Mechanistic studies on the salicylate-catalyzed peroxyoxalate chemiluminescence in aqueous medium
| Autor: | Glalci Alves de Souza, Liena Valero Bello, Maidileyvis Castro Cabello, Wilhelm J. Baader |
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| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
010401 analytical chemistry Inorganic chemistry General Medicine 01 natural sciences Biochemistry Peroxyoxalate Oxalate Dimethoxyethane 0104 chemical sciences law.invention chemistry.chemical_compound chemistry law Anhydrous TROCA IÔNICA Singlet state Physical and Theoretical Chemistry TCPO Hydrogen peroxide Chemiluminescence |
| Zdroj: | Repositório Institucional da USP (Biblioteca Digital da Produção Intelectual) Universidade de São Paulo (USP) instacron:USP |
| Popis: | The peroxyoxalate reaction is one of the most efficient chemiluminescence transformations known and the only system occurring by an intermolecular chemically initiated electron exchange luminescence (CIEEL) mechanism with confirmed high quantum yields. The peroxyoxalate chemiluminescence (PO-CL) is mainly studied in anhydrous organic medium; however, for bioanalytical application, it should be performed in aqueous media. In the present work, we study the peroxyoxalate system in a binary 1,2-dimethoxyethane/water mixture with bis(2,4,6-trichlorophenyl) oxalate (TCPO), bis(4-methylphenyl) oxalate (BMePO) and bis[2-(methoxycarbonyl)phenyl] oxalate (DMO), catalyzed by sodium salicylate, in the presence of rhodamine 6G as activator. Reproducible kinetic results are obtained for all systems; emission decay rate constants depend on the salicylate as well as hydrogen peroxide concentration, and the occurrence of a specific base catalysis is verified. Although singlet quantum yields determined are lower than in anhydrous media in comparable conditions, they are still considerably high and adequate for analytical applications. The highest singlet quantum yields are obtained for the "ecologically friendly" derivative DMO indicating that this derivative might be the most adequate substrate for the use of the peroxyoxalate system in bioanalytical applications. |
| Databáze: | OpenAIRE |
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