Numerical revelation of the kinetic significance of individual steps in the reaction mechanism of methyl linoleate peroxidation inhibited by alpha-tocopherol.
A kinetic model was constructed to describe the reactions involved in the oxidation of methyl linoleate (ML) inhibited by alpha-tocopherol (TH). The initial model of the reaction mechanism included 53 individual steps, which were numerically analyzed by the value method based on Hamiltonian systematization of kinetic equations. Good accord was obtained with experimental data at 40 and 50 degrees C. The dominant steps responsible for the antioxidant and pro-oxidant properties of TH in the process of ML peroxidation were revealed. Tocopherol-mediated peroxidation (TMP) and generation of alkoxyl radicals as a result of the reduction of hydroperoxides by TH or the decomposition tocopherol alkyl peroxides are the dominant reactions responsible for the pro-oxidant activities of alpha-tocopherol. The extreme behavior of reaction induction period in relation to TH initial concentration is related to the increase in the ratios of [tocopheroxyl radical]/[peroxyl radical] and the TMP rate/rate of termination by combination of tocopheroxyl and peroxyl radicals.
Tavadyan
Levon
L
A.B. Nalbandyan Institute of Chemical Physics of National Academy of Sciences of Armenia, 5/2 Sevak str. 375014, Yerevan, Armenia. tavadyan@ichph.sci.am
Khachoyan
Avet
A
Martoyan
Gagik
G
Kamal-Eldin
Afaf
A
D007700:Kinetics; D008041:Linoleic Acids / Q000737:chemistry*; D015227:Lipid Peroxidation; D024502:alpha-Tocopherol / Q000737:chemistry*
D008041:Linoleic Acids; C005575:methyl linoleate; D024502:alpha-Tocopherol