Journal of the American Chemical Society · 2013 · 143 citations · 37 references
Life SciencesBiochemistryChemistryBiocatalysisEnzyme MechanismEnzymologyCatalytic MechanismsCytochrome P450 EnzymesPhotocatalysisPhotochemistryRedox EnzymesCytochrome P450 CatalysisCytochrome P450 IsoenzymesCytochrome P450-mediated HydroxylationFunctionalizationHeme EnzymesHydroxylationPhotosensitizersStereoselective C-h Functionalization
P450s are heme thiolate enzymes that catalyze the regio- and stereoselective functionalization of unactivated C-H bonds using molecular dioxygen and two electrons delivered by the reductase. We have developed hybrid P450 BM3 heme domains containing a covalently attached Ru(II) photosensitizer in order to circumvent the dependency on the reductase and perform P450 reactions upon visible light irradiation. A highly active hybrid enzyme with improved stability and a modified Ru(II) photosensitizer is able to catalyze the light-driven hydroxylation of lauric acid with total turnover numbers of 935 and initial reaction rate of 125 mol product/(mol enzyme/min).
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Harry B. Gray, Jay R. Winkler · Proceedings of the National Academy of Sciences · 2005 · 850 citations · Full text
Natural Sciences, Chemistry, Physics +17