Effects of alpha-tocopherol and ascorbyl palmitate on the isomerization and decomposition of methyl linoleate hydroperoxides.

Abstract

In order to study antioxidant action on lipid hydroperoxide decomposition, the effects of alpha-tocopherol (TOH) and ascorbyl palmitate on the decomposition rate and reaction sequences of 9- and 13-cis,trans methyl linoleate hydroperoxide (cis,trans ML-OOH) decomposition in hexadecane were studied at 40 degrees C. Decomposition of cis,trans ML-OOH as well as the formation and isomeric configuration of methyl linoleate hydroxy and ketodiene compounds were followed by high-performance liquid chromatographic analysis. TOH effectively inhibited the decomposition of ML-OOH. The decomposition rate was two times slower at 0.2 mM and more than 10 times slower at 2 and 20 mM of TOH. Ascorbyl palmitate (0.2, 2, and 20 mM) slightly accelerated the decomposition of ML-OOH. Both compounds had an effect on the reaction sequences of ML-OOH decomposition. At high levels TOH inhibited the isomerization of cis,trans ML-OOH to trans,trans ML-OOH through peroxyl radicals and increased the formation of hydroxy compounds. Further, the majority of the hydroxy and ketodiene compounds formed had a cis,trans configuration, indicating that cis,trans ML-OOH decomposed through alkoxyl radicals without isomerization. These results suggest that when inhibiting the decomposition of hydroperoxides, TOH can act as a hydrogen atom donor to both peroxyl and alkoxyl radicals. In the presence of ascorbyl palmitate, cis,trans ML-OOH decomposed rapidly but without isomerization. In contrast to TOH, the majority of hydroxy compounds were cis,trans, but the ketodiene compounds were trans,trans isomers. This indicates that ascorbyl palmitate reduced cis,trans ML-OOH to the corresponding hydroxy compounds. However, the simultaneous formation of trans,trans ketodiene compounds suggests that ML-OOH decomposition, similar to the control sample, also occurred in these samples. Thus, under these experimental conditions, the reduction of ML-OOH to more stable hydroxy compounds did not occur to an extent significant enough to inhibit the radical chain reactions of ML-OOH decomposition.