The mechanism of methane and dioxygen activation in the catalytic cycle of methane monooxygenase
- 27 March 1995
- journal article
- Published by Wiley in FEBS Letters
- Vol. 362 (1) , 5-9
- https://doi.org/10.1016/0014-5793(95)00195-f
Abstract
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 O22− 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 OO 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 suggestedKeywords
This publication has 28 references indexed in Scilit:
- Reactions of Non-Heme Iron(II) Centers with Dioxygen in Biology and ChemistryChemical Reviews, 1994
- First Diferric Complex with an Fe2(.mu.-O)(.mu.-OH) Core. Structure and Reactivity of [Fe2(.mu.-O)(.mu.-OH)(6TLA)2](ClO4)3Journal of the American Chemical Society, 1994
- Theoretical model for electrophilic oxygen-atom insertion into hydrocarbonsJournal of the American Chemical Society, 1993
- Activation of the hydroxylase of sMMO from Methylococcus capsulatus (Bath) by hydrogen peroxideBiochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology, 1993
- On the Strength of the C-H…︁O Hydrogen Bond and the Eclipsed Arrangement of the Methyl Group in a Tricyclic Orthoamide TrihydrateAngewandte Chemie International Edition in English, 1993
- Oxygen transfer catalysis by chemical analogs of monooxygenasesRussian Chemical Bulletin, 1993
- The active site structure of methane monooxygenase is closely related to the binuclear iron center of ribonucleotide reductaseFEBS Letters, 1992
- The crystal structure of the oxygenated form of Limulus polyphemus subunit II hemocyanin.Journal of Inorganic Biochemistry, 1992
- Proteins containing oxo-bridged dinuclear iron centers: a bioinorganic perspectiveChemical Reviews, 1990
- Elementary electronic excitations and the mechanism of cytochrome P450Journal of the American Chemical Society, 1989