Lophine derivatives as activators in peroxyoxalate chemiluminescence

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dc.contributor.authorAlves, J.
dc.contributor.authorBoaro, A.
dc.contributor.authorSilva, J. S. da [UNIFESP]
dc.contributor.authorFerreira, T. L. [UNIFESP]
dc.contributor.authorKeslarek, V. B.
dc.contributor.authorCabral, C. A.
dc.contributor.authorOrfao, R. B.
dc.contributor.authorCiscato, L. F. M. L.
dc.contributor.authorBartoloni, F. H.
dc.contributor.institutionUniversidade Federal do ABC (UFABC)
dc.contributor.institutionUniversidade Federal de São Paulo (UNIFESP)
dc.date.accessioned2016-01-24T14:39:51Z
dc.date.available2016-01-24T14:39:51Z
dc.date.issued2015-01-01
dc.description.abstractLophine and four of its derivatives were used as activators (ACTs) of the chemiluminescent peroxyoxalate (PO) reaction of bis(2,4,6-trichlorophenyl) oxalate with H2O2, catalysed by imidazole. Kinetic emission assays have shown that with the tested compounds the reaction mechanism, regarding the formation of the high energy intermediate (HEI) of the PO reaction, occurs as previously seen for commonly used ACTs. A bimolecular interaction of the compounds with the HEI leads to chemiexcitation through the chemically initiated electron exchange luminescence (CIEEL) mechanism, as confirmed by a linear free-energy correlation between the relative catalytic rate constants and the oxidation potentials of the compounds. the yields of excited state formation and light emission, in the range of 10(-2)-10(-3) E mol(-1), are comparable to the ones seen with commonly used ACTs. A Hammett plot with rho = -0.90 indicates the buildup of a partial positive charge on the transition step of the catalytic process, consistent with the formation of a radical cation of the ACT, being an additional validation of the CIEEL mechanism in this system.en
dc.description.affiliationUniv Fed ABC, Ctr Ciencias Nat & Humanas, Santo Andre, SP, Brazil
dc.description.affiliationUniversidade Federal de São Paulo, Inst Ciencias Ambientais Quim & Farmaceut, Diadema, SP, Brazil
dc.description.affiliationUnifespUniversidade Federal de São Paulo, Inst Ciencias Ambientais Quim & Farmaceut, Diadema, SP, Brazil
dc.description.sourceWeb of Science
dc.description.sponsorshipFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.description.sponsorshipCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
dc.description.sponsorshipIDFAPESP: 2013/17332-6
dc.description.sponsorshipIDFAPESP: 2011/17587-9
dc.description.sponsorshipIDFAPESP: 2012/02428-5
dc.description.sponsorshipIDFAPESP: 2012/13807-7
dc.format.extent320-328
dc.identifierhttp://dx.doi.org/10.1039/c4pp00311j
dc.identifier.citationPhotochemical & Photobiological Sciences. Cambridge: Royal Soc Chemistry, v. 14, n. 2, p. 320-328, 2015.
dc.identifier.doi10.1039/c4pp00311j
dc.identifier.issn1474-905X
dc.identifier.urihttp://repositorio.unifesp.br/handle/11600/38599
dc.identifier.wosWOS:000349364700013
dc.language.isoeng
dc.publisherRoyal Soc Chemistry
dc.relation.ispartofPhotochemical & Photobiological Sciences
dc.rightsinfo:eu-repo/semantics/restrictedAccess
dc.titleLophine derivatives as activators in peroxyoxalate chemiluminescenceen
dc.typeinfo:eu-repo/semantics/article
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