External electric field can control the catalytic cycle of cytochrome P450_cam: A QM/MM study

This Letter presents a systematic study of effects of external electric fields (EEFs) on the key species and steps in the catalytic cycle of cytochrome P450_cam. The QM/MM/EEF results demonstrate that an EEF can exert significant effects on the entire catalytic cycle of P450. The EEF will control the initial gating of the cycle, its rate-determining step, its O₂ uptake, the geometry of its resting state, and the spin-state ordering and electronic structure of its various active species. Furthermore, the EEF has a potential of controlling the bond activation reactions of the active species as well. These effects are pronounced when the EEF is aligned perpendicular to the porphyrin plane.