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Here, the fusion product of orange protein (ATCUN\u2010ORP) was used as an in vitro model system containing an amino terminal Cu(II)\u2010 and Ni(II)\u2010binding motif (ATCUN) tag at the N\u2010terminus and a native tyrosine residue in the metal\u2010cofactor\u2010binding region for the formation of 3\u2010NO<jats:sub>2<\/jats:sub>\u2010Tyr (3\u2010NT). It is shown that Ni<jats:sup>II<\/jats:sup>\u2010ATCUN unusually performs nitration of tyrosine at physiological pH in the presence of the NO<jats:sub>2<\/jats:sub><jats:sup>\u2212<\/jats:sup>\/SO<jats:sub>3<\/jats:sub><jats:sup>2\u2212<\/jats:sup>\/O<jats:sub>2<\/jats:sub> system, which is revealed by a characteristic absorbance band at 430\u2005nm in basic medium and 350\u2005nm in acidic medium (fingerprint of 3\u2010NT). Kinetics studies showed that the formation of 3\u2010NT depends on sulfite concentration over nitrite concentration suggesting key intermediate products, identified as oxysulfur radicals, which are detected by spin\u2010trap EPR study by using 5,5\u2010dimethyl\u20101\u2010pyrroline\u2010N\u2010oxide (DMPO). This study describes a new route in the formation of 3\u2010NT, which is proposed to be linked with the sulfur metabolism pathway associated with the progression of disease occurrence in vivo.<\/jats:p>","DOI":"10.1002\/chem.201806228","type":"journal-article","created":{"date-parts":[[2019,2,4]],"date-time":"2019-02-04T15:23:40Z","timestamp":1549293820000},"page":"4309-4314","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Ni<sup>II<\/sup>\u2010ATCUN\u2010Catalyzed Tyrosine Nitration in the Presence of Nitrite and Sulfite"],"prefix":"10.1002","volume":"25","author":[{"given":"Biplab K.","family":"Maiti","sequence":"first","affiliation":[{"name":"LAQV, REQUIMTE, Departamento de Qu\u00edmica, Faculdade de Ci\u00eancias e Tecnologia Universidade Nova de Lisboa (FCT NOVA)  Campus de Caparica 2829-516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6901-6591","authenticated-orcid":false,"given":"Luisa B.","family":"Maia","sequence":"additional","affiliation":[{"name":"LAQV, REQUIMTE, Departamento de Qu\u00edmica, Faculdade de Ci\u00eancias e Tecnologia Universidade Nova de Lisboa (FCT NOVA)  Campus de Caparica 2829-516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0971-4977","authenticated-orcid":false,"given":"Isabel","family":"Moura","sequence":"additional","affiliation":[{"name":"LAQV, REQUIMTE, Departamento de Qu\u00edmica, Faculdade de Ci\u00eancias e Tecnologia Universidade Nova de Lisboa (FCT NOVA)  Campus de Caparica 2829-516 Caparica Portugal"}]},{"given":"Jos\u00e9 J. 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