Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Structural Determination of Fatty Acyl Groups of Phospholipids by Fast Atom Bombardment Tandem Mass Spectrometry of Sodium Adduct Molecular Ions

  • Published : 1997.08.20
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Abstract

Various classes of phospholipids were investigated for the structural determination of fatty acyl groups by fast atom bombardment tandem mass spectrometry (FAB-MS/MS). Phospholipids were desorbed by FAB as molecules chelated with sodium ion (or ions). Collision-induced dissociation (CID) of intact sodium adduct molecular ions ([M+Na]+, [M-H+2Na]+ or [M+Na-2H]-) produced a series of homologous fragment ions via the charge-remote fragmentation along the fatty acid chains. These ions were found useful to locate the double bond positions even for the polyunsaturated fatty acid chains. The regiospecificity of the acyl chain linkages in phosphatidylcholine (PC) could also be determined based on the ratio of relative abundance of the product ions (i.e., [M+Na-85-R2COOH]+ vs [M+Na-85-R1COOH]+) in CID-MS/MS of [M+Na]+. These are generated by the loss of fatty acyl groups at sn-1 and sn-2, respectively, together with the choline group. In all the phospholipid compounds investigated, loss of the fatty acid at the sn-2 position was dominant. The present method was applied to the structural determination of molecular species of phosphatidylglycerols (PG) isolated from cyanobacterium Synechocystis sp. PCC 6803.

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