ECL of several amines containing different numbers of hydroxyl and amino groups was investigated. N-butyldiethanolamine is found to be more effective than 2-(dibutylamino)ethanol at gold and platinum electrodes, and is the most effective coreactant reported until now. Surprisingly, ECL intensities of monoamines, such as 2-(dibutylamino)ethanol and N-butyldiethanolamine, are much stronger than that of diamines including N,N,N′,N′-tetrakis-(2-hydroxyethyl)-ethylenediamine and N,N,N′,N′-tetrakis-(2-hydroxypropyl)ethlenediamine. The striking contrast between ECL signals of the investigated monoamines and diamines may result from more significant side reactions of diamines, such as the intramolecular side reactions between oxidative amine cation radicals and reductive amine free radicals.

•CE–ECL technique was developed for the determination of two antipsychotic drugs perphenazine (PPH) and fluphenazine (FPH).•High sensitivity, wide linear range, and good repeatability could be obtained by this method.•The proposed method was applied for the analysis of PPH and FPH in human urine.The coupling of end-column tris (2,2′-bipyridyl) ruthenium (II) electrochemiluminescence (ECL) detection with capillary electrophoresis (CE) was developed for the analysis of two antipsychotic drugs, perphenazine (PPH) and fluphenazine (FPH). The parameters related to CE separation and ECL detection, including the detection potential, the buffer pH value and concentration, the separation voltage, and Ru(bpy)32+ concentration, were investigated in detail. Under optimum conditions, PPH and FPH were well separated and detected within 11 min. The linear ranges were 0.1–5 μM for PPH, and 0.1–7.5 μM for FPH, respectively. The limits of detection of PPH and FPH were 5 and 10 nM (S/N=3). The relative standard deviations (n=3) of the ECL intensity and the migration time were less than 2.5 and 0.65% in a day, and less than 3.4 and 1.7% in different three days. The proposed method was successfully applied to determine PPH and FPH in spiked urine samples with satisfactory results.Based on the fact that the light emission of Ru(bpy)32+ ECL could be enhanced by PPH and FPH containing a tertiary amines group dramatically, CE–ECL has been established for rapid separation and sensitive detection of PPH and FPH. The proposed method was successfully applied to the analysis of two analytes in human urine samples.