Characterization of a Peroxodiiron(III) Intermediate in the T201S Variant of Toluene/o-Xylene Monooxygenase Hydroxylase from Pseudomonas sp. OX1
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Lippard_Characterization of a peroxodiiron.pdf
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Author(s)
Song, Woon Ju
Behan, Rachel K.
Naik, Sunil G.
Huynh, Boi Hanh
Lippard, Stephen J.
Date Issued
April 2009
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Song, Woon Ju, Rachel K. Behan, Sunil G. Naik, Boi Hanh Huynh, and Stephen J. Lippard. “Characterization of a Peroxodiiron(III) Intermediate in the T201S Variant of Toluene/o-Xylene Monooxygenase Hydroxylase from Pseudomonas sp. OX1.” Journal of the American Chemical Society 131, no. 17 (May 6, 2009): 6074-6075.
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Author's final manuscript
Abstract
We report the observation of a novel intermediate in the reaction of a reduced toluene/o-xylene monooxygenase hydroxylase (ToMOH[subscript red]) T201S variant, in the presence of a regulatory protein (ToMOD), with dioxygen. This species is the first oxygenated intermediate with an optical band in any toluene monooxygenase. The UV−vis and Mössbauer spectroscopic properties of the intermediate allow us to assign it as a peroxodiiron(III) species, T201S[subscript peroxo], similar to H[subscript peroxo] in methane monooxygenase. Although T201S generates T201S[subscript peroxo] in addition to optically transparent ToMOH[subscript peroxo], previously observed in wild-type ToMOH, this conservative variant is catalytically active in steady-state catalysis and single-turnover experiments and displays the same regiospecificity for toluene and slightly different regiospecificity for o-xylene oxidation.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja9011782
