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Use of a metallopeptide-based mimic provides evidence for a proton-coupled electron-transfer mechanism for superoxide reduction by nickel-containing superoxide dismutase.


ABSTRACT: Sneaky little SOD! A metallopeptide-based mimic of nickel-containing superoxide dismutase was used to probe the mechanism of superoxide reduction by the metalloenzyme. Kinetic studies suggest a proton-coupled electron-transfer mechanism; large H/D kinetic isotope effects (KIE) are observed. XAS studies suggest the transferred H-atom is in the form of a Ni(II) -S(H)-Cys moiety.

SUBMITTER: Shearer J 

PROVIDER: S-EPMC3752415 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature

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Use of a metallopeptide-based mimic provides evidence for a proton-coupled electron-transfer mechanism for superoxide reduction by nickel-containing superoxide dismutase.

Shearer Jason J  

Angewandte Chemie (International ed. in English) 20130122 9


Sneaky little SOD! A metallopeptide-based mimic of nickel-containing superoxide dismutase was used to probe the mechanism of superoxide reduction by the metalloenzyme. Kinetic studies suggest a proton-coupled electron-transfer mechanism; large H/D kinetic isotope effects (KIE) are observed. XAS studies suggest the transferred H-atom is in the form of a Ni(II) -S(H)-Cys moiety. ...[more]

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