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Two reactions, mediated by the vanadium complexes, with environmental and biological significance, were observed in this system, namely, reduction of nitrite to N<jats:sub>2<\/jats:sub>O and oxidation of water to molecular oxygen. The reduction of nitrite, as studied by DFT calculations, occurs through the formation of NO (\u0394<jats:italic>G<\/jats:italic><jats:sup>\u2260<\/jats:sup>=14.3\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>), which is strongly dependent on pH and slightly endergonic, and is then easily converted into N<jats:sub>2<\/jats:sub>O, with an overall activation barrier of \u0394<jats:italic>G<\/jats:italic><jats:sup>\u2260<\/jats:sup>=11.8\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>. The later process includes dimerisation of NO assisted by one molecule of the V complex, protonation and oxidation of the formed ONNO<jats:sup>.\u2212<\/jats:sup> ligand by another amavadin molecule or by nitrite, and NO bond cleavage\/proton transfer in the ONNOH<jats:sup>\u2212<\/jats:sup> ligand. The results indicate that amavadin exhibits an unusual nitrite reductase type activity that could be involved in nitrogen metabolism of <jats:italic>Amanita muscaria<\/jats:italic> and other fungi containing this vanadium complex.<\/jats:p>","DOI":"10.1002\/chem.201705385","type":"journal-article","created":{"date-parts":[[2017,11,27]],"date-time":"2017-11-27T08:43:18Z","timestamp":1511772198000},"page":"2474-2482","source":"Crossref","is-referenced-by-count":11,"title":["Nitrite Reduction in Aqueous Solution Mediated by Amavadin Homologues: N<sub>2<\/sub>O Formation and Water Oxidation"],"prefix":"10.1002","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2437-5141","authenticated-orcid":false,"given":"L\u00facia","family":"Dias","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural Instituto Superior T\u00e9cnico Universidade de Lisboa  Av. 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