Study On The Synthesis And Character Of Five New Calixarene Derivatives And Their Application In ElectroanalyticalChemistry

Because of the simple synthesis and the especial structure, calixarene has been a kind of star supermolecule. Especially, the functional modification of calixarene plays an important role for extending their quality and application of calixarene. In this dissertation, we have synthesized five kinds of new calix[4]arene derivatives containing heterocycle thiadiazole functional groups tethered by ether bridges at lower rims. New compounds were characterised by techniques and the structures of molecule were confirmed. The electrochemical behavior and the forming LB film properties of five new calix[4]arene derivatives(CA)were investigated by electro-chemical methods and Langmuir-Blodgett(LB)film techniques.The synthesized calix[4]arene derivative was modified on the electrode surface by the LB film teniques as a new voltammetric sensors for Ag+. A new stripping voltammetric method for recognizing and determining of trace of Ag+ was researched. The main work and results are summarized as following:1. Five 2-(2-heterocycle-2-ylthio)ethoxy)ethanols 1a～1e were prepared by the reaction of 2-(2-chloroethoxy)ethanol and 2-mercapto-heterocycles using sodium iodide as catalyst. Consequently, the compounds 1a～1e reacted with tosyl chloride to afford corresponding tosylates 2a～2e. A series of p-tert-butylcalix[4]arene derivatives 3a-3e which contain heterocycle functional groups tethered by ether bridges were synthesized by the reaction of p-tert-butylcalix[4]arene with 2a-2e in the presence of potassium carbonate, respectively. All new compounds were characterized by 1H NMR, 13C NMR, IR, MS and elemental analysis. Meanwhile, the structures of calix[4]arene derivatives 3a,3b and 3d were identified by X-ray diffraction analysis.2. The electrochemical behaviors of five new CAs were investigated by electrochemical methods. The supporting electrolyte was tetrabutylammonium perchