isoprenoid fatty acid, accompanies the major fatty acid 4,8,12-trimethyltridecanoic acid (19.7%). The monomethyl branched fatty acids (22%) identified include 23-methylpentacosanoic acid (anteiso-26∶0), not previously observed in sponged. The major long-chain fatty acids encountered were the known 17-tetracosenoic 19-heptacosadienoic and 5,9,23-tricontatrienoic acid. Some sixty fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry.     

Evidence for the probable presence of sulfur-containing fatty acids as minor constituents in canola oil

Three isomeric epithio stearic acids have been concentrated as possible minor sulfur-bearing components of unprocessed canola oil. Chromatographic and mass spectral evidence is presented in support of these novel fatty acid structures, tentatively identified as isomeric 9, 12; 8, 11; and 7, 10 epithio stearic acids, each with a methyl substituent on the ring. Presented in part at the AOCS Canadian Section meeting in Guelph, Ontario, October 1986.     

Analytik und Biophysik von verzweigtkettigen Fettsäuren in Lipiden

Analytics and biophysics of branched fatty acids in lipids . Objects of our investigations are long chain fatty acids with methyl groups in different positions and fatty acids with a different length of the sidegroup in α-position. The separation of racemic branched fatty acid methyl esters by gas chromatography on a chiral column depends on the structure of the branched fatty acid. Diastereomeric amides and phosphatidylcholines with α-branched fatty acid residues were separated preparatively. The branched fatty acids were incorporated into 1,2-diacyl-, 1-acyl-2-hexadecyl- and 2-acyl-1-hexadecyl-glycerophosphocholines and characterized by differential scanning calorimetry and X-ray diffraction.     

Synthesis of alkyl‐branched fatty acids

Alkyl‐branched fatty compounds are of interest for industrial products in the cosmetics and lubricant areas. In this review, clay‐ and zeolite‐catalyzed isomerizations of unsaturated fatty compounds, especially of oleic acid, are discussed. While clay‐catalyzed reactions give most complex mixtures of dimeric fatty acids and of monomeric so‐called “isostearic acid”, the zeolite‐catalyzed process yields preferentially an isomeric mixture of isostearic acids having the methyl branch on the 8–14 positions of the alkyl chain. Synthetically useful additions of alkyl radicals can only be performed on ω‐unsaturated fatty compounds, whereas perfluoroalkyl iodides were added to fatty compounds with terminal as well as internal double bonds using electron transfer‐initiated radical addition reactions. Electrophilic additions of alkyl carbenium ions generated by decomposition of alkyl chloroformates by ethylaluminum sesquichloride give well‐defined alkyl‐branched oleochemicals with good yields.     

The role of the conserved threonine in P450 BM3 oxygen activation: substrate-determined hydroxylation activity of the Thr268Ala mutant

The hydroxylation activity of the Thr268Ala mutant of P450(BM3) has been shown to occur to varying degrees with small alterations in the structure of a fatty-acid substrate. Ten substrates were investigated, including straight chain, branched chain and cis-cyclopropyl substituted fatty acids with a straight-chain length that varied between 12 and 16 carbon atoms. The efficacy of the hydroxylation activity appeared to be governed by the chain length of the substrate. Substrates possessing 14 to 15 carbons afforded the highest levels of activity, which were comparable with the wild-type enzyme. Outside of this window, straight-chain fatty acids showed reduced activity over the other substrate types. These results provide a cautionary tale concerning the loss of ferryl activity in such cytochrome P450 threonine to alanine mutants, as the nature of the substrate can determine the extent to which hydroxylation chemistry is abolished.     

Branched‐chain fatty acids as activators of peroxisome proliferator‐activated receptors

We observed earlier that phytanic acid activated subtype α of the peroxisome proliferator‐activated receptor (PPAR) via the cytosolic liver‐type fatty acid‐binding protein (L‐FABP). In a further search for minor lipid nutrients that interact with genes, we explored here the potential of branched‐chain fatty acids to serve as agonists for the PPAR subtypes α, β and γ in rodent and human molecular test systems. Beyond chlorophyll‐derived pristanic and phytanic acids, bacteria‐derived iso‐ and anteiso‐fatty acids and avian‐derived ‘uropygial’ fatty acids were tested by transactivation assay. In addition, we studied binding of these fatty acids to recombinantly expressed PPAR ligand binding domains (LBDs) and to L‐FABP by competition with fluorescent parinaric acid. In contrast to single methyl‐branched agonists, multi methyl‐branched fatty acids had high transactivation potentials in either test system; in addition, some agonists of the latter were highly subtype selective. Multi methyl‐branched chain fatty acids were superior activators of human PPARγ, a preference not seen in the murine test system. High‐affinity binding of isoprenoid‐derived pristanic and phytanic acids to PPARγ‐LBD and to L‐FABP was observed, and also of pristanic acid to PPARα‐LBD. Polyketidic uropygial fatty acids bound to PPARγ‐LBD only, though weakly. As both isoprenoid and polyketidic fatty acids showed high activation potentials, it became clear that binding data determined in vitro cannot predict biological activity as determined by transactivation assay. For pristanic acid, however, a signalling path similar to that found for phytanic acid can be concluded. Taken together, multi methyl‐branched fatty acids of the human food chain can affect cellular metabolism through regulating gene expression.     

