The role of CO2 in metal-catalyzed peroxidations.
Transition metals, such as Cu(+2), Mn(+2), and Co(+2), have been seen to catalyze the bicarbonate enhanced oxidation of a variety of substrates by H(2)O(2). In several of these cases it has been demonstrated that CO(2), rather than bicarbonate, is the enhancing species. Mechanisms that are in accord with the data involve a hypervalent state that may be written (MO)(+n), or (MOH)(+n+1), or (M)(+n+2). This metal centered oxidant then oxidizes CO(2) to the carbonate radical; that is then the proximal oxidant of the various substrates. Whether a similar process has in vivo reality remains to be demonstrated.
Liochev
Stefan I
SI
The Department of Biochemistry, Box 3711, Duke University Medical Center, Durham, NC 27710, USA.
Fridovich
Irwin
I
D001639:Bicarbonates / Q000737:chemistry / Q000378:metabolism; D002245:Carbon Dioxide / Q000737:chemistry* / Q000378:metabolism; D002384:Catalysis; D006861:Hydrogen Peroxide / Q000737:chemistry* / Q000378:metabolism; D013482:Superoxide Dismutase / Q000737:chemistry; D028561:Transition Elements / Q000737:chemistry* / Q000378:metabolism
D001639:Bicarbonates; D028561:Transition Elements; D002245:Carbon Dioxide; D006861:Hydrogen Peroxide; D013482:Superoxide Dismutase