Sensors Based On Novel Immobilization Methods Of Tris(2,2’-bipyridyl)Ruthenium(Ⅱ)

Electrochemiluminescence (ECL) is a technology that combines traditional electrochemistry and chemiluminescence (CL). It not only has the characteristics of CL like high sensitivity, simple apparatus and wide linear range, but also owns merits such as good controllability and multi-informational acquisition. So it is now becoming a widely used analytical tool. Among all ECL system, Ru(bpy)32+(or its derivatives) is the most widely used due to the simple mechanisms, high ECL efficiency and good solubility in both aqueous and organic solutions. Although traditional Ru(bpy)32+ECL systems are generally based on reactions in liquid phase (esp. aqueous solution), solid-state ECL sensors based on the immobilization of Ru(bpy)32+have advantages of saving reagents, reusability, high ECL intensity, etc. Therefore, study on the different immobilization methods of Ru(bpy)32+is of vital importance to the applications of Ru(bpy)32+modified electrodes.Based on the discussion above, the main work of this thesis is summarized as follows:1. Based on thiol-ene "click" reaction, a solid-state ECL sensor was constructed by the immobilization of Ru(bpy)32+. Alkenyl functionalized Ru(bpy)32+derivative Ru’was synthesized and characterized, and it was sucessfully immobilized on indium tin oxid (ITO) substrate pretreated with mercaptopropyltrimethoxysilane (MPTMS) through thiol-ene "click" reaction. The silianization treatment and "click" reaction time were optimized. The ECL response of the modified electrode to tertiary amines was investigated using tripropylamine (TPA) as a model analyte. The fabrication of the sensor was simple, fast and efficient. The sensor exhibited excellent stability in organic solvent, and satisfactory ECL behavior to TPA, indicating its potential application as the ECL detector in liquid chromatography or capillary electrophoresis.2. Based on electrodeposition technology, Ru(bpy)32+was directly modified at the carbon nanotubes (CNTs) modified glassy carbon electrode (GCE) surface, and an electrochemical sensor for the detection of tertiary amines was constructed. It has been found that the presence of CNTs on GCE surface enhanced the electrochemical activity of immobilized Ru(bpy)32+. The potential cycle number for the electrodeposition process was optimized. Amperometric detection was employed to verify the sensor’s response using TPA as a model analyte. Then the modified electrode was used for the amperometric determination of a herbicide (flufenacet), and preferable response signals and linear range were obtained.