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The combination of an ion-pair extraction detection system with peroxyoxalate chemiluminescence detection has been investigated. Ion-pairs of protonated tertiary amines with a chemiluminescent counter ion are on-line post-column extracted to 1,2-dichloroethane containing bis(2,4,6-trichlorophenyl)oxalate (TCPO). Hydrogen peroxide is added to the organic phase by means of a solid-state perhydrit reactor. The influence of the base catalyst (imidazole) on the chemiluminescence reaction in apolar solvents was studied. Some sulfonated chemiluminophores were compared with respect to their chemiluminescence, ion-pairing and extraction properties, and 5-dimethylaminonaphthalene-1-sulfonate was found to be the most suitable reagent. The detection limit of the potential drug secoverine is in the sub-nanogram range.

A peroxyoxalate chemiluminescence detection system for liquid chromatography is described. The excitation of fluorophores is generated by the reaction of bis-(2,4,6-trichlorophenyl)oxalate or bis(2,4-dinitrophenyl)oxalate and hydrogen peroxide, which are added to the column effluent. The influence of the solvents and the concentrations of the reagents have been investigated. The influence of the flow cell volume on sensitivity and on band broadening have also been studied and a “chemical band narrowing effect” has been observed. Different types of apparatus have been compared for detection of the emitted light. The system has been used for the detection of the dansyl derivative of a drug with a secondary amine functional group in serum samples. The detection limits are in the 1–10pg range.