Electronic properties of pentacoordinated heme complexes in cytochrome P450 enzymes: search for an Fe(i) oxidation state
Literature Information
Cristina S. Porro, Devesh Kumar, Sam P. de Visser
The cytochrome P450s are versatile enzymes that catalyze a range of monoxygenation reactions. Their catalytic cycle includes molecular oxygen binding and two reduction and protonation steps to create the active species, Compound I. In an anaerobic environment, however, only two reduction steps starting from the resting state can take place. Currently, very little information is known on this doubly-reduced species; therefore, we have performed a detailed density functional theory (DFT) and combined quantum mechanics/molecular mechanics (QM/MM) study on this complex. In principle, the doubly-reduced pentacoordinated heme can exist in two possible electronic configurations, namely an Fe(I) with closed-shell heme or an Fe(II) coupled to a heme anion radical [FeII Por−˙]. Our calculations show that there are several close-lying spin states with a [FeII Por−˙] configuration and these states are much lower in energy than the alternative [FeI Por0] situation. We have calculated spectroscopic parameters of the lowest lying sextet spin state, including IR spectra and EPR parameters.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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