Radical peroxidation of palmitoyl-lineloyl-glycerophosphocholine liposomes: Identification of long-chain oxidised products by liquid chromatography-tandem mass spectrometry.

Liquid chromatography coupled with electrospray tandem mass spectrometry (LC-MS/MS) was used to identify palmitoyl-lineloyl-glycerophosphatidylcholine oxidation products (PL(O(1-6))PC). Structural and positional isomers of keto, hydroxy and/or epoxy, and hydroperoxide derivatives of PLPC were identified based on MS/MS data, namely product ions attributed to lyso-phosphatidylcholines, product ions formed by loss of nH(2)O and H(2)O(2) from [MH](+) ions groups, and product ions involving the hydroxy groups, providing information about the position of these groups and of the double bonds along the carbon chain of lineloyl moiety.

Identification of linoleic acid free radicals and other breakdown products using spin trapping with liquid chromatography-electrospray tandem mass spectrometry.

Linoleic acid radical products formed by radical reaction (Fenton conditions) were trapped using 5,5-dimethyl-1-pyrrolidine-N-oxide (DMPO) and analysed by reversed-phase liquid chromatography coupled to electrospray mass spectrometry (LC-MS). The linoleic acid radical species detected as DMPO spin adducts comprised oxidized linoleic acid and short-chain radical species that resulted from the breakdown of carbon and oxygen centred radicals. Based on the m/z values, the short-chain products were identified as alkyl and carboxylic acid DMPO radical adducts that exhibited different elution times. The ions identified as DMPO radical adducts were studied by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The LC-MS/MS spectra of linoleic acid DMPO radical adducts exhibited the fragment ion at m/z 114 and/or the loss of neutral molecule of 113 Da (DMPO) or 131 Da (DMPO + H2O), indicated to be DMPO adducts. The short-chain products identified allowed inference of the radical oxidation along the linoleic acid chain by abstraction of hydrogen atoms in carbon atoms ranging from C-8 to C-14. Other ions containing the fragment ion at m/z 114 in the LC-MS/MS spectra were attributed to DMPO adducts of unsaturated aldehydes, hydroxy-aldehydes and oxocarboxylic acids. The identification of aldehydic products formed by radical oxidation of linoleic acid peroxidation products, as short-chain product DMPO adducts, is a means of identifying lipid peroxidation products.