Spectroscopic Characterization of a Hydroperoxo-Heme Intermediate: Conversion of a Side-On Peroxo to an End-On Hydroperoxo Complex

摘要

The ferric hydroperoxo-heme species [Fe-OOH] (compound 0) is well known as a common key intermediate in the catalytic cycles of heme-containing monooxygenase and peroxidase enzymes.The catalytic cycles of nitric oxide synthase, cytochrome P450, and heme oxygenase (HO) generally involve single-electron reduction of an oxy-ferrous intermediate to form a ferric peroxo species. This process is often coupled with proton transfer to the distal oxygen atom of the peroxo intermediate to afford the ferric hydroperoxo species.