The chemiluminescent peroxyoxalate system: state of the art almost 50 years from its discovery

Almost fifty years after the discovery of the peroxyoxalate reaction by E. A. Chandross in the early nineteen sixties, this review article intends to give a general overview on mechanistic aspects of this system and to describe the principles of its analytical application. After a short general introduction on the principles of chemiluminescence and the history of peroxyoxalate discovery, mechanistic aspects of high-energy intermediate formation, its structure and its reaction with an activator in the peroxyoxalate system are discussed. Finally, analytical applications of peroxyoxalate chemiluminescence are exemplified using representative recent examples, including oxalic acid detection in biological samples.

Effect of some surfactants on the chemiluminescent reactions of bis(2,4,6-trichlorophenyl)oxalate and bis(2-nitrophenyl)oxalate with hydrogen peroxide

The chemiluminescent reactions of bis(2,4,6-trichlorophenyl)oxalate (TCPO) and bis(2-nitrophenyl)oxalate (2-NPO) with hydrogen peroxide in acetonitrile/water micellar systems (anionic, cationic, and non-ionic) and gamma-cyclodextrin were studied in the presence of fluoranthene or 9,10-diphenylanthracene, imidazole, and two buffer solutions, HTRIS+/TRIS and H2PO4-/HPO42-. The relative chemiluminenscence (CL) intensity is higher in the presence of the cationic (DDAB, CTAC, DODAC, and OTAC), anionic (SDS), and non-ionic (Tween 80) surfactants. In the presence of some non-ionic surfactants (Brij 35, Brij 76, and Tween 20), the CL intensity was partially quenched compared with the reaction with no surfactant. The sensitivity for hydrogen peroxide determination in the range 0.01 x 10(-4) to 1.0 x 10(-4) mol L-1, considering the slope of the calibration curves (maximum peak height of CL vs. concentration), improved with the introduction of DDAH, CTAB, and SDS in HTRIS+/TRIS buffer.

Hydroxythiazole-Based Fluorescent Probes for Fluoride Ion Detection

This work describes the synthesis of five O-silyloxy-1,3-thiazoles and their use as fast-response turn-on probes for fluoride ion detection in polar aprotic solvents and in aqueous cetyltrimethylammonium bromide micellar medium. The fluoride-triggered deprotection of these silyl ethers results in ca. 180-nm shifts in the fluorescence emission wavelengths. All compounds are suitable for the detection of fluoride ions with a detection limit in DMSO of 107 mol?L1; derivatives containing a 2-pyridyl moiety in the thiazole system are more efficient than those with a 3- or 4-pyridyl moiety. Typical anionic interferents, such as acetate or chloride, are not detected by O-silyloxy-1,3-thiazoles, making these compounds very specific for fluoride.