H/D Kinetic Solvent Isotope Effect in the Oxidation of Methyl Linoleate in Triton X-100 Micelles

Moskalenko, I. V.; Тихонов, И. В.

doi:10.1134/s1990793122040121

Cited by 1 publication

(2 citation statements)

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“…Another important component from which the oxidation mechanism can be attributed is the initiator; however, the influence of only the water-soluble AAPH (2,2'-Azobis(2-methylpropionamidine) dihydrochloride) initiator on the oxidation mechanism was previously considered. [10,[20][21][22] The Figure 1a shows the scheme of PUFA oxidation in micelles upon initiation with a water-soluble initiator and the proposed scheme of PUFA oxidation upon initiation with a lipid-soluble initiator.…”

Section: Introductionmentioning

confidence: 99%

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

2023

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This article discusses the oxidation of methyl linoleate in micelles, initiated by the lipid-soluble initiator 2,2'-azobis (2,4dimethylvaleronitrile) (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 * ), the k i depends on the concentration > NO * , 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.

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Section: Introductionmentioning

confidence: 99%

“…Another important component from which the oxidation mechanism can be attributed is the initiator; however, the influence of only the water‐soluble AAPH (2,2′‐Azobis(2‐methylpropionamidine) dihydrochloride) initiator on the oxidation mechanism was previously considered [10,20–22] …”

Section: Introductionmentioning

confidence: 99%