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Mechanistic Studies of Reactions of Peroxodiiron(III) Intermediates in T201 Variants of Toluene/<i>o</i>-Xylene Monooxygenase Hydroxylase

Cited 17 time in Web of Science Cited 19 time in Scopus
Authors

Song, Woon Ju; Lippard, Stephen J.

Issue Date
2011-06
Publisher
AMER CHEMICAL SOC
Citation
BIOCHEMISTRY, Vol.50 No.23, pp.5391-5399
Abstract
Site-directed mutagenesis studies of a strictly conserved T201 residue in the active site of toluene/o-xylene monooxygenase hydroxylase (ToMOH) revealed that a single mutation can facilitate kinetic isolation of two distinctive peroxodiiron(III) species, designated T201(peroxo). and ToMOH(peroxo), during dioxygen activation. Previously, we characterized both oxygenated intermediates by UV-vis and Mossbauer spectroscopy, proposed structures from DFT and QM/MM computational studies, and elucidated chemical steps involved in dioxygen activation through the kinetic studies of T201(peroxo) formation. In this study, we investigate the kinetics of T201(peroxo) decay to explore the reaction mechanism of the oxygenated intermediates following O-2 activation. The decay rates of T201(peroxo) were monitored in the absence and presence of external (phenol) or internal (tryptophan residue in an I100W variant) substrates under pre-steady-state conditions. Three possible reaction models for the formation and decay of T201(peroxo) were evaluated, and the results demonstrate that this species is on the pathway of arene oxidation and appears to be in equilibrium with ToMOH(peroxo).
ISSN
0006-2960
URI
https://hdl.handle.net/10371/203490
DOI
https://doi.org/10.1021/bi200340f
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  • College of Natural Sciences
  • Department of Chemistry
Research Area Biochemistry, Inorganic, 무기화학, 생화학

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