Novel approaches for the accumulation of oxygenated intermediates to multi-millimolar concentrations

► Spectroscopy on intermediate states has illuminated the mechanisms of O2-activating metalloenzymes. ► The modest solubility of O2 can limit the concentration and purity of target intermediate states. ► Long-lived intermediates can be built up further by direct exposure of reactant complexes to O2(...

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Bibliographic Details
Published in:Coordination chemistry reviews 2013-01, Vol.257 (1), p.234-243
Main Authors: Krebs, Carsten, Dassama, Laura M.K., Matthews, Megan L., Jiang, Wei, Price, John C., Korboukh, Victoria, Li, Ning, Bollinger, J. Martin
Format: Article
Language:English
Subjects:
Ferryl
Intermediate
Iron
Non-heme
Oxygen
Peroxo
Superoxo
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Summary:► Spectroscopy on intermediate states has illuminated the mechanisms of O2-activating metalloenzymes. ► The modest solubility of O2 can limit the concentration and purity of target intermediate states. ► Long-lived intermediates can be built up further by direct exposure of reactant complexes to O2(g). ► Chlorite dismutase (Cld) can rapidly generate a ∼10mM pulse of O2 from ClO2−. ► O2 evolved by Cld can yield oxygenated intermediates at high concentration and purity. Metalloenzymes that utilize molecular oxygen as a co-substrate catalyze a wide variety of chemically difficult oxidation reactions. Significant insight into the reaction mechanisms of these enzymes can be obtained by the application of a combination of rapid kinetic and spectroscopic methods to the direct structural characterization of intermediate states. A key limitation of this approach is the low aqueous solubility (
ISSN:0010-8545
1873-3840
DOI:10.1016/j.ccr.2012.06.020