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Designed catalysts for bright and fast peroxyoxalate chemiluminescence Tobias Jonsson; Malin A R Stigbrand*; Knut Irgum Dept. of Chemistry, Analytical Chemistry, Umea University, S-901 87 Umea, SWEDEN      *(msd@chem.umu.se) Chemiluminescence detection systems for miniaturized liquid chromatographic and electrophoretic separation systems must be based on reactions with fast kinetics and high light intensities. This work describes how high-intensity light can be generated within less than 50 milliseconds by using azoles or 4-aminopyridines as single nucleophilic catalysts or alternatively by employing a two-component catalyst mixture where a non-nucleophilic base assists the nucleophilic catalyst by accepting one of its protons. Stopped-flow studies identified base promoted reagent and intermediate breakdown as one of the major limitations to achieving high light intensities. This translates into a need of matching the basicity of the catalyst with the basicity of the leaving group from the reagent and a similar requirement of carefully controlling the concentration of the ancillary base in the two-component catalyst mixture. [Poster: stigbran.malina.50632]

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