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Báo cáo khoa học: Models and mechanisms of O-O bond activation by cytochrome P450 A critical assessment of the potential role of multiple active intermediates in oxidative catalysis

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Cytochrome P450 enzymes promote a number of oxidativebiotransformations including the hydroxylation of unacti-vated hydrocarbons. Whereas the long-standing consensusview of the P450 mechanism implicates a high-valent iron-oxene species as the predominant oxidant in the radicalarhydrogen abstraction/oxygen rebound pathway, morerecent studies on isotope partitioning, product rearrange-ments withradical clocks, and the impact of threoninemutagenesis in P450s on hydroxylation rates support thenotion of the nucleophilic and/or electrophilic (hydro)peroxo-iron intermediate(s) to be operative in P450 catalysisin addition to the electrophilic oxenoid-iron entity; this maycontribute to the remarkable versatility of P450s in substratemodification....
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Báo cáo khoa học: Models and mechanisms of O-O bond activation by cytochrome P450 A critical assessment of the potential role of multiple active intermediates in oxidative catalysis

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