Abstract

Recent developments in mass spectrometry (MS) designed to accommodate high molecular weight molecules such as polypeptides and polynucleotides have also revolutionized the MS of complex lipid molecules. Soft ionization MS techniques such as fast atom bombardment (FAB), thermospray (TS) and electrospray (ES) have the ability to ionize lipid molecules without causing extensive fragmentation. This generally leads to mass spectra characterized by [M + 1]+ (positive ion mode) or [M - 1]- (negative ion mode) ions. Fragmentation of the molecular ion species produced by soft ionization processes is achieved in a second mass spectrometer (MS/MS) by collision-induced dissociation (CID). The FAB/MS and TS/MS methods with or without online high-pressure liquid chromatography (HPLC) provided the initial successes in unravelling the structure of complex lipids. Subsequently ES/MS and ES/MS/MS with flow injection (Han and Gross, 1994; Kerwin, Tuininga and Ericsson, 1994) and ES/MS with HPLC (LC/ES/MS) (Kim, Wang and Ma, 1994; Myher et al., 1994) proved superior to the earlier approaches and are currently being applied in the analyses of molecular species from minimal amounts of complex lipids without derivatization.

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