Study On The Confinement Properties Of Ru（bpy）₃²⁺ And Its Application

Nano-cavity material is a kind of nanomaterial containing nano-cavity structure. Nano-cavity material is considered as model materials for the study of atoms or molecules in confined space. On the other hand, nanomaterials built up based on nano-cavity material commonly exhibit the unique properties due to confinement effect. The performance of these nanomaterials is affected by the properties of nano-cavity materials, the interaction between nano-cavity materials and confined molecular, and the properties of confined molecular. As these issues to be addressed, the present thesis using Ru(bpy)32+as a model molecular focus on preparing the stable nano-cavity materials, exploring the interaction between nano-cavity material and confined Ru(bpy)32+molecular, and the properties of confined Ru(bpy)32+molecular. the following researches have been carried out.1. Ru(bpy)32+/graphene composites with enhanced solid-state electrochemiluminescent (ECL) efficiency for sensitive immunosensorThis part of the work describes a novel strategy to fabricate a solid-state ECL immunosensor based on Ru(bpy)32+/3,4,9,10-perylenetetracarboxylic acid (PTCA)/graphene nanocomposites (Ru-PTCA/G). It is found that immobilization of PTCA and reduction of GO can be simultaneously achieved in one-pot synthesis method, forming PTCA/G nanocomposite. Further covalent attachment of derivative Ru(bpy)32+to the PTCA assembled on graphene sheets produces the functional Ru-PTCA/G nanocomposite which shows good electrochemical activity and ca.21times higher luminescence quantum efficiency than the adsorbed derivative Ru(bpy)32+. The Ru-PTCA/G nanocomposite based solid-state ECL sensor exhibits high stability toward the determination of tripropylamine (TPA) coreactant. In addition, a new ECL immunosensor based on steric hindrance effect is fabricated by cross-linking a-fetoprotein antibody (anti-AFP) with chitosan covered on Ru-PTCA/G composites modified electrode for detection of cancer biomarker AFP. The ECL immunosensor shows an extremely sensitive response to AFP in a linear range of5pg·mL-1-10ng-mL-1with a detection limit of0.2pg-mL-1.2. Highly stable and luminescent Ru(bpy)32+/LDHs interlayer restricted nanospace materials for sensitive detection of TNT explosiveIn this part, layered double hydroxides (LDHs) intercalated with of the carboxyl groups derivative Ru(bpy)32+(Ru/LDHs) are prepared via ionic-exchange way. The resultant Ru/LDHs composites exhibit lower than100nm scale particles and retain high ordered layer state. The thermal stability of derivative Ru(bpy)32+increases largely by ca.70℃, its photo stability increases by ca.3times, luminescence luminescence quantum efficiency increases by ca.1.7times, and lifetime also increases by ca.1times. These results are probably due to protecting the intercalated derivative Ru(bpy)32+by the rigid host structure and the interaction between cationic layers and derivative Ru(bpy)32+anion via dominant electrostatic and hydrogen band. Combined with high surface area and good adsorption capacity of LDHs, a new platform based on fluorescence quenching effect is fabricated for high sensitive detection of TNT with a detection limit of4.4μM.3. Preparation and characterization of Ru(bpy)32+/SiO2nanopore/channel restricted nanospace materialsPhenanthroline containing silicone group (Phen) was firstly synthesized. Using surfactant molecules as s template, different pore sizes of Phen-mesoporous silicas were prepared containing via co-condensation method. Further coordination reaction by Ru(bpy)2Cl2and Phen-mesoporous silicas produced a series of Ru(bpy)32+/Si02(Ru@SiO2) nanopore/channel materials, which pore sizes were2.64,5.15and7.42nm, respectively. The structures and morphologies of these materials were then characterized and specific behavior of Ru(bpy)32+were researched by using various analysis techniques. The experimental results show that Ru(bpy)32+molecules with uniform dispersion were decorated on the inner surfaces of the mesoporous silicas, its photo stability and luminescence quantum efficiency improved significantly, and changed with different pore size.