Unusual kinetic isotope effects of deuterium reinforced polyunsaturated fatty acids in tocopherol-mediated free radical chain oxidations.

Lamberson CR, Xu L, Muchalski H, Montenegro-Burke JR, Shmanai VV, Bekish AV, McLean JA, Clarke CF, Shchepinov MS, Porter NA
J Am Chem Soc. 2014 136 (3): 838-41

PMID: 24380377 · PMCID: PMC4578730 · DOI:10.1021/ja410569g

Substitution of -CD2- at the reactive centers of linoleic and linolenic acids reduces the rate of abstraction of D by a tocopheryl radical by as much as 36-fold, compared to the abstraction of H from a corresponding -CH2- center. This H atom transfer reaction is the rate-determining step in the tocopherol-mediated peroxidation of lipids in human low-density lipoproteins, a process that has been linked to coronary artery disease. The unanticipated large kinetic isotope effects reported here for the tocopherol-mediated oxidation of linoleic and linolenic acids and esters suggests that tunneling makes this process favorable.

MeSH Terms (8)

Deuterium Fatty Acids, Unsaturated Free Radicals Humans Kinetics Lipoproteins, LDL Oxidation-Reduction Tocopherols

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