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Mechanism of Nitrate Reduction by Desulfovibrio desulfuricans Nitrate Reductase—A Theoretical Investigation
Author(s) -
Leopoldini Monica,
Russo Nino,
Toscano Marirosa,
Dulak Marcin,
Wesolowski Tomasz Adam
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500790
Subject(s) - oniom , nitrate , chemistry , nitrate reductase , catalysis , enzyme , active site , computational chemistry , mechanism (biology) , density functional theory , molecular orbital , stereochemistry , biochemistry , organic chemistry , molecule , physics , quantum mechanics
The oxidative half‐reaction of oxygen atom transfer from nitrate to an Mo IV complex has been investigated at various levels of theory. Two models have been used to simulate the enzyme active site. In the second, more advanced model, additional amino acid residues capable of significantly affecting the catalytic efficiency of the enzyme were included. B3LYP/6–31+G*, ONIOM, and orbital‐free embedding approaches have been used to construct the potential energy profile and to qualitatively compare the results of a QM/MM study with those obtained by a full quantum mechanical strategy. The study has confirmed the utility of the orbital‐free embedding method in the description of enzymatic processes.