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

FEBS Letters

Shteinman, Albert A.¹ 

[1] Institute of Chemical Physics, Chernogolovka, 142432, Russian Federation

关键词: Methane monooxygenase;    Alkane oxidation;    Oxygen transfer catalysis;    O2 activation;    CH4 activation;   

DOI  :  10.1016/0014-5793(95)00195-F

学科分类：生物化学/生物物理

来源: John Wiley & Sons Ltd.

【 摘 要 】

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 O₂, which involves side-on binding of O₂ ²⁻ to iron atoms followed by its conversion to the bis-μ-oxo complex considered as an alternative of ferryl in CH₄ activation. This mechanism results in the sequence of the cleavage of the O—O bond of peroxide O/O²⁻ instead of the opposite sequence O²⁻/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 O₂ to an active intermediate. The experiment for checking this hypothesis is suggested.

【 授权许可】

Unknown