title: 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.
authors: Department of Chemistry, University of Nevada, Reno, NV 89557, USA. shearer@unr.edu
authors: Jason
authors: J
authors: Shearer
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry; D002413:Cations, Divalent / Q000737:chemistry; D004579:Electron Transport; D007700:Kinetics; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D011522:Protons; D013482:Superoxide Dismutase / Q000737:chemistry* / Q000378:metabolism; D013481:Superoxides / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D002413:Cations, Divalent; D011522:Protons; D013481:Superoxides; D009532:Nickel; D013482:Superoxide Dismutase