Atenolol (AT) and metoprolol (ME) are antihypertensive drugs that belong to the family of selective β(1)-adrenergic receptor antagonists (β-blockers), which are widely used in the treatment of hypertension, angina pectoris, cardiac arrhythmias and myocardial infarction. 1 Due to their sedative effect, they are also used as doping agents in sports. An overdose of β-blockers may lead to bradycardia, hypotension, aggravation of cardiac failure, bronchospasm, hypoglycemia, and fatigue.2 Therefore, it is necessary to develop a sensitive and simple analytical method to determine β-blockers in many fields, including doping control, forensic analysis, toxicology and pharmacokinetic study.As a consequence of the widespread use of AT and ME, several analytical techniques have been developed for their determination in recent years, including spectrophotometry [3][4][5] and differential pulse voltammetry. 6,7 However, the sensitivity of these methods was limited. The most widely used were chromatographic techniques, such as gas chromatography (GC), 8,9 high-performance liquid chromatography (HPLC) [10][11][12][13][14][15][16][17] and urtra-performance liquid chromatography (UPLC). 18 Among them, expensive columns and costly apparatus were needed, and the analysis time was relatively long.The capillary electrophoresis (CE) technique has been developed for over 20 years, and has become a mature and wellestablished analytical tool. CE is characterized as a powerful separation technique because of its high efficiency, relatively short analysis time, and low sample and reagent consumption. As an alternative and complementary technique to HPLC for routine analysis, CE-UV has been used for AT and ME analysis.
19-22Because of the small sample volume being assayed, this method has encountered the problem of poor sensitivity, which has limited its application in practice. He et al. 23 developed an on-line ion-exchange preconcentration method for improving the detection sensitivity of CE-UV. The proposed method enhanced the detection sensitivity of CE-UV by about 5000 times for metoprolol compared with the normal electrokinetic injection.However, the preparation of a preconcentration column was complex for a general laboratory. Thus, it is very important to develop a simple and sensitive method to detect AT and ME.Electrochemiluminescence (also called electrogenerated chemiluminescence) is a means of converting electrical energy into radiative energy. 24 It has been proved to be a powerful analytical tool that combines the simplicity of electrochemistry and the inherent sensitivity and the wide linear range of the chemiluminescence method.
25Among the ECL systems, tris(2,2′-bipyridyl)ruthenium(II) Ru(bpy)3 2+ -based ECL is the most valuable in fundamental studies and applications because of its stability and capability of undergoing ECL at room temperature in aqueous solutions and its regenerating during the ECL process.
26Since the first report of Ru(bpy)3 2+ ECL in 1972, 27 Ru(bpy)3 2+ ECL as a sensitive detection method has been...