Study And Application On Electrochemiluminescence Of Ruthenium (Ⅱ) And Its Complexs

In this thesis, the principles, main reaction systems, mechanism and the application of electrochemiluminesence (ECL) were reviewed. New methods based on SI-ECL have been developed for determining hydroxyurea, spermine and NO. The work was summarized as follows:1. The development of a sequential injection electrochemiluminescence(SI-ECL) method for the determination of hydroxyurea and spermine. It is based on the facts that hydroxyurea could inhibit the ECL of Ru(bpy)₃²⁺ and spermine could enhance the ECL of Ru(bpy)₃²⁺. Under the optimal conditions, the determination of hydroxyurea: a linear range of 2×10^-61×10^-3 mol/L was derived along with RSD values of 1.0% at 2×10^-6 mol/L, and a detection limit of 3.63×10^-7 mol/L was achieved; the determination of spermine: a linear range of 5×10^-75×10^-4 mol/L was derived along with RSD values of 3.0% at 5×10^-7 mol/L, and a detection limit of 3.03×10^-7 mol/L was achieved. The recoveries were in the range of 94.9%¹08.6% for the determination of hydroxyurea in hydroxyurea tablet, human blood serum and urine samples.2. A novel ECL sensor with high sensitivity and long-term stability was prepared by immobilizing Ru(bpy)₃²⁺ on the surface of Chitosan/MCM-41 composite films modified Pt electrode via an ion-exchange process and their electrogenerated chemiluminescence were investigated.The experimental results showed that the immobilized Ru(bpy)₃²⁺ maintained its electrochemistry behaviors very well. The modified electrode showed a fast ECL response to TprA. Meanwhile, the modified electrode was applied to the detection of hydroxyurea and spermine. The electrode could be easily regenerated and exhibited good stability which make it a promising candidate for sensitive electrochemical sensors for hydroxyurea and spermine.3. A ruthenium(II) complex based turn-on ECL probe for the detection of nitric oxide and turn-off ECL probe for the detection of hydroxyurea. A selective and sensitive ECL method for the detection of NO in aqueous and biological samples using a modified Ru(bpy)₃²⁺ complex, [Ru(bpy)₂(dabpy)]²⁺, as a probe was described. Compared to the reported ECL quenching method, the new ECL enhancement method has the advantages of higher selectivity and sensitivity, and wider linear range, which allows it to be favorably useful for the ECL detection of NO in complicated biological samples. Additionally, the ECL probe was successfully applied to the detection of hydroxyurea. Under the optimal conditions, a linear range of 2×10^-65×10^-4 mol/L was derived along with RSD values of 3.7% at 2×10^-6 mol/L. The recoveries were in the range of 95.6%¹09.2% for the determination of hydroxyurea in hydroxyurea tablet, human blood serum and urine samples.