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Inorganics 2015, 3(2), 219-229; doi:10.3390/inorganics3020219

Manganese-Substituted Myoglobin: Characterization and Reactivity of an Oxidizing Intermediate towards a Weak C-H Bond

Benedictine University, 5700 College Road, Lisle, IL 60532
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Academic Editor: Duncan Gregory
Received: 9 January 2015 / Revised: 14 May 2015 / Accepted: 19 May 2015 / Published: 27 May 2015
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Abstract

Metal-substituted hemoproteins have been examined by biochemists for decades, but their potential for diverse functionalities has not been thoroughly investigated. By replacing hemoproteins with non-native metals, heme-containing proteins could be capable of performing a range of chemistries not allowed for in the native protein. The metal within the heme of the oxygen-carrying hemoprotein, myoglobin, can readily be replaced with other first row transition metals such as cobalt, chromium and manganese. Upon oxidation with two-electron oxidants (ex. meta-chloroperbenzoic acid), an oxidizing intermediate is produced in manganese-substituted myoglobin. Electron paramagnetic resonance analyses confirm the oxidation of Mn(III) to Mn(IV). With the addition of weak C-H bonds of 1,4 cyclohexadiene, hydrogen atom abstraction is exhibited by the oxidizing intermediate that displays a second-order rate constant of 2.79 +/− 0.22 M−1 s−1 by the metal-oxo species. The replacement of the iron ion with a manganese ion at the active site of myoglobin displays oxidative capabilities that are not shown in native myoglobin. View Full-Text
Keywords: myoglobin; metal-oxo; manganese-substituted hemoprotein myoglobin; metal-oxo; manganese-substituted hemoprotein
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Stone, K.L.; Hua, J.; Choudhry, H. Manganese-Substituted Myoglobin: Characterization and Reactivity of an Oxidizing Intermediate towards a Weak C-H Bond. Inorganics 2015, 3, 219-229.

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