title: Characterizing the Intermediates Compound I and II in the Cytochrome P450 Catalytic Cycle with Nonlinear X-ray Spectroscopy: A Simulation Study.
abstract: Cytochrome P450 enzymes are an important family of biocatalysts that oxidize chemically inert CH bonds. There are many unresolved questions regarding the catalytic reaction intermediates, in particular P450 Compound I (Cpd-I) and II (Cpd-II). By using simple molecular models, we simulate various X-ray spectroscopy signals, including X-ray absorption near-edge structure (XANES), resonant inelastic X-ray scattering (RIXS), and stimulated X-ray Raman spectroscopy (SXRS) of the low- and high-spin states of Cpd-I and II. Characteristic peak patterns are presented and connected to the corresponding electronic structures. These X-ray spectroscopy techniques are complementary to more conventional infrared and optical spectroscopy and they help to elucidate the evolving electronic structures of transient species along the reaction path.
authors: Dept. of Chemistry, University of California, 450 Rowland Hall, Irvine, California 92697 (USA). yuz10@uci.edu.
authors: Yu
authors: Y
authors: Zhang
authors: Dept. of Chemistry, University of California, 450 Rowland Hall, Irvine, California 92697 (USA).
authors: Jason D
authors: JD
authors: Biggs
authors: Dept. of Chemistry, University of California, 450 Rowland Hall, Irvine, California 92697 (USA). smukamel@uci.edu.
authors: Shaul
authors: S
authors: Mukamel
mesh_terms: D055162:Biocatalysis; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry / Q000378:metabolism*; D056004:Molecular Dynamics Simulation; D011487:Protein Conformation; D013059:Spectrum Analysis, Raman; D056928:X-Ray Absorption Spectroscopy
chemical_list: D003577:Cytochrome P-450 Enzyme System
keywords: Raman spectroscopy; X-ray absorption spectroscopy; density functional calculations; molecular modeling; reaction mechanisms