Acetonitrile chemical ionization tandem mass spectrometry to locate double bonds in polyunsaturated fatty acid methyl esters.
A rapid method is presented for determining the location of double bonds in polyunsaturated fatty acid methyl esters (FAME) using an ion-trap mass spectrometer. The mass spectrum of the chemical ionization reagent acetonitrile in an ion trap includes a m/z 54 ion, identified previously as 1-methyleneimino-1-ethenylium ion. We show that it reacts with double bonds of polyunsaturated FAME to yield a series of covalent product ions all appearing at (M + 54)+. Collisional dissociation of these ions yields diagnostic fragments, permitting unambiguous localization of double bonds. For methylene-interrupted and conjugated FAME, one of these fragments results from loss of the hydrocarbon end of the chain, while the other involves loss of the methyl ester. Major diagnostic-fragment ions for monoene and diene FAME occur as a result of cleavage adjacent to either allylic sites or double bonds in the original analyte and appear at one mass unit above the mass expected for homolytic cleavage. Fragmentation of polyene FAME yields major diagnostic ions resulting from cleavage between double bonds that appear one mass unit lower. The method is shown to produce highly characteristic spectra for FAME with 1 to 6 double bonds. Identification of double-bond position in highly unsaturated fatty acids is demonstrated in a mixture of unknown polyunsaturated FAME from an extract of cultured Y79 human retinoblastoma cells.
Van Pelt
C K
CK
Division of Nutritional Sciences, Cornell University, Ithaca, New York 14853, USA.
Brenna
J T
JT
D000097:Acetonitriles; D004952:Esters / Q000737:chemistry; D005231:Fatty Acids, Unsaturated / Q000737:chemistry*; D006801:Humans; D013058:Mass Spectrometry; D008970:Molecular Weight; D014407:Tumor Cells, Cultured
D000097:Acetonitriles; D004952:Esters; D005231:Fatty Acids, Unsaturated