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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Chemiluminescence Efficiency of Catalyzed 1,2-Dioxetanone Decomposition Determined by Steric Effects

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Author(s):
Bartoloni, Fernando Heering [1] ; de Oliveira, Marcelo Almeida [1] ; Monteiro Leite Ciscato, Luiz Francisco [1] ; Augusto, Felipe Alberto [1] ; Bastos, Erick Leite [1] ; Baader, Wilhelm Josef [1]
Total Authors: 6
Affiliation:
[1] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, BR-05508000 Sao Paulo - Brazil
Total Affiliations: 1
Document type: Journal article
Source: Journal of Organic Chemistry; v. 80, n. 8, p. 3745-3751, APR 17 2015.
Web of Science Citations: 19
Abstract

The chemiluminescent decomposition of 1,2-dioxetanones (alpha-peroxylactones), catalyzed by an appropriate fluorescent activator, is an important simple model for efficient bioluminescent transformations. In this work, we report experimental data on the catalyzed decomposition of two spiro-substituted 1,2-dioxetanone derivatives, which support the occurrence of an intermolecular electron transfer from the activator to the peroxide. The low efficiency of the studied systems is associated with steric hindrance during the chemiexcitation sequence, rationalized using the concept of supermolecule formation between the peroxide and the catalyst. This approach explains the difference in the chemiexcitation efficiencies in the decomposition of four-membered cyclic peroxide derivatives: 1,2-dioxetanes, 1,2-dioxetanones, and 1,2-dioxetanedione (the intermediate in the peroxyoxalate reaction), which are the most important model compounds for excited-state formation in chemiluminescence and bioluminescence processes. (AU)

FAPESP's process: 12/02428-5 - Cyclic organic peroxides: synthesis and mechanism of reduction
Grantee:Luiz Francisco Monteiro Leite Ciscato
Support type: Regular Research Grants
FAPESP's process: 12/13807-7 - New tools for the study of electron transfer reactions in PS II model systems
Grantee:Fernando Heering Bartoloni
Support type: Regular Research Grants
FAPESP's process: 14/14866-2 - Intermolecular interactions involving betalains
Grantee:Erick Leite Bastos
Support type: 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 type: Research Projects - Thematic Grants