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Please use this identifier to cite or link to this item: http://hdl.handle.net/1843/50329
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dc.creatorJuan Pablo Marcolongopt_BR
dc.creatorMateus Fernandes Venânciopt_BR
dc.creatorWillian Ricardo Rochapt_BR
dc.creatorFabio Doctorovichpt_BR
dc.creatorJosé Antonio Olabept_BR
dc.date.accessioned2023-02-23T18:24:52Z-
dc.date.available2023-02-23T18:24:52Z-
dc.date.issued2019-
dc.citation.volume58pt_BR
dc.citation.issue22pt_BR
dc.citation.spage14981pt_BR
dc.citation.epage14997pt_BR
dc.identifier.doihttps://doi.org/10.1021/acs.inorgchem.9b01978pt_BR
dc.identifier.issn1520-510Xpt_BR
dc.identifier.urihttp://hdl.handle.net/1843/50329-
dc.description.resumoThe redox chemistry of H2S with NO and other oxidants containing the NO group is discussed on a mechanistic basis because of the expanding interest in their biological relevance, with an eye open to the chemical differences of H2S and thiols RSH. We focus on the properties of two “crosstalk” intermediates, SNO– (thionitrite) and SSNO– (perthionitrite, nitrosodisulfide) based in the largely controversial status on their identity and chemistry in aqueous/nonaqueous media, en route to the final products N2O, NO2–, NH2OH/NH3, and S8. Thionitrous acid, generated either in the direct reaction of NO + H2S or through the transnitrosation of RSNO’s (nitrosothiols) with H2S at pH 7.4, is best described as a mixture of rapidly interconverting isomers, {(H)SNO}. It is reactive in different competitive modes, with a half-life of a few seconds at pH 7.4 for homolytic cleavage of the N–S bond, and could be deprotonated at pH values of up to ca. 10, giving SNO–, a less reactive species than {(H)SNO}. The latter mixture can also react with HS–, giving HNO and HS2– (hydrogen disulfide), a S0(sulfane)-transfer reagent toward {(H)SNO}, leading to SSNO–, a moderately stable species that slowly decomposes in aqueous sulfide-containing solutions in the minute–hour time scale, depending on [O2]. The previous characterization of HSNO/SNO– and SSNO– is critically discussed based on the available chemical and spectroscopic evidence (mass spectrometry, UV–vis, 15N NMR, Fourier transform infrared), together with computational studies including quantum mechanics/molecular mechanics molecular dynamics simulations that provide a structural and UV–vis description of the solvatochromic properties of cis-SSNO– acting as an electron donor in water, alcohols, and aprotic acceptor solvents. In this way, SSNO– is confirmed as the elusive “yellow intermediate” (I412) emerging in the aqueous crosstalk reactions, in contrast with its assignment to polysulfides, HSn–. The analysis extends to the coordination abilities of {(H)SNO}, SNO–, and SSNO– into heme and nonheme iron centers, providing a basis for best unraveling their putative specific signaling roles.pt_BR
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológicopt_BR
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Geraispt_BR
dc.description.sponsorshipCAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorpt_BR
dc.description.sponsorshipOutra Agênciapt_BR
dc.languageengpt_BR
dc.publisherUniversidade Federal de Minas Geraispt_BR
dc.publisher.countryBrasilpt_BR
dc.publisher.departmentICX - DEPARTAMENTO DE QUÍMICApt_BR
dc.publisher.initialsUFMGpt_BR
dc.rightsAcesso Restritopt_BR
dc.subjectAbsorptionpt_BR
dc.subjectKetonespt_BR
dc.subjectMolecular structurept_BR
dc.subjectSolution chemistrypt_BR
dc.subjectSolventspt_BR
dc.subject.otherFísico-químicapt_BR
dc.subject.otherQuímica inorgânicapt_BR
dc.subject.otherCinética químicapt_BR
dc.subject.otherEstrutura molecularpt_BR
dc.subject.otherSolução (Química)pt_BR
dc.subject.otherAbsorçãopt_BR
dc.subject.otherSolventespt_BR
dc.subject.otherMecânica quânticapt_BR
dc.subject.otherFuncionais de densidadept_BR
dc.subject.otherAnálise espectralpt_BR
dc.subject.otherEspectrometria de massapt_BR
dc.subject.otherFourier, Espectroscopia de infravermelho por transformada dept_BR
dc.subject.otherEspectroscopia de ressonância nuclearpt_BR
dc.subject.otherEspectroscopia visívelpt_BR
dc.subject.otherEspectroscopia de ultravioletapt_BR
dc.titleNO/H2S “crosstalk” reactions. The role of thionitrites (SNO−) and perthionitrites (SSNO−)pt_BR
dc.typeArtigo de Periódicopt_BR
dc.url.externahttps://pubs.acs.org/doi/10.1021/acs.inorgchem.9b01978pt_BR
dc.identifier.orcidhttps://orcid.org/0000-0001-9711-4095pt_BR
dc.identifier.orcidhttps://orcid.org/0000-0002-8088-447Xpt_BR
dc.identifier.orcidhttps://orcid.org/0000-0002-0025-2158pt_BR
dc.identifier.orcidhttps://orcid.org/0000-0003-1088-2089pt_BR
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