Incorporation of ubiquinones into lipid vesicles and inhibition of lipid peroxidation.

Ubiquinone incorporation into vesicles to evaluate its antioxidative effect on lipid peroxidation has been studied. Only sonication and not vortication allows comparable incorporation patterns of the various ubiquinone homologues into lipid vesicles. The measure of malondialdehyde, a convenient index for determining the extent of autoxidation, shows that both the naturally occurring homologues and synthetic shorter-chain ones, also in the oxidized form, possess similar antioxidant efficiency.

Phospholipid polar heads affect the generation of oxygen active species by Fe2+ autoxidation.

The possibility that phospholipid polar heads may influence Fe2+ reaction with molecular oxygen and, thus, the generation of oxygen active species was investigated. Dipalmitoyl phosphatidylcholine (DPPC) and DPPC/dipalmitoyl phosphatidic acid (DPPA) were utilized as model liposomes. Fe2+ oxidation, oxygen consumption, nitro blue tetrazolium reduction and 2-deoxyribose degradation were the parameters evaluated. Comparison of the results obtained clearly shows that the two types of polar heads differently affect iron chemistry. DPPC liposomes are ineffective. By contrast, Fe2+ oxidation by oxygen occurs in the presence of DPPC/DPPA liposomes. During this reaction, species able to reduce nitro blue tetrazolium and to degrade 2-deoxyribose are generated. The results obtained indicate that the polar heads of phospholipids, by influencing Fe2+ autoxidation, generate dangerous oxygen species which may exert an active role in the oxidation of the associated hydrophobic components of the phospholipids.

The influence of polyunsaturated fatty acids on spermine inhibition of lipoperoxidation. Studies on liposomes prepared with microsomal and mitochondrial phospholipids of sea bass (Dicentrarchus labrax L.) and rat liver.

1. Composition of phospholipids extracted from different organelles of European sea bass liver was determined and compared with that of phospholipids extracted from the same organelles of rat liver. 2. Spermine binding to the vesicles prepared from microsomal and mitochondrial phospholipids and their aggregation was studied: these parameters indicate that only the presence of acidic phospholipids and not their unsaturation was essential for polyamine action. 3. No correlation exists between polyunsaturated fatty acid and spermine inhibition of lipid peroxidation. In fact microsomal phospholipids, which have a low content of acidic phospholipids, and a prevalent presence of phosphatidylinositol, are not protected by spermine. 4. Mitochondrial phospholipids, which have high content of cardiolipin, elicit the capability of spermine to inhibit lipid peroxidation.

The influence of phospholipid polar head on the lipid hydroperoxide dependent initiation of lipid peroxidation.

In a buffer (Mes) and at a pH (6.5) where Fe2+ is very stable, we have studied the peroxidation of liposomes catalyzed by FeCl2. The liposomes studied, prepared by sonolysis, contained either phosphatidylcholine or 1:1 molar ratio of phosphatidylcholine and phosphatidic acid. The presence of the negatively charged phospholipid causes: 1) rapid Fe2+ oxidation and oxygen consumption; 2) increased generation of lipid hydroperoxides; 3) decreased generation of thiobarbituric acid-reactive materials; 4) very low inhibition of Fe2+ oxidation and lipid hydroperoxide generation by BHT; 5) inhibition of the termination phase of lipid peroxidation at high FeCl2 concentrations. A hypothesis is proposed to explain the results obtained.

Antioxidant behaviour of ubiquinone and beta-carotene incorporated in model membranes.

Experiments with model membranes, in which ubiquinone was incorporated, were performed in order to clarify the mechanism by which ubiquinone can prevent or control chain lipid peroxidation in biomembranes. Comparing the behavior of ubiquinone-containing vesicles with beta-carotene containing vesicles we suggest that a possible explanation of the ubiquinone antioxidant effect could be to scavenge singlet oxygen and to affect structurally the lipid bilayer inhibiting hydroperoxide decomposition.