Gas chromatography-mass spectrometry determination of metabolites of conjugated cis-9,trans-11,cis-15 18:3 fatty acid.
Structural determination of polyunsaturated fatty acids by gas chromatography-mass spectrometry (GC-MS) requires currently the use of nitrogen containing derivatives such as picolinyl esters, 4,4-dimethyloxazoline or pyrrolidides derivatives. The derivatization is required in most cases to obtain low energy fragmentation that allows accurate location of the double bonds. In the present work, the following metabolites of rumelenic (cis-9,trans-11,cis-15 18:3) acid, from rat livers, were identified: cis-8,cis-11,trans-13,cis-17 20:4, cis-5,cis-8,cis-11,trans-13,cis-17 20:5, cis-7,cis-10,cis-13,trans-15,cis-19 22:5, and cis-4,cis-7,cis-10,cis-13,trans-15,cis-19 22:6 acids by GC-MS as their 4,4-dimethyloxazoline and methyl esters derivatives. Specific fragmentation of the methyl ester derivatives revealed some similarity with their corresponding DMOX derivatives. Indeed, intense ion fragments at m/z=M+-69, corresponding to a cleavage at the center of a bis-methylene interrupted double bond system were observed for all identified metabolites. Moreover, intense ion fragments at m/z=M+-136, corresponding to allylic cleavage of the n-12 double bonds were observed for the C20:5, C22:5, C22:6 acid metabolites. For the long chain polyunsaturated fatty acids from the rumelenic metabolism, we showed that single methyl esters derivatives might be used for both usual quantification by GC-FID and identification by GC-MS.
Destaillats
Frédéric
F
Department of Food Science and Nutrition, and Dairy Research Center (STELA), Université Laval, Québec, QC, Canada, G1K 7P4.
Sébédio
Jean-Louis
JL
Berdeaux
Olivier
O
Juanéda
Pierre
P
Angers
Paul
P
D000818:Animals; D004952:Esters / Q000138:chemical synthesis; D005231:Fatty Acids, Unsaturated / Q000737:chemistry* / Q000378:metabolism*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D008099:Liver / Q000378:metabolism; D000432:Methanol / Q000737:chemistry; D010080:Oxazoles / Q000737:chemistry* / Q000378:metabolism*; D051381:Rats
D004952:Esters; D005231:Fatty Acids, Unsaturated; D010080:Oxazoles; C502940:rumelenic acid; C057549:4,4-dimethyloxazoline; D000432:Methanol