| Full text | |
| Author(s): |
Khalid, Muhammad
[1]
;
Souza, Jr., Sergio P.
[1]
;
Ciscato, Luiz F. M. L.
[2]
;
Bartoloni, Fernando H.
[2]
;
Baader, Wilhelm J.
[1]
Total Authors: 5
|
| Affiliation: | [1] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Sao Paulo - Brazil
[2] Univ Fed ABC, Ctr Ciencias Nat & Humanas, Santo Andre, SP - Brazil
Total Affiliations: 2
|
| Document type: | Journal article |
| Source: | PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES; v. 14, n. 7, p. 1296-1305, 2015. |
| Web of Science Citations: | 10 |
| Abstract | |
The effects of the medium viscosity on the chemiexcitation quantum yields of the induced decomposition of 1,2-dioxetanes (highly efficient intramolecular CIEEL system) and the catalyzed decomposition of diphenoyl peroxide and a 1,2-dioxetanone derivative (model systems for the intermolecular CIEEL mechanism, despite their low efficiency) are compared in this work. Quantum yields of the rubrene catalyzed decomposition of diphenoyl peroxide and spiro-adamantyl-1,2-dioxetanone as well as the fluoride induced decomposition of a phenoxy-substituted 1,2-dioxetane derivative are shown to depend on the composition of the binary solvent mixture toluene/diphenyl ether, which possess similar polarity parameters but different viscosities. Correlations of the quantum yield data with the medium viscosity using the diffusional and the frictional (free-volume) models indicate that the induced 1,2-dioxetane decomposition indeed occurs by an entirely intramolecular process and the low efficiency of the intermolecular chemiluminescence systems (catalyzed decomposition of diphenoyl peroxide and 1,2-dioxetanone derivative) is not primarily due to the cage escape of radical ion species. (AU) | |
| FAPESP's process: | 05/58320-4 - Efeito da estrutura e do meio de reação sobre a quimiluminescência de dioxetanonas |
| Grantee: | Fernando Heering Bartoloni |
| Support Opportunities: | Scholarships in Brazil - Doctorate (Direct) |
| FAPESP's process: | 12/02428-5 - Cyclic organic peroxides: synthesis and mechanism of reduction |
| Grantee: | Luiz Francisco Monteiro Leite Ciscato |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 06/03420-7 - Estudos sobre o mecanismo da decomposicao induzida de 1,2-dioxetanos e da reacao peroxi-oxalato; aplicacoes da quimiluminescencia do luminol. |
| Grantee: | Joséf Wilhelm Baader |
| Support Opportunities: | Regular Research Grants |