Fatty acid and aldehyde composition of major phospholipids in salt gland of marine birds and spiny dogfish

The lipophilic components of choline phosphoglycerides and ethanolamine phosphoglycerides obtained from the salt gland of herring gull and eider duck and from the rectal gland of spiny dogfish were investigated by means of thin-layer chromatography, gas chromatography, and gas chromatography-mass spectrometry. All phospholipids analyzed were shown to contain small amounts of plasmalogens, and mainly C16, C18, and C18∶1 aldehyde was detected. The fatty acids were composed of saturated, unsaturated, straight chain, and branched chain types, ranging between 14–22 carbon atoms. The lipophilic composition of the rectal gland phospholipids showed a higher degree of unsaturation and the presence of more branched chain fatty acids than that of the birds, possibly related to body temperature.     

Biochemical and physiological studies of certain ticks (Ixodoidea): Isolation and partial identification of a new fatty acid in eggs ofDermacentor andersoni Stiles (Ixodidae)

Gas liquid chromatographic analysis of the fatty acid methyl esters from eggs ofDermacentor andersoni Stiles (Ixodidae) revealed the presence of significant quantities (15% total fatty acids) of an unidentified component with a retention time between C_18∶3−C_22∶0 fatty acids. Smaller amounts of the unidentified component (ca. 5% total fatty acid) also were detected in host rabbit serum. Purified, the unidentified component's methyl ester collected from the tick eggs by preparative gas liquid chromatography was partially identified and characterized by chemical and spectroscopic analyses. The evidence suggests that the unidentified component is a methyl branched C₁₅ tricarboxylic acid containing two vicinal carboxylic acid groups. Biosynthesis of the unidentified component by the tick is under investigation.     

New process for the production of branched-chain fatty acids

Fatty acids are the primary natural starting materials for the production of surfactant and detergent molecules. Derived from vegetable (oil) and animal (fat) triglyceride sources, the fatty acids are linear aliphatic carboxylic acids. Industrial interest in branched-chain fatty acids is driven by the needs for products with enhanced performance benefits including higher solubility, ease of handling, better hard water tolerance, and improved oxidative stability. Therefore, catalytic processes have been developed for the conversion of linear fatty acids to branched ones. High yields of branched acids are obtained from unsaturated fatty acids over acidic zeolites, particularly those with large pores. Fatty esters also are readily isomerized to branched ones by means of the same catalyst and process. It is postulated that the isomerization of fatty acids proceeds through three- and four-membered ring carbocation intermediates formed inside the largepore zeolites. This is supported by evidence of methyl and ethyl branching in the primary and final products. The total number of carbon atoms in the fatty acid molecule is unchanged. Surfactants derived from branched fatty acids show favorable physical properties, including a lower viscosity and improved handling, even as intended performance characteristics are maintained.     

单体酸混合物成分的GC-MS分析

研究了生产二聚酸时得到的副产品单体酸的化学组成的GC MS分析方法,样品首先用质量浓度为140g/L KOH M eOH进行甲酯化,然后用GC MS进行分析和鉴定,共鉴定出棕榈酸、肉豆蔻酸、10甲基月桂酸、12甲基十四烷酸、十八烯酸等13种物质,总脂肪酸的质量分数占76.71%,其中饱和酸占66.36%,不饱和酸占10.35%,其中直链酸占饱和脂肪酸的41.02%,支链酸即异构酸占饱和脂肪酸的58.98%。     

C18‐unsaturated branched‐chain fatty acid isomers: Characterization and physical properties

Iso‐oleic acid is a mixture of C₁₈‐unsaturated branched‐chain fatty acid isomers with a methyl group on various positions of the alkyl chain, which is the product of the skeletal isomerization reaction of oleic acid and is the intermediate used to make isostearic acid (C₁₈‐saturated branched‐chain fatty acid isomers). Methyl iso‐oleate, a mixture of C₁₈‐unsaturated branched‐chain fatty acid methyl ester isomers, is obtained via acid catalyzed esterification of iso‐oleic acid with methanol. The branched‐chain materials are liquid at room temperature and their “oiliness” property makes them an attractive candidate for the lubricant industry. In this paper, we report characterization of these branched‐chain materials using comprehensive two‐dimensional GC with time‐of‐flight mass spectrometry (GC × GC/TOF‐MS) and their physical and lubricity properties using tribology measurements.     

Characterization of branched-chain fatty acids from fallow deer perinephric triacylglycerols by gas chromatography-mass spectrometry

Branched-chain fatty acids of perinephric triacylglycerols of semi-feral fallow deer (Dama dama dama) were analyzed by high resolution gas chromatography-mass spectrometry. Of the total fatty acids, 15.50% were Branched-chain components including 8.96% iso acids, mostly 14-methylpentacanoic acid, 2.85% anteiso acids and 1.73% of other monomethyl-substituted acids; dimethyl-branched acids with an iso structure (1.05%) and with an anteiso structure (0.18%) were also present. Whereas the predominant iso acids and methyl-substituted iso acids had chain lengths of 13 and 15 carbon atoms, the anteiso acids and methyl-substituted anteiso acids had chain lengths of 14 and 16 carbon atoms. Methyl substitution occurred on the even numbered carbon atoms relative to the carboxyl group. The general composition is also given of the fatty acids comprising the triacylglycerols of subcutaneous (rump area) and perinephric adipose tissue.     

新鲜椰子果肉脂肪酸成分的GC-MS分析

以海南产新鲜高种椰为原料,参照国家标准GB/T 14772-93和GB5009.6-85,分别采用索氏抽提法和酸水解法提取新鲜椰肉脂肪酸成分,再经过氢氧化钾碱催化法进行脂肪酸的甲酯化处理后,通过气相色谱/质谱联用技术分析测定脂肪酸的组成。共检出9种脂肪酸成分,主要成分为以月桂酸为主的C6至C18系列饱和脂肪酸。