Oxidation decomposition of unsaturated fatty acids by singlet oxygen in phospholipid bilayer membranes.

Oxidation decomposition of unsaturated fatty acids with singlet oxygen generated from a photosensitizing agent was investigated in liposome bilayer membranes under a light irradiation condition. The liposome of which the bilayer membrane was composed of L-alpha-dipalmitoylphosphatidylcholine (DPPC), protoporphyrin IX (PpIX), and an unsaturated fatty acid (oleic acid, linoleic acid, alpha-linolenic acid, or arachidonic acid) were prepared with Bangham's method. In irradiating the liposome dispersion with light ranged from 550 to 750 nm, the unsaturated fatty acid was decomposed through an oxidation reaction with singlet oxygen. The decomposition rate constant was obeyed as the following order: arachidonic acid > oleic acid > alpha-linolenic acid > linoleic acid. This result indicates that oleic acid is readily degraded despite its lower unsaturated degree. In addition, micropolarity and microfluidity of the hydrocarbon region in the liposome bilayer membrane including the unsaturated fatty acid and PpIX decreased with an increase in light irradiation time. These findings suggest that interaction among the hydrocarbon chains of DPPC in the liposome bilayer membrane is promoted by migration of the oxidized unsaturated fatty acid from the hydrocarbon region, leading to form close-packed and well-ordered orientation of the hydrocarbon chains.