Fast-atom-bombardment and tandem mass spectrometry for determining structures of fatty acids as their picolinyl ester derivatives

Picolinyl ester derivatives of common fatty acids can be readily desorbed by fast atom bombardment (FAB) as positive ions and then collisionally activated. Collisionally activated spectra of the (M + H)⁺ ions of the derivatives reveal that structurally informative remote-charge-site fragmentations occur. The presence of substitutents such as double bond, branch points, cyclopropane rings, hydroxy groups, and epoxy rings interrupts the fragmentation process in such a way that the substituent can be identified and its location on the alkyl chain can be determined. This method is also applicable to the picolinyl esters of short-chain fatty acids and to the analysis of mixtures of fatty acid derivatives. The approach is advantageous becasue the epicolinyl ester derivatives are also amenable to gas chromatography/mass spectrometry (GC/MS). Therefore, the FAB-MS/MS approach developed here is complementary to GC/MS.