Oxidation of Methyl Linoleate in Triton X-100 Micelles Initiated by Lipid-soluble Initiator 2,2 '-Azobis (2,4-dimethylvaleronitrile)

This article discusses the oxidation of methyl linoleate in micelles, initiated by the lipid-soluble initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (AMVN). It was shown that the rate constant (k(i)) is initiated in micelles for AMVN significantly lower than the known rate constant of initiation in true solutions. This can be explained by the reduced probability of AMVN radicals leaving the cage and an increase in the rate of chain termination between initiator radicals under conditions of low oxygen content. This conclusion was confirmed by quantum chemical calculations. Surprisingly, when determining the AMVN initiation rate constant for the consumption of nitroxyl radicals (>NO center dot), the ki depends on the concentration >NO center dot, this is due to the dependence of the probability of the nitroxyl radical and initiator radicals in micelles meeting on their concentration. Upon initiation of AMVN, no hydroperoxyl radical is expelled.

Automated summary

This article discusses the oxidation of methyl linoleate in micelles initiated by lipid-soluble initiator AMVN. It was found that the initiation rate constant (k(i)) of AMVN in micelles is significantly lower than in true solutions. This can be explained by the reduced probability of AMVN radicals leaving the cage and an increase in the rate of chain termination under low oxygen conditions. Quantum chemical calculations confirm this conclusion. Surprisingly, the initiation rate constant of AMVN for the consumption of nitroxyl radicals (>NO center dot) depends on the >NO center dot concentration, due to the probability of nitroxyl radicals and initiator radicals meeting in micelles being dependent on their concentration. No hydroperoxyl radicals are expelled upon AMVN initiation.