Effect of molybdenum and tungsten on the reduction of nitrate in nitrate reductase, a DFT study

• Verfasst von: Habib, Uzma [VerfasserIn]
• Verfasst von: Hofmann, Matthias [VerfasserIn]
• Titel: Effect of molybdenum and tungsten on the reduction of nitrate in nitrate reductase, a DFT study
• Verf.angabe: Uzma Habib and Matthias Hoffmann
• E-Jahr: 2017
• Jahr: 26 April 2017
• Umfang: 12 S.
• Fussnoten: Gesehen am 17.09.2018
• Titel Quelle: Enthalten in: Chemistry central journal
• Ort Quelle: London : BioMed Central, 2007
• Jahr Quelle: 2017
• Band/Heft Quelle: 11(2017) Artikel-Nummer 35, 12 Seiten
• ISSN Quelle: 1752-153X
• DOI: doi:10.1186/s13065-017-0263-7
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1581037945

Abstract

The molybdenum and tungsten active site model complexes, derived from the protein X-ray crystal structure of the first W-containing nitrate reductase isolated from Pyrobaculum aerophilum, were computed for nitrate reduction at the COSMO-B3LYP/SDDp//B3LYP/Lanl2DZ(p) energy level of density functional theory. The molybdenum containing active site model complex (Mo-Nar) has the largest activation energy (34.4 kcal/mol) for the oxygen atom transfer from the nitrate to the metal center as compared to the tungsten containing active site model complex (W-Nar) (12.0 kcal/mol). Oxidation of the educt complex is close to thermoneutral (-1.9 kcal/mol) for the Mo active site model complex but strongly exothermic (-34.7 kcal/mol) for the W containing active site model complex, however, the MVI to MIV reduction requires equal amount of reductive power for both metal complexes, Mo-Nar or W-Nar.