Formation of platelet-activating factor-like phospholipids by Fe2+/ascorbate/EDTA-induced lipid peroxidation.

We have identified novel phospholipids together with platelet-activating factor and its 1-acyl analogues in purified fractions from a bovine brain lipid extract. These novel compounds were phospholipids with an sn-2-short-chain monocarboxylyl, dicarboxylyl or omega-hydroxymonocarboxylyl group. The profiles of these three types of phospholipids suggest that they were formed by lipid peroxidation. To examine this possibility, we peroxidized synthetic phosphatidylcholines (PC) with an sn-2-polyunsaturated fatty acyl group and PC from bovine brain, with Fe2+/ascorbate/EDTA, and analyzed the secondary degradation products retaining a glycerol backbone by fast atom bombardment-mass spectrometry and GC-MS. Results showed the formation of four kinds of PC with a short-chain monocarboxylate, dicarboxylate, dicarboxylate semialdehyde or omega-hydroxymonocarboxylate moiety. The chain lengths of these PC were related to the position of the double bond vicinal to the esterified carbonyl group in the sn-2-long-chain acyl moiety of the parent PC. The molecular heterogeneity of secondary products formed by the oxidative degradation of bovine brain PC resembled those of the unique phospholipids that we previously detected in the fractions with platelet-activating factor-like activity purified from a bovine brain lipid extract, although the former lacked the species with an acetyl group. These results suggest that all the novel phospholipids with a short-chain acyl group in the brain lipid extract except that with an acetyl group were produced by lipid peroxidation.