Critical role of deep hydrogen tunneling to accelerate the antioxidant reaction of ubiquinol and vitamin e

Taichi Inagaki, Takeshi Yamamoto

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

In biomembranes a variety of antioxidants work to suppress oxidative damage. Vitamin E and ubiquinol are among the most important lipid-soluble antioxidants, which trap lipid peroxyl radicals directly or work cooperatively in the regeneration of vitamin E radicals by ubiquinol. Here, we investigate the latter regeneration reaction by using variational transition-state theory with multidimensional tunneling corrections. The result shows that the system forms a compact H-bonded complex by significantly rearranging the donor and acceptor moieties, which leads to a rather narrow potential barrier for H transfer and a very large tunneling effect with a transmission coefficient >4000. In accord with experiment, the Arrhenius activation energy is found to be very small (∼1 kcal/mol), which is interpreted here in terms of mean tunneling energy through the barrier. Regarding the electronic structure, we demonstrate that the present reaction proceeds via a proton-coupled electron transfer (PCET) mechanism and suggest that the PCET character also contributes to the large tunneling effect by sharpening the potential barrier. Finally, a systematic comparison is made among relevant reactions and it is indicated that the antioxidant defense of biomembranes may benefit rather significantly from quantum tunneling to enhance the reaction efficiency.

Original languageEnglish
Pages (from-to)937-950
Number of pages14
JournalJournal of Physical Chemistry B
Volume118
Issue number4
DOIs
Publication statusPublished - 2014 Jan 30
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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