A novel tris(2,2 ' -bipyridyl)ruthenium(IH) [Ru(bpy)(3)(3+)]-based electrochemiluminescence (ECL) detector for capillary electrophoresis (CE) has been developed. The detector was of the wall-jet configuration and an indium/tin oxide (ITO)-coated glass plate was used as the working electrode for end-column detection. Potential control of the ITO electrode was provided using a DC battery, without decoupling the detector from the CE field. Electrochemical behavior of Ru(bpy)(3)(2+) at the ITO electrode was found to be analogous to that at a Pt electrode. In the presence of tertiary or some secondary amines, ECL emission due to reaction between in situ generated Ru(bpy)(3)(3+) and analytes can be observed at the ITO surface. With 15 mM sodium borate (pH 9.5) plus 1 mM Ru(bpy)(3)(2+) present in the detection cell and the ITO electrode biased at 1.5 V (vs. Pt wire reference), a detection limit of 1 muM proline with a theoretical plate number of 4000 was obtained using the developed CE-ECL detection system. The detector response was found to be analyte-dependent, e.g. tryptophan gives no response, and the response for histidine is about 13-fold lower than that of proline. (C) 2001 Elsevier Science B.V. All rights reserved.