The Application And Study Of Electrogenerated Chemiluminescence With Tris(2,2-dipyridyl)ruthenium (Ⅱ) In Pharmaceutical Analysis

In the Electrochemical Luminescence （ECL） analysis, the reaction betweenluminescent material and the reactants mainly happened on the interface of the workelectrode and reactants solution. So the micro-environmental of the surface on the workelectrode has significant effect on the ECL intensity of [Ru（bpy）₃]²⁺system. Therefore, inthis paper some materials were chosen as addition agent, such as anionic surfactantsodium dodecyl benzene sulfonate （SDBS） and halide ions. Meanwhile a modifiedworked electrod was fabricated which was self-assembly modified by penicillamine onthe gold electrode. Some highly sensitive methods were established to detected somedrugs in this paper, due to the ECL intensity of [Ru（bpy）₃]²⁺system could significantlyenhanced by the surface active agent or the SAM modified electrode. The characteristics,orderliness, mechanism, and analysis application of the [Ru（bpy）₃]²⁺system were studiedby the method explained above. The main results were shown as follows:Due to the addition of Azithromycin would further lead to an enhancement of ECLintensity of [Ru（bpy）₃]²⁺, the electrochemical and ECL behaviors of thisAzithromycin-[Ru（bpy）₃]²⁺system were studied, with the gold electrode as the workelectrode. And a new ECL method was established for determination of the Azithromycin.Under the optimal conditions, the ECL peak counts increased linearly with theconcentration of Azithromycin in the range of2.00×10^-4～4.00×10^-7mol/L, linearregression equation: I（counts）=22.848×10⁶C+221.8（r=0.9981, n=12）, with the detectionlimit3.00×10^-9mol/L （S/N=3）. The RSD for10times determination of1.00×10^-5mol/LAzithromycin was2.09%. The results of recovery test were between95.19～101.80%, andthe RSD was2.40%. This proposed method was applied in the determination ofAzithromycin capsule with satisfactory results.In the presence of6.50×10^-3mol/L SDBS, the electrochemical and ECLcharacteristics of the [Ru（bpy）₃]²⁺-benzhexol hydrochloride （BH） system at the Auelectrode were studied by cyclic voltammetric and ECL method. The results showed thatthe ECL intensity of [Ru（bpy）₃]²⁺on the Au electrode was enhanced significantly in thepresence of BH. In the presence of SDBS, the ECL intensity of [Ru（bpy）₃]²⁺-BH systemswas enhanced about16times. Based on this, a new ECL method was established for thedetermination of BH. Under the optimum condition, the enhanced ECL intensities hadgood linear relationship with concentration of BH in the range of1.00×10^-44.00×10^-7mol/L, with detection limit of1.11×10^-9mol/L. The relative standard deviations （RSD）（n=10） of ECL intensities for ten times determinations of1.00×10^-5mol/L BH was3.20%.The results of recovery test were between96%and108%, with RSD of4.3%. Thisproposed method showed high selectivity and sensitivity, and was applied in thedetermination of BH in real sample with satisfactory results.The electrochemical and ECL behaviors of [Ru（bpy）₃]²⁺-Ketotifen Fumarate system on the Au electrode were studied in the presence of halide ions. The results showed that anenhancement electrochemical activity and ECL response were exhibited in the presence ofBr-. Based on this, a new ECL method with highly sensitivity and simplified manipulationwas established for the determination of Ketotifen Fumarate. Under the optimumexperimental conditions, the RSD for6times determination of1.00×10^-5mol/L KetotifenFumarate was4.71%. The ECL intensities had good linear relationship with theconcentration of the Ketotifen Fumarate in the range of1.00×10^-41.00×10^-7mol/L, andthe linear regression equation was obtained as follows: I（counts）=173.24×10⁶C+188.15（R2=0.9989）. The detection limit （S/N=3） was7.81×10-10mol/L. The results of recoverywere between99.5¹05.0%, with the RSD2.32%. This proposed method showed highselectivity, sensitivity, the sensitivity, and the disposal method of the sample was simple.A gold electrode modified with a self-assembled monolayer of penicillamine wasprepared. The cyclic voltammetric and ECL behaviors of Sulpiride-[Ru（bpy）₃]²⁺systemwas studied on the PCA/SAM/Au electrode. The results showed that Sulpiride wouldlead to an efficient enhancement of ECL intensity of [Ru（bpy）₃]²⁺on the PCA/SAM/Auelectrode. Under the optimum experimental condition, the enhanced ECL intensities wereproportional to the concentration of Sulpiride in the range from1.00×10^-7mol/L to1.00×10^-4mol/L, with a detection limit of4.90×10^-9mol/L. The linear regressionequation was obtained as follows: I（counts）=32.091×10⁶C+35.654（r=0.9972）. Moreover,this modified gold electrode was also characterized by excellent repeatability, showing arelative standard deviation of3.20%for ten successive measurements of1.00×105mol/LSulpiride. The results of recovery test were between98.5¹07.5%, and the RSD ofrecovery test （n=5） was3.40%. This penicillamine modified gold electrode was useful todetect the Sulpiride with a satisfactory result.