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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Detalles Bibliográficos
Publicado en:Journal of the American Chemical Society Vol. 138; no. 13; pp. 4358 - 4362
Autores principales: Beal, Nathan J., O'Malley, Patrick J.
Formato: Artículo
Publicado: American Chemical Society 4/6/2016
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Acceso en línea:Ver este registro en EBSCOhost
Descripción
Sumario: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.