| Texto completo | |
| Autor(es): |
Augusto, Felipe A.
;
Frances-Monerris, Antonio
;
Galvan, Ignacio Fdez
;
Roca-Sanjuan, Daniel
;
Bastos, Erick L.
;
Baader, Wilhelm J.
;
Lindh, Roland
Número total de Autores: 7
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Physical Chemistry Chemical Physics; v. 19, n. 5, p. 3955-3962, FEB 7 2017. |
| Citações Web of Science: | 12 |
| Resumo | |
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. (AU) | |
| Processo FAPESP: | 14/14866-2 - Interações intermoleculares envolvendo betalaínas |
| Beneficiário: | Erick Leite Bastos |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |
| Processo FAPESP: | 14/22136-4 - Uso de solventes verdes e suas misturas na otimização de processos químicos |
| Beneficiário: | Omar Abou El Seoud |
| Modalidade de apoio: | Auxílio à Pesquisa - Temático |