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Mechanism of activa...
Mechanism of activated chemiluminescence of cyclic peroxides : 1,2-dioxetanes and 1,2-dioxetanones
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- Augusto, Felipe A. (author)
- Uppsala universitet,Teoretisk kemi,Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Av Prof Lineu Prestes 748, Sao Paulo, Brazil.
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- Francés-Monerris, Antonio (author)
- Uppsala universitet,Teoretisk kemi,Univ Valencia, Inst Ciencia Mol, POB 22085, Valencia 46071, Spain.
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- Fdez. Galván, Ignacio, 1977- (author)
- Uppsala universitet,Teoretisk kemi
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- Roca-Sanjuán, Daniel (author)
- Univ Valencia, Inst Ciencia Mol, POB 22085, Valencia 46071, Spain.
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- Bastos, Erick L. (author)
- Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Av Prof Lineu Prestes 748, Sao Paulo, Brazil.
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- Baader, Wilhelm J. (author)
- Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Av Prof Lineu Prestes 748, Sao Paulo, Brazil.
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- Lindh, Roland, 1958- (author)
- Uppsala universitet,Teoretisk kemi
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(creator_code:org_t)
- 2017
- 2017
- English.
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In: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 19:5, s. 3955-3962
- Related links:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Subject headings
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- Almost all chemiluminescent and bioluminescent reactions involve cyclic peroxides. The structure of the peroxide and reaction conditions determine the quantum efficiency of light emission. Oxidizable fluorophores, the so-called activators, react with 1,2-dioxetanones promoting the former to their first singlet excited state. This transformation is inefficient and does not occur with 1,2-dioxetanes; however, they have been used as models for the efficient firefly bioluminescence. In this work, we use the SA-CASSCF/CASPT2 method to investigate the activated chemiexcitation of the parent 1,2-dioxetane and 1,2-dioxetanone. Our findings suggest that ground state decomposition of the peroxide competes efficiently with the chemiexcitation pathway, in agreement with the available experimental data. The formation of non-emissive triplet excited species is proposed to explain the low emission efficiency of the activated decomposition of 1,2-dioxetanone. Chemiexcitation is rationalized considering a peroxide/activator supermolecule undergoing an electron-transfer reaction followed by internal conversion.
Subject headings
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
- NATURVETENSKAP -- Fysik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences (hsv//eng)
Publication and Content Type
- ref (subject category)
- art (subject category)
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