Study Of New Electrogenerated Chemiluminescence Method Based On Tris (2,2'-bipyridyl)Ruthenium(Ⅱ)

This thesis included a review and a research section. In the review section, the history, basic principles, characteristics, main reaction systems and the mechanism of electrogenerated chemiluminescence(ECL) were introduced. Moreover, the applications of those ECL systems in recent years were reviewed. In addition, a general introduction was proposed about the ECL coupled with some other techniques as well as their applications in pharmaceutical analysis. We have also reviewed the applications of chemical modification technique as well as the nano technology in ECL in recent years.The research section contained the following subunits:1. A capillary electrophoresis with an end-colum electrogenerated chemiluminescence detection method which based on the fact that verapamil can increase tris(2,2'-bipyridyl)ruthenium(Ⅱ)(Ru(bpy)32+) electrogenerated chemiluminescence was developed for the detection of verapamil chloride in pharmaceuticals and human urine. Under optimized conditions, the ECL intensity was linear with the concentration of verapamil over the range from 7.0×10-7to 5.0×10-4 M with a detection limit of 4.6×10-8 M. The RSD of transition time and peak height were 1.2% and 2.08%, respectively. This method was successfully applied for the detection of verapamil in pharmaceuticals and human urine. The interaction of verapamil with bovine hemoglobin was also investigated. The binding constant(K) and the maximum binding capacity(αmax) were calculated to be 3.72×103 L/mol and 1.375×10-4 mol, respectively.2. A facile approach was proposed to immobilize Ru(bpy)32+on the GO by chemical polymerization of DA and electrostatic interaction between Ru(bpy)32+and the negatively charged groups of GO. With the perfect electric conductivity, large specific surface area of GO and the chemical stability of PDA, the modified electrode could be utilized as an excellent ECL sensor for the detection of TPA with high sensitivity and good stability. The constructed sensor showed a linear range for the detection of TPA from 5.0×10-9 to 1.0×10-5 M with a detection limit of 1.0 nM. The ECL sensor kept 79% and 83% activity towards 0.1 mM TPA after being stored in air and in 0.1M pH 8.0 phosphate buffer solution (PBS) for a month, respectively. This facile, versatile and efficient approach enables a promising prospect for the wide applications of such novel kinds of Ru(bpy)32+based nanocomposites materials and, therefore, hold great promise for solid-state ECL detection in capillary electrophoresis(CE) or CE microchips.3. A novel ECL sensor was prepared by immobilizing PDA-AuNPs-Ru(bpy)32+ mesoporous nanocomposite films on the electrode surface. The electrochemical and ECL characters with the coreagent, tripropylamine(TPA), were investigated in PBS. Under the optimized conditions, this sensor was able to detect TPA in a wide linear range from 5.0x10-8 to 6.0x10-5 M with a detection limit of 1x10-8 M. The ECL sensor kept 77% and 89% activity after being stored in air and in 0.1M pH 7.8 PBS for a month, respectively, which shows good stability of this ECL sensor.4. Based on the large surface area, good adsorbability and ion exchange capacity of montmorillonite(MMT), together with the big surface area and the negatively charged groups of GO, we prepared GO/MMT/Ru(bpy)32+ nanocomposites and developed a novel ECL sensor. The electrochemical and ECL characters with the coreagent, tripropylamine(TPA), were investigated in PBS. The constructed sensor showed a linear range for the detection of TPA from 5.0x10-8 to 6.0x10-5 M with a detection limit of 5x10-9 M. The ECL sensor kept 76% and 81% activity towards 0.1 mM TPA after being stored in air and in 0.1 M pH 8.0 PBS for a month, respectively. These results indicated that the sensor showed good stability. The good stability and adsorbability of MMT, perfect electric conductivity of GO make the sensor hold great promise for solid-state ECL detection of medicament.