The autoxidation of unsaturated lipids in micelles. Synergism of inhibitors vitamins C and E

Abstract

The kinetics of thermally (30 °C) initiated autoxidations of unsaturated lipids, linoleic acid, and methyl linoleate are studied in 0.50 M sodium dodecyl sulfate (SDS) micelles. The rate of chain initiation, R1, was controlled by using known amounts of the thermal initiator, di-tert-butylhyponitrite (DBHN). The initiator efficiency, e, determined by the induction period method with x-tocopherol, was 0.30 for linoleic acid and varied (0.30 to 0.36) for methyl linoleate autoxiation as the concentration of the ester increased. The rate of autoxidation of linoleic acid follows the classical rate law since it is proportional to the substrate concentration and to the square root of chain initiation. The oxidizability of linoleic acid measured in micelles is 4.09 × 10−2 M−1/2 s−1/2. The oxidizability of methyl linoleate varied from 2.37 × 10−2 to 6.92 × 10−2 M−1/2 s−1/2 as the amount of solubilized ester increased. The latter results are indicative of pooling of the ester in the micellar phase. Additions of aqueous solutions of ascorbic acid to α-tocopherol-inhibited micellar autoxidations result in very significant extensions of the efficient inhibition period compared to that obtained with α-tocopherol alone. The mechanism of this synergism is briefly discussed.