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Nitrate reductases (NRs) are enzymes that catalyze reduction of nitrate to nitrite using a molybdenum cofactor. In an alternative reaction, plant NRs have also been shown to catalyze reduction of nitrite to nitric oxide, and this appears to be a major source of nitric oxide synthesis in plants, although other pathways have also been shown. Here, density functional theory (DFT) results are shown, indicating that although nitrate is thermodynamically the preferred substrate for the NR active site, both nitrite and nitrate are easily reduced to nitrite and NO, respectively. These mechanisms require a Mo(IV) state. Additionally, in the case of the nitrite, linkage isomerism is at work and controlled by the metal oxidation state, and reduction is, unlike in the nitrate case, dependent on protonation. The data may be relevant to other molybdenum enzymes with similar active sites, such as xanthine oxidase. Copyright © 2011 Elsevier Inc. All rights reserved.


Radu Silaghi-Dumitrescu, Mihaela Mich, Csongor Matyas, Chris E Cooper. Nitrite and nitrate reduction by molybdenum centers of the nitrate reductase type: computational predictions on the catalytic mechanism. Nitric oxide : biology and chemistry / official journal of the Nitric Oxide Society. 2012 Jan 1;26(1):27-31

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PMID: 22138423

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