Cytochrome P450: the active oxidant and its spectrum

J Rittle, JM Younker, MT Green - Inorganic chemistry, 2010 - ACS Publications
J Rittle, JM Younker, MT Green
Inorganic chemistry, 2010ACS Publications
This Forum focuses on the nature of the elusive oxidizing intermediate in P450 catalysis.
The identity of this species has reemerged as a topic of contentious debate. It was recently
reported that laser flash photolysis (LFP) can be used to generate P450 compound I (P450-I)
quantitatively. Kinetic analyses of the reaction of the LFP-generated intermediate with
substrates have been suggested to indicate that compound I is not the active oxidant in
P450 catalysis. We evaluate these claims via an analysis of the UV/visible spectrum of the …
This Forum focuses on the nature of the elusive oxidizing intermediate in P450 catalysis. The identity of this species has reemerged as a topic of contentious debate. It was recently reported that laser flash photolysis (LFP) can be used to generate P450 compound I (P450-I) quantitatively. Kinetic analyses of the reaction of the LFP-generated intermediate with substrates have been suggested to indicate that compound I is not the active oxidant in P450 catalysis. We evaluate these claims via an analysis of the UV/visible spectrum of the LFP-generated intermediate. The techniques of singular value decomposition and target testing are used to obtain the spectrum of P450-I in a model-independent manner from stopped-flow data of the reaction of P450 with m-chloroperbenzoic acid. It is shown that the LFP-generated spectrum bears no similarity to the P450-I spectrum. One may conclude that the LFP-generated intermediate is not P450-I.
ACS Publications
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