Manganese Oxidation State Assignment for Manganese Catalase.

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 N, O, and H hyperfine couplings. Experimental results have been interpreted to in...

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Published in:Journal of the American Chemical Society Vol. 138; no. 13; pp. 4358 - 4362
Main Authors: Beal, Nathan J., O'Malley, Patrick J.
Format: Article
Published: American Chemical Society 4/6/2016
Subjects:
Online Access:View this record in EBSCOhost
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      dt: 4/6/2016
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      pub: American Chemical Society
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        10.1021/jacs.6b02600
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        atl: Manganese Oxidation State Assignment for Manganese Catalase.
      aug:
        au:
          Beal, Nathan J.
          O'Malley, Patrick J.
        affil: School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom
      su:
        Oxidation
        Manganese
        Catalase
        Density functional theory
        Hyperfine coupling
      sug:
        subj:
          Oxidation
          Manganese
          Catalase
          Density functional theory
          Hyperfine coupling
      ab: 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 N, O, and 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.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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