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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
Author(s) -
Shearer Jason
Publication year - 2013
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201209746
Subject(s) - superoxide , chemistry , electron transfer , mechanism (biology) , superoxide dismutase , oxygen reduction , moiety , nickel , photochemistry , enzyme , stereochemistry , biochemistry , electrochemistry , philosophy , epistemology , organic chemistry , electrode
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 (see graph).