Oxidation of lipids. 7. Oxidation of phosphatidylcholines in homogeneous solution and in water dispersion.

The rates and products of the oxidations of phosphatidylcholines (PCs) in organic homogeneous solutions and as multilamellar liposomes in an aqueous dispersion were studied at 50 degrees C initiated by oil-soluble and water-soluble azo compounds and with the aim primarily of elucidating the effect of substrate and the reaction medium. Polyunsaturated fatty acids were oxidized exclusively among the fatty acids in PC. The product distribution was determined by the number of double bonds: in the oxidation of methyl linoleate and dilinoleoyl PC, the conjugated diene hydroperoxides were formed almost quantitatively, whereas in the oxidation of PC and polyunsaturated fatty acids having three or more double-bonds, cyclic peroxides were also formed. The oxidizability of PC was dependent on the content of doubly allylic hydrogens and their reactivities were suggested to be similar, independent of parent substrate and reaction medium, although the oxidizability of PC in nonpolar organic solvents is markedly enhanced by the formation of reverse-phase micelles.