Double bond localization in minor homoallylic fatty acid methyl esters using acetonitrile chemical ionization tandem mass spectrometry

Double bond position in natural fatty acids is critical to biochemical properties, however, common instrument-based methods cannot locate double bonds in fatty acid methyl esters (FAME), the predominant analysis form of fatty acids. A recently described mass spectrometry (MS) method for locating double bonds in FAME is reported here for the analysis of minor (< 1%) components of real FAME mixtures derived from three natural sources; golden algae (Schizochytrium sp.), primate brain white matter, and transgenic mouse liver. Acetonitrile chemical ionization tandem MS was used to determine double bond positions in 39 FAME, most at concentrations well below 1% of all fatty acid methyl esters. FAME identified in golden algae are 14: In - 6, 14:3n - 3, 16: In - 7, 16:2n - 6, 16:3n - 6, 16:3n - 3, 16:4n - 3, 18:2n - 7, 18:3n - 7, 18:3n - 8, 18:4n - 3, 18:4n - 5, 20:3n - 7, 20:4n - 3, 20:4n - 5, 20:4n - 7, 20:5n - 3, and 22:4n - 9. Additional FAME identified in primate brain white matter are 20:ln - 7, 20:ln - 9, 20:2n - 7, 20:2n - 9, 22: 1 n - 7, 22: 1 n - 9, 22: 1 n - 13, 22:2n - 6, 22:2n - 7, 22:2n - 9, 22:3n - 6, 22:3n - 7, 22:3n - 9, 22:4n - 6, 24: 1 n - 7, 24: 1 n - 9, and 24:4n - 6. Additional FAME identified in mouse liver are 26:5n - 6, 26:6n - 3, 28:5n - 6, and 28:6n - 3. The primate brain 22:3n - 7 and algae 18:4n - 5 are novel fatty acids. These results demonstrate the usefulness of the technique for analysis of real samples. Tables are presented to aid in interpretation of acetonitrile CIMS/MS spectra. (C) 2002 Elsevier Science (USA). All rights reserved.