Driving Force for Oxygen‐Atom Transfer by Heme‐Thiolate Enzymes
作者： Xiaoshi Wang , Sebastian Peter , René Ullrich , Martin Hofrichter , John T. Groves
关键词: Chemistry 、 Chloride peroxidase 、 Mixed Function Oxygenases 、 Ferric 、 Reaction rate constant 、 Photochemistry 、 Reactivity (chemistry) 、 Bromide 、 Oxidizing agent 、 Redox
摘要: The heme-thiolate peroxygenase AaeAPO from Agrocybe aegerita is an important biocatalyst and P450 analog. We have found that compound I can be formed via oxidation of the ferric protein with HOBr HOCl. rate constant for formation AaeAPO-I induced by at pH 5.0, 4 °C was 7.1 × 10 M−1s−1. reacts bromide chloride ions to regenerate resting protein. Similar measurements were made chloroperoxidase (CPO). reaction ion 2.6 105 By measuring rates forward reverse reactions over a wide range pH, Nernst plots driving force oxygen atom transfer CPO-I constructed. It two-electron redox potential similar about 200 mV less than Interestingly, are both much more oxidizing HRP I. results informative regard reactivity these proteins toward C–H bonds.
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