Solvation and proton-coupled electron transfer reduction potential of ²NO• to ¹HNO in aqueous solution: a theoretical investigation

Mateus Fernandes Venâncio; Fabio Doctorovich; Willian Ricardo Rocha

Please use this identifier to cite or link to this item: http://hdl.handle.net/1843/50319

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DC Field	Value	Language
dc.creator	Mateus Fernandes Venâncio	pt_BR
dc.creator	Fabio Doctorovich	pt_BR
dc.creator	Willian Ricardo Rocha	pt_BR
dc.date.accessioned	2023-02-23T15:16:21Z	-
dc.date.available	2023-02-23T15:16:21Z	-
dc.date.issued	2017	-
dc.citation.volume	121	pt_BR
dc.citation.issue	27	pt_BR
dc.citation.spage	6618	pt_BR
dc.citation.epage	6625	pt_BR
dc.identifier.doi	https://doi.org/10.1021/acs.jpcb.7b03552	pt_BR
dc.identifier.issn	1520-5207	pt_BR
dc.identifier.uri	http://hdl.handle.net/1843/50319	-
dc.description.resumo	In this work, quantum mechanical calculations and Monte Carlo statistical mechanical simulations were carried out to investigate the solvation properties of HNO in aqueous solution and to evaluate the proton-coupled one electron reduction potential of ²NO to ¹HNO, which is essential missing information to understand the fate of ²NO in the biological medium. Our results showed that the ¹HNO molecule acts mainly as a hydrogen bond donor in aqueous solution with an average energy of −5.5 ± 1.3 kcal/mol. The solvation free energy of ¹HNO in aqueous solution, computed using three approaches based on the linear response theory, revealed that the current prediction of the hydration free energy of HNO is, at least, 2 times underestimated. We proposed two pathways for the production of HNO through reduction of NO. The first pathway is the direct reduction of NO through proton-coupled electron transfer to produce HNO, and the second path is the reduction of the radical anion HONO•–, which is involved in equilibrium with NO in aqueous solution. We have shown that both pathways are viable processes under physiological conditions, having reduction potentials of E°′ = −0.161 V and E°′ ≈ 1 V for the first and second pathways, respectively. The results shows that both processes can be promoted by well-known biological reductants such as NADH, ascorbate, vitamin E (tocopherol), cysteine, and glutathione, for which the reduction potential at physiological pH is around −0.3 to −0.5 V. The computed reduction potential of NO through the radical anion HONO•– can also explain the recent experimental findings on the formation of HNO through the reduction of NO, promoted by H2S, vitamin C, and aromatic alcohols. Therefore, these results contribute to shed some light into the question of whether and how HNO is produced in vivo and also for the understanding of the biochemical and physiological effects of NO.	pt_BR
dc.description.sponsorship	CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico	pt_BR
dc.description.sponsorship	FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais	pt_BR
dc.description.sponsorship	Outra Agência	pt_BR
dc.language	eng	pt_BR
dc.publisher	Universidade Federal de Minas Gerais	pt_BR
dc.publisher.country	Brasil	pt_BR
dc.publisher.department	ICX - DEPARTAMENTO DE QUÍMICA	pt_BR
dc.publisher.initials	UFMG	pt_BR
dc.rights	Acesso Restrito	pt_BR
dc.subject	Free energy	pt_BR
dc.subject	Noncovalent interactions	pt_BR
dc.subject	Redox reactions	pt_BR
dc.subject	Solution chemistry	pt_BR
dc.subject	Solvation	pt_BR
dc.subject.other	Físico-química	pt_BR
dc.subject.other	Gibbs, Energia livre de	pt_BR
dc.subject.other	Solução (Química)	pt_BR
dc.subject.other	Solvação	pt_BR
dc.subject.other	Óxido nítrico	pt_BR
dc.subject.other	Mecânica quântica	pt_BR
dc.subject.other	Método de Monte Carlo	pt_BR
dc.title	Solvation and proton-coupled electron transfer reduction potential of ²NO• to ¹HNO in aqueous solution: a theoretical investigation	pt_BR
dc.type	Artigo de Periódico	pt_BR
dc.url.externa	https://pubs.acs.org/doi/10.1021/acs.jpcb.7b03552	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0002-8088-447X	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0003-1088-2089	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0002-0025-2158	pt_BR
Appears in Collections:	Artigo de Periódico

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