Radical delivery and fragmentation for structural analysis of glycerophospholipids

摘要: Abstract Conventional tandem mass spectrometry relies on even-electron fragmentation that provides limited structural information for glycerophospholipids (GP), which are key constituents of all cell membranes. Different GP classes chemically very similar and subtle variations in carbon-carbon bonding features linkages can lead to numerous isomeric structures challenging distinguish with traditional spectrometry. In this study, we demonstrate the primary amine groups many be modified either noncovalent attachment crown ether derivatives containing an iodobenzoyl moiety, or by direct covalent moiety. Radical lipids generated using these modifications via photoactivation labile carbon-iodine bonds, providing rich about headgroup fatty acid chain structure. The method is demonstrated lipid standards various carbon motifs linkages, as well phospholipids extracted from a soybean mixture. Numerous were examined, including plasmalogen-, lyso-, diacyl- types mono-/poly- unsaturated (FA) substituents, branched-/nonbranched-FA chains. Interestingly, presence double bond and/or vinyl linkage leads formation signature fragment ion facilitates rapid identification.