Electrogenerated chemiluminescences (ECLs) based on tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)) and lupin alkaloids, for instance, sophoridine (SRI), matrine (NIT), sophoranol (SR) and sophocarpine (SC) in an aqueous alkaline buffer solution (pH 9.0) are studied. The light emission is mainly caused by an Electro-oxidation reaction between tertiary amino group on the alkaloid compounds and Ru(bpy)(3)(2+) in a thin layer flow cell equipped with a glassy carbon disc electrode (22.1 mm(2)) at the potential of +1.50 V (versus Ag/AgCl). The luminescence wavelength of 610 nm confirmed that ECL is caused by Ru(bpy)(3)(2+)* to its ground state. ECL intensities of these lupin alkaloids are affected by the substituent character, three-dimensional conformation of hydrogen on beta-carbon atom. Ionization potentials taken from calculation data further confirm the experimental results. In addition, the factors affecting the determination and HPLC separation of the four alkaloids are also investigated. (C) 2002 Elsevier Science B.V. All rights reserved.