title: Theoretical exploration of the mechanism of formylmethanofuran dehydrogenase: the first reductive step in CO2 fixation by methanogens.
abstract: A theoretical exploration of the possible active site models of methanofuran dehydrogenase reveals that the free energy of the reduction of the carbamate group is substantially negative and is driven by the electron withdrawing amide group next to the carbonyl carbon. Comparison of the computed transition state energies with the experimental energy barrier indicates that the active site is likely to have an axial oxo and equatorial hydrosulfide ligand, the substrate is likely to be protonated and a second-sphere hydrogen-bonding interaction with the axial ligand can, substantially, lower the barrier of this reaction which involves reduction of the carbonyl center of the a carbamate to form an N-formyl group via a hydride shift from a Mo(IV) center.
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, 700032, West Bengal, India.
authors.forename: Atanu
authors.initials: A
authors.lastname: Rana
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, 700032, West Bengal, India. icad@iacs.res.in.
authors.forename: Abhishek
authors.initials: A
authors.lastname: Dey
mesh_terms: D000445:Aldehyde Oxidoreductases / Q000378:metabolism*; D002245:Carbon Dioxide / Q000737:chemistry / Q000378:metabolism*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D010084:Oxidation-Reduction; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D002245:Carbon Dioxide; D000445:Aldehyde Oxidoreductases; C060639:formylmethanofuran dehydrogenase
keywords: CO2 Reduction; Chemistry; Computational; DFT; MFR-dehydrogenase; Mechanism