Hypobromous acid, a powerful endogenous electrophile: Experimental and theoretical studies

dc.contributorUniversidade Estadual Paulista (UNESP)
dc.creatorXimenes, Valdecir Farias
dc.creatorMorgon, Nelson Henrique
dc.creatorSouza, Aguinaldo Robinson de
dc.date2015-10-21T21:06:55Z
dc.date2016-10-25T21:09:12Z
dc.date2015-10-21T21:06:55Z
dc.date2016-10-25T21:09:12Z
dc.date2015-05-01
dc.date.accessioned2017-04-06T09:09:54Z
dc.date.available2017-04-06T09:09:54Z
dc.identifierJournal Of Inorganic Biochemistry. New York: Elsevier Science Inc, v. 146, p. 61-68, 2015.
dc.identifier0162-0134
dc.identifierhttp://hdl.handle.net/11449/129445
dc.identifierhttp://acervodigital.unesp.br/handle/11449/129445
dc.identifierhttp://dx.doi.org/10.1016/j.jinorgbio.2015.02.014
dc.identifierWOS:000353252600008
dc.identifierhttp://www.sciencedirect.com/science/article/pii/S0162013415000574
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/940000
dc.descriptionHypobromous acid (HOBr) is an inorganic acid produced by the oxidation of the bromide anion (Br-). The blood plasma level of Br- is more than 1,000-fold lower than that of chloride anion (Cl-). Consequently, the endogenous production of HOBr is also lower compared to hypochlorous acid (HOCl). Nevertheless, there is much evidence of the deleterious effects of HOBr. From these data, we hypothesized that the reactivity of HOBr could be better associated with its electrophilic strength. Our hypothesis was confirmed, since HOBr was significantly more reactive than HOCl when the oxidability of the studied compounds was not relevant. For instance: anisole (HOBr, k(2) = 2.3 x 10(2) M-1 s(-1), HOCl non-reactive); dansylglycine (HOBr, k(2) = 7.3 x 10(6) M-1 s(-1), HOCl, 5.2 x 10(2) M-1 s(-1)); salicylic acid (HOBr, k(2) = 4.0 x 10(4) M-1 s(-1), non-reactive); 3-hydroxybenzoic acid (HOBr, k(2) = 5.9 x 10(4) M-1 s(-1), HOCl, k(2) = 1.1 x 10(1) M-1 s(-1)); uridine (HOBr, k(2) = 13 x 10(3) M-1 s(-1), HOCl non-reactive). The compounds 4-bromoanisole and 5-bromouridine were identified as the products of the reactions between HOBr and anisole or uridine, respectively, i.e. typical products of electrophilic substitutions. Together, these results show that, rather than an oxidant, HOBr is a powerful electrophilic reactant. This chemical property was theoretically confirmed by measuring the positive Mulliken and ChelpG charges upon bromine and chlorine. In conclusion, the high electrophilicity of HOBr could be behind its well-established deleterious effects. We propose that HOBr is the most powerful endogenous electrophile. (C) 2015 Elsevier Inc. All rights reserved.
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.languageeng
dc.publisherElsevier B.V.
dc.relationJournal Of Inorganic Biochemistry
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.subjectReactive electrophilic species
dc.subjectReactive oxygen species
dc.subjectHypobromous acid
dc.subjectHypochlorous acid
dc.subjectMyeloperoxidase
dc.titleHypobromous acid, a powerful endogenous electrophile: Experimental and theoretical studies
dc.typeOtro


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