title: A QM/MM study of the nature of the entatic state in plastocyanin.
abstract: Plastocyanin is a copper containing protein that is involved in the electron transfer process in photosynthetic organisms. The active site of plastocyanin is described as an entatic state whereby its structure represents a compromise between the structures favored by the oxidized and reduced forms. In this study, the nature of the entatic state is investigated through density functional theory-based hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations. The strain energy is computed to be 12.8 kcal/mol and 14.5 kcal/mol for the oxidized and reduced forms of the protein, indicating that the active site has an intermediate structure. It is shown that the energy gap between the oxidized and reduced forms varies significantly with the fluctuations in the structure of the active site at room temperature. An accurate determination of the reorganization energy requires averaging over conformation and a large region of the protein around the active site to be treated at the quantum mechanical level. © 2016 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
authors.forename: Catherine A
authors.initials: CA
authors.lastname: Hurd
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
authors.forename: Nicholas A
authors.initials: NA
authors.lastname: Besley
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
authors.forename: David
authors.initials: D
authors.lastname: Robinson
mesh_terms: D020134:Catalytic Domain; D004579:Electron Transport; D056004:Molecular Dynamics Simulation; D010084:Oxidation-Reduction; D010970:Plastocyanin / Q000737:chemistry*; D011487:Protein Conformation; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D010970:Plastocyanin
keywords: QM/MM; electron transfer; plastocyanin