title: Manganese Oxidation State Assignment for Manganese Catalase.
abstract: The oxidation state assignment of the manganese ions present in the superoxidized manganese (III/IV) catalase active site is determined by comparing experimental and broken symmetry density functional theory calculated (14)N, (17)O, and (1)H hyperfine couplings. Experimental results have been interpreted to indicate that the substrate water is coordinated to the Mn(III) ion. However, by calculating hyperfine couplings for both scenarios we show that water is coordinated to the Mn(IV) ion and that the assigned oxidation states of the two manganese ions present in the site are the opposite of that previously proposed based on experimental measurements alone.
authors.affiliation: School of Chemistry, The University of Manchester , Oxford Road, Manchester, M13 9PL, United Kingdom.
authors.forename: Nathan J
authors.initials: NJ
authors.lastname: Beal
authors.affiliation: School of Chemistry, The University of Manchester , Oxford Road, Manchester, M13 9PL, United Kingdom.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: O'Malley
mesh_terms: D002374:Catalase / Q000378:metabolism*; D020134:Catalytic Domain; D004578:Electron Spin Resonance Spectroscopy; D008345:Manganese / Q000737:chemistry*; D017895:Manganese Compounds / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D045332:Photosystem II Protein Complex / Q000737:chemistry; D016963:Thermus thermophilus / Q000378:metabolism; D014867:Water / Q000737:chemistry
chemical_list: D017895:Manganese Compounds; D010087:Oxides; D045332:Photosystem II Protein Complex; D014867:Water; D008345:Manganese; C027424:manganese oxide; D002374:Catalase; D009584:Nitrogen