Homologs of methyl esters of very polar fatty acids were obtained by methanolysis of cerebrin phosphate isolated from baker's yeast. The major ester component was isolated by preparative gas-liquid chromatography and was found to be 2,3-dihydroxyhexacosanoic acid as deduced from the mass spectra of its trimethylsilyl ether and isopropylidene derivative, reaction with periodate, and comparison of its chromatographic behavior with that of synthetic erythro- and threo-dihydroxy acids. Its infrared spectrum supported the above conclusions. From their retention times by gas-liquid chromatography, the homologs were found to be saturated, unbranched 2,3-dihydroxy fatty acids with 24-27 carbon atoms. The synthesis of the new fatty acids, erythro- and threo-2,3-dihydroxyhexacosanoic acids, is also reported. A method for separating trans-2-hexacosenoic acid, a key intermediate of the above synthesis, and its isomer, trans-3-hexacosenoic acid, both formed by dehydrobromination of 2-bromohexacosanoic acid, is also described.

Chromatography, Gas↗

PubMed1973

Branched-chain and odd-numbered fatty acids and aldehydes in the nervous system of a patient with deranged vitamin B 12 metabolism.

A mixture of isomers of methylhexadecanoic acid was isolated from glycerolipids of brain, spinal cord, and sciatic nerve of a patient who died from methylmalonic aciduria, a disease in which vitamin B(12) is not converted to deoxyadenosyl B(12). The isomers were identified by gas-liquid chromatographic-mass spectrometric analyses, and the data indicated that the points of methyl branching are located predominantly on the even-numbered carbon atoms. The concentration of these branched-chain acids among the glycerolipid fatty acids in the patient's nervous system was at least 0.3-0.9%, while the control tissues contained no more than a trace amount, if any, of these acids. In the spinal cord, these branched acids were distributed among all phosphatides and were in highest concentration on the beta position of phosphatidylcholine. On the other hand, most extraneural tissues contained these acids in much lower concentrations; there were only trace amounts in liver, kidney, muscle, and skin, and 0.2, 0.2, and 0.5% in total ester-linked fatty acids in spleen, duodenum, and lung, respectively. A second abnormality was the 6-13-fold increase in 15:0 and 17:0 fatty acids in all of the glycerolipids in the nervous system of the patient. This abnormality was also observed to a somewhat smaller extent in every extraneural tissue examined. The C(17) aldehydes of phosphatidylethanolamine plasmalogens from the spinal cord of the patient were identified by converting them to the corresponding dimethylacetals. 17:0 dimethylacetal accounted for nearly 10% of total dimethylacetals. There were no abnormalities in total lipids, cholesterol, cerebrosides, and sphingomyelins.

Acids↗

PubMed1973

Esterification of fatty acids at room temperature by chloroform-methanolic HCl-cupric acetate.

A new procedure for the preparation of methyl esters from free fatty acids under mild conditions was investigated. Free fatty acids are dissolved in a mixture of chloroform-methanolic HCl-cupric acetate and kept at room temperature for 30 min for complete esterification. The method is suitable for esterification of long-chain acids, such as 18:0, and for very long chain acids, such as 24:0. Fatty acids from brain glycerophosphatides, which included a high concentration of polyenes such as 20:4 (n - 6), 22:4 (n - 6), and 22:6 (n - 3), were also esterified by the same procedure, and neither artifact formation nor loss of unsaturated acids was observed.

Carbon Isotopes↗

PubMed1972