| Full text | |
| Author(s): |
Khalid, Muhammad
[1]
;
Oliveira, Marcelo A.
[1]
;
Souza, Jr., Sergio P.
[1]
;
Ciscato, Luiz F. M. L.
[2]
;
Bartoloni, Fernando H.
[2]
;
Baader, Wilhelm J.
[1]
Total Authors: 6
|
| Affiliation: | [1] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, BR-05508000 Sao Paulo, SP - Brazil
[2] Univ Fed ABC, Ctr Ciencias Nat & Humanas, Santo Andre - Brazil
Total Affiliations: 2
|
| Document type: | Journal article |
| Source: | JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY; v. 312, p. 81-87, NOV 1 2015. |
| Web of Science Citations: | 8 |
| Abstract | |
Chemiluminescence transformations have found widespread analytical and bioanalytical application, however, a general principle which governs the efficiency of chemiluminescence transformations, specifically the catalyzed and unimolecular decomposition of cyclic peroxides, is still not known. Thus, the solvent viscosity influence on the singlet quantum yield in catalyzed diphenoyl peroxide and spiro-adamantyl-1,2-dioxetanone decomposition is studied in the present work. Both reactions do not show significant quantum yield increase within the viscosity range studied (0.56-2.57 cP) using binary toluene/diphenylmethane mixtures. However, the induced decomposition of a phenoxy-substituted 1,2-dioxetane derivative in identical conditions showed to be more sensitive to solvent viscosity effects. These results indicate, for the first time, that the classical intermolecular electron transfer initiated chemiluminescence systems, catalyzed decomposition of diphenoyl peroxide and 1,2-dioxetanones, are not subject to significant solvent cavity effects. Therefore, their low quantum efficiencies cannot be due to solvent cavity escape of intermediate radical ion species during the chemiexcitation process. Additionally, it can be concluded that the highly efficient induced decomposition of phenoxy-substituted 1,2-dioxetanes should occur mainly by an entirely intramolecular process. (C) 2015 Elsevier B.V. All rights reserved. (AU) | |
| 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: | 14/22136-4 - Use of green solvents and their mixtures for optimizing chemical processes |
| Grantee: | Omar Abou El Seoud |
| Support Opportunities: | Research Projects - Thematic Grants |