Manganese-Substituted Myoglobin: Characterization and Reactivity of an Oxidizing Intermediate towards a Weak C-H Bond
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Academic Editor: Duncan Gregory
Inorganics 2015, 3(2), 219-229; https://doi.org/10.3390/inorganics3020219
Received: 9 January 2015
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Revised: 14 May 2015
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Accepted: 19 May 2015
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Published: 27 May 2015
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.
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Keywords:
myoglobin; metal-oxo; manganese-substituted hemoprotein
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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. https://doi.org/10.3390/inorganics3020219
AMA Style
Stone KL, Hua J, Choudhry H. Manganese-Substituted Myoglobin: Characterization and Reactivity of an Oxidizing Intermediate towards a Weak C-H Bond. Inorganics. 2015; 3(2):219-229. https://doi.org/10.3390/inorganics3020219
Chicago/Turabian StyleStone, Kari L., Joey Hua, and Humdoon Choudhry. 2015. "Manganese-Substituted Myoglobin: Characterization and Reactivity of an Oxidizing Intermediate towards a Weak C-H Bond" Inorganics 3, no. 2: 219-229. https://doi.org/10.3390/inorganics3020219
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