Peroxyoxalate-chemiluminescence of Tinopal CBS as a commercially important optical brightener: Mechanistic study and quantification

The peroxyoxalate-chemiluminescence arising from reaction of bis(2,4,6-trichlorophenyl)oxalate with hydrogen peroxide in the presence of a brightener Tinopal CBS (2,2′-((1,1′-biphenyl)-4,4′-diyldi-2.1-ethenediyl)bisbenzene sulfonic acid, disodium salt) has been studied. The relationship between the chemiluminescence intensity and concentrations of bis(2,4,6-trichlorophenyl)oxalate, sodium salicylate (as catalyst), hydrogen peroxide and Tinopal CBS is reported. The chemiluminescence parameters including intensity at maximum chemiluminescence, time at maximum intensity, total light yield, theoretical maximum level of intensity and pseudo-first-order rate constants for the rise and fall of the chemiluminescence burst (k_r and k_f) were evaluated from computer fitting of the resulting intensity-time plots. The activation parameters E_a, ΔH^‡, ΔS^‡ and ΔG^‡ for the rise and fall steps were evaluated from the temperature dependence of k_r and k_f values. The results were discussed in terms of chemically initiated electron transfer between a reactive intermediate and Tinopal CBS as fluorescence activator. A possible mechanism involving dioxetanone derivatives as intermediates is proposed. Since there is a linear relationship between reciprocal of chemiluminescence intensity and reciprocal of fluorescer concentration, an analytical method based on partial least squares (PLS) regression was proposed for quantitative determination of Tinopal CBS. Satisfactory results were obtained with percent relative prediction error (RPE%) of 2.52 and detection limit of 2.7×10⁻⁵ M.     

Quenching effect of some heavy metal ions on the fast peroxyoxalate-chemiluminescence of 1-(dansylamidopropyl)-1-aza-4,7,10-trithiacyclododecane as a novel fluorophore

The fast chemiluminescence (CL) arising from the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in the presence of 1-(dansylamidopropyl)-1-aza-4,7,10-trithiacyclododecane (L) as a novel fluorophore, and imidazole as catalyst, has been studied in ethyl acetate solution. The relationships between the chemiluminescence intensity and concentrations of TCPO, imidazole, hydrogen peroxide and L are reported. In the presence of imidazole as catalyst, the entire CL signal was completed in less than 3 s. The quenching effect of Cu²⁺, Pb²⁺, Cd²⁺, Hg²⁺ and Ag⁺ ions on the chemiluminescent system was investigated, the resulting Stern–Volmer plots were obtained and the K_Q values were calculated. It was found that the quenching effect of metal ions on the chemiluminescence of L decreases in the order Cu²⁺ > Pb²⁺ > Cd²⁺ > Hg²⁺ > Ag⁺.