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(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

Excited singlet molecular O-2 ((1)Delta g) is generated enzymatically from excited carbonyls in the dark

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Autor(es):
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Mano, Camila M. [1] ; Prado, Fernanda M. [1] ; Massari, Julio [1] ; Ronsein, Graziella E. [1] ; Martinez, Glaucia R. [2] ; Miyamoto, Sayuri [1] ; Cadet, Jean [3] ; Sies, Helmut [4, 5] ; Medeiros, Marisa H. G. [1] ; Bechara, Etelvino J. H. [1, 6] ; Di Mascio, Paolo [1]
Número total de Autores: 11
Afiliação do(s) autor(es):
[1] Univ Sao Paulo, Inst Quim, Dept Bioquim, BR-05513970 Sao Paulo - Brazil
[2] Univ Fed Parana, Dept Bioquim & Biol Mol, Set Ciencias Biol, BR-80060000 Curitiba, Parana - Brazil
[3] CEA Grenoble, Inst Nanosci & Cryogenie, F-38054 Grenoble 9 - France
[4] Univ Dusseldorf, Inst Biochem & Mol Biol 1, Dusseldorf - Germany
[5] Univ Dusseldorf, Leibniz Res Inst Environm Med, Dusseldorf - Germany
[6] Univ Fed Sao Paulo, Inst Ciencias Ambientais Quim & Farmaceut, Dept Ciencias Exatas & Terra, Sao Paulo - Brazil
Número total de Afiliações: 6
Tipo de documento: Artigo Científico
Fonte: SCIENTIFIC REPORTS; v. 4, AUG 4 2014.
Citações Web of Science: 25
Resumo

In mammalian tissues, ultraweak chemiluminescence arising from biomolecule oxidation has been attributed to the radiative deactivation of singlet molecular oxygen {[}O-2 ((1)Delta(g))] and electronically excited triplet carbonyl products involving dioxetane intermediates. Herein, we describe evidence of the generation of O-2 ((1)Delta(g)) in aqueous solution via energy transfer from excited triplet acetone. This involves thermolysis of 3,3,4,4-tetramethyl-1,2-dioxetane, a chemical source, and horseradish peroxidase-catalyzed oxidation of 2-methylpropanal, as an enzymatic source. Both sources of excited carbonyls showed characteristic light emission at 1,270 nm, directly indicative of the monomolecular decay of O-2 ((1)Delta(g)). Indirect analysis of O2 (1Dg) by electron paramagnetic resonance using the chemical trap 2,2,6,6-tetramethylpiperidine showed the formation of 2,2,6,6-tetramethylpiperidine-1-oxyl. Using {[}O-18]-labeled triplet, ground state molecular oxygen {[}O-18(2) ((3)Sigma(g) -)], chemical trapping of O-18(2) ((1)Delta(g)) with disodium salt of anthracene-9,10-diyldiethane-2,1-diyl disulfate yielding the corresponding double-{[}O-18]-labeled 9,10-endoperoxide, was detected through mass spectrometry. This corroborates formation of O-2 ((1)Delta(g)). Altogether, photoemission and chemical trapping studies clearly demonstrate that chemically and enzymatically nascent excited carbonyl generates O-18(2) ((1)Delta(g)) by triplet-triplet energy transfer to ground state oxygen O-2 ((1)Delta(g)), and supports the long formulated hypothesis of O-2 ((1)Delta(g)) involvement in physiological and pathophysiological events that might take place in tissues in the absence of light. (AU)

Processo FAPESP: 12/12663-1 - Oxigênio singlete e peróxidos em química biológica
Beneficiário:Paolo Di Mascio
Linha de fomento: Auxílio à Pesquisa - Temático
Processo FAPESP: 13/07937-8 - Redoxoma
Beneficiário:Ohara Augusto
Linha de fomento: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
Processo FAPESP: 06/56530-4 - Estresse redox e carbonílico associado a alfa-aminocetonas e beta-cetoácidos endógenos: mecanismos e biomarcadores
Beneficiário:Etelvino José Henriques Bechara
Linha de fomento: Auxílio à Pesquisa - Temático