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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.)

Cyclic Peroxidic Carbon Dioxide Dimer Fuels Peroxyoxalate Chemiluminescence

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Author(s):
da Silva, Sandra M. [1] ; Lang, Andre P. [1] ; dos Santos, Ana Paula F. [1] ; Cabello, Maidileyvis C. [1] ; Ciscato, Luiz Francisco M. L. [1] ; Bartoloni, Fernando H. [2] ; Bastos, Erick L. [1] ; Baader, Wilhelm J. [1]
Total Authors: 8
Affiliation:
[1] Univ Sao Paulo, Dept Quim Fundamental, Inst Quim, BR-05508000 Sao Paulo, SP - Brazil
[2] Univ Fed ABC, Ctr Ciencias Nat & Humanas, Santo Andre, SP - Brazil
Total Affiliations: 2
Document type: Journal article
Source: Journal of Organic Chemistry; v. 86, n. 17, p. 11434-11441, SEP 3 2021.
Web of Science Citations: 0
Abstract

Peroxyoxalate chemiluminescence is used in self-contained light sources, such as glow sticks, where oxidation of aromatic oxalate esters produces a high-energy intermediate (HEI) that excites fluorescence dyes via electron transfer chemistry, mimicking bioluminescence for efficient chemical energy-to-light conversion. The identity of the HEI and reasons for the efficiency of the peroxyoxalate reaction remain elusive. We present here unequivocal proof that the HEI of the peroxyoxalate system is a cyclic peroxidic carbon dioxide dimer, namely, 1,2-dioxetanedione. Oxalic peracids bearing a substituted phenyl group were unable to directly excite fluorescent dyes; hence, they could be ruled out as the HEI. However, base-catalyzed cyclization of these species results in bright chemiluminescence, with decay rates and chemiexcitation quantum yields that are influenced by the electronic phenylic substituent properties. Hammett (rho = +2.2 +/- 0.1) and Bronsted (beta = -1.1 +/- 0.1) constants for the cyclization step preceding chemiexcitation imply that the loss of the phenolateleaving group and intramolecular nucleophilic attack of the percarboxylate anion occur in a concerted manner, generating 1,2-dioxetanedione as the unique outcome. The presence of better leaving groups influences the reaction mechanism, favoring the chemiluminescent reaction pathway over the nonemissive formation of aryl-1,2-dioxetanones. (AU)

FAPESP's process: 19/06391-8 - Photophysical characterization and anti-inflammatory potential of 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