The mechanism of methane and dioxygen activation in the catalytic cycle of methane monooxygenase

The binuclear structure of the active center of methane monooxygenase plays a determining role in dioxygen activation and in selectivity and specificity of alkane oxidation with this enzyme. A new mechanism is suggested for binding and activation of O 2, which involves side-on binding of O 2 2− to i...

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Bibliographic Details
Published in:FEBS letters 1995-03, Vol.362 (1), p.5-9
Main Author: Shteinman, Albert A.
Format: Article
Language:English
Subjects:
Alkane oxidation
CH 4 activation
CH4 activation
Iron - metabolism
Kinetics
Methane - metabolism
Methane monooxygenase
Methylococcus capsulatus
O 2 activation
O2 activation
Oxidation-Reduction
Oxygen - metabolism
Oxygen transfer catalysis
Oxygenases - metabolism
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Summary:The binuclear structure of the active center of methane monooxygenase plays a determining role in dioxygen activation and in selectivity and specificity of alkane oxidation with this enzyme. A new mechanism is suggested for binding and activation of O 2, which involves side-on binding of O 2 2− to iron atoms followed by its conversion to the bis-μ-oxo complex considered as an alternative of ferryl in CH 4 activation. This mechanism results in the sequence of the cleavage of the OO bond of peroxide O/O 2− instead of the opposite sequence O 2−/O, which takes place in the case of heme monooxygenase cytochrome P-450. Therefore, in this case there is no necessity of the charge relay system [N.B. Gerber and S.G. Sligar, J. Am. Chem. Soc. 114 (1992) 8742] for the transformation of O 2 to an active intermediate. The experiment for checking this hypothesis is suggested.
ISSN:0014-5793
1873-3468
DOI:10.1016/0014-5793(95)00195-F