Positional isomers of unsaturated fatty acids in rat liver lipids.

The fatty acids of liver lipids from rats raised on a fat free diet from the 30th to the 90th day after birth were analyzed with special regard to the detection of positional isomers of mono-, di-, tri-, and tetraenoic fatty acids. The methyl esters obtained after transesterification of total lipids were separated by argentation chromatography into five fractions: I saturated, II monoenoic, III dienoic, IV dienoic nonmethylene interrupted, V tri- and tetraenoic fatty acid esters. After hydroxylation of the double bonds with osmium tetroxide, the analysis of the poly-O-trimethylsilyl derivatives by gas liquid chromatography on S.C.O.T. columns combined with mass spectrometry revealed the presence of 19 monoenoic, 15 dienoic, and 9 trienoic as well as 3 tetraenoic fatty acid isomers including the normally occurring representatives of the (n-3), (n-6), (n-7), and (n-9) fatty acid families. The majority of the identified isomers can be coordinated to one of these families like 7-16:1; 11-20:1; 6,9-18:2; 8,11-20:2; 5,11-20:2; 5,8,11-20:3; 7,10,13-22:3 to the (n-9) family, 11-18:1; 13-20:1; 5,11-18:2; 7,13-20:2; 6,11-18:2; 6,9-16:2; 8,11-18:2; 10,13-20:2; 5,8,11-18:3; 7,10,13-20:3; 4,7,10,13-20:4 to the (n-7) family and 11,14-20:2; 5,11,14-20:3; 6,9,12-18:3; 8,11,14-20:3; 5,8,11,14-20:4; 7,10,13,16-22:4 to the (n-6) family. All these naturally occuring isomers can be placed into a network of desaturation and chain elongation steps which allows certain conclusions about the substrate specificity of the delta6-, delta5- and delta4-desaturase systems. The great number of isomers found in the (n-7) family indicates that the members of this family are actively metabolized in partial essential fatty acid deficiency.