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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.

Peroxyoxalate chemiluminescence is used in selfcontained 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 (ρ = +2.2 ± 0.1) and Brønsted (β = −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 1,2dioxetanedione 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.

The peroxyoxalate reaction is being widely used for various analytical and bioanalytical applications, and however, few mechanistic studies are performed in aqueous media, important mainly for bioanalytical applications, where low chemiluminescence emission quantum yields are obtained. In this sense, we report here kinetic studies on the peroxyoxalate reaction, using two commercially available and widely utilized esters, bis(2,4‐dinitrophenyl) oxalate (DNPO) and bis(2,4,6‐trichlorophenyl) oxalate (TCPO), in 1,2‐dimethoxyethane:water mixtures. The reaction of the much more reactive DNPO, in anhydrous and aqueous media, occurs by a direct nucleophilic attack of H2O2 to the oxalic ester, not involving nucleophilic catalysis by imidazole. Contrary, in the reaction of the less reactive TCPO with H2O2, imidazole acts mainly as nucleophilic catalyst. For both esters, experimental conditions are established where precise kinetic data and emission quantum yields can be obtained. Interestingly, the quantum yields in 1,2‐dimethoxyethane water mixtures increase up to a water concentration of 0.7 mol L–1 and decrease significantly with higher concentrations.

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Bioluminescence (BL) and chemiluminescence (CL) are interesting and intriguing phenomena that involve the emission of visible light as a consequence of chemical reactions. The mechanistic basis of BL and CL has been investigated in detail since the 1960s, when the synthesis of several models of cyclic peroxides enabled mechanistic studies on the CL transformations, which led to the formulation of general chemiexcitation mechanisms operating in BL and CL. This review describes these general chemiexcitation mechanisms—the unimolecular decomposition of cyclic peroxides and peroxide decomposition catalyzed by electron/charge transfer from an external (intermolecular) or an internal (intramolecular) electron donor—and discusses recent insights from experimental and theoretical investigation. Additionally, some recent representative examples of chemiluminescence assays are given.