NO/H2S “crosstalk” reactions. The role of thionitrites (SNO−) and perthionitrites (SSNO−)

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dc.creatorJuan Pablo Marcolongo
dc.creatorMateus Fernandes Venâncio
dc.creatorWillian Ricardo Rocha
dc.creatorFabio Doctorovich
dc.creatorJosé Antonio Olabe
dc.date.accessioned2023-02-23T18:24:52Z
dc.date.accessioned2025-09-09T00:07:50Z
dc.date.available2023-02-23T18:24:52Z
dc.date.issued2019
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais
dc.description.sponsorshipCAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
dc.description.sponsorshipOutra Agência
dc.identifier.doihttps://doi.org/10.1021/acs.inorgchem.9b01978
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/1843/50329
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.rightsAcesso Restrito
dc.subjectFísico-química
dc.subjectQuímica inorgânica
dc.subjectCinética química
dc.subjectEstrutura molecular
dc.subjectSolução (Química)
dc.subjectAbsorção
dc.subjectSolventes
dc.subjectMecânica quântica
dc.subjectFuncionais de densidade
dc.subjectAnálise espectral
dc.subjectEspectrometria de massa
dc.subjectFourier, Espectroscopia de infravermelho por transformada de
dc.subjectEspectroscopia de ressonância nuclear
dc.subjectEspectroscopia visível
dc.subjectEspectroscopia de ultravioleta
dc.subject.otherAbsorption
dc.subject.otherKetones
dc.subject.otherMolecular structure
dc.subject.otherSolution chemistry
dc.subject.otherSolvents
dc.titleNO/H2S “crosstalk” reactions. The role of thionitrites (SNO−) and perthionitrites (SSNO−)
dc.typeArtigo de periódico
local.citation.epage14997
local.citation.issue22
local.citation.spage14981
local.citation.volume58
local.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.
local.identifier.orcidhttps://orcid.org/0000-0001-9711-4095
local.identifier.orcidhttps://orcid.org/0000-0002-8088-447X
local.identifier.orcidhttps://orcid.org/0000-0002-0025-2158
local.identifier.orcidhttps://orcid.org/0000-0003-1088-2089
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE QUÍMICA
local.publisher.initialsUFMG
local.url.externahttps://pubs.acs.org/doi/10.1021/acs.inorgchem.9b01978

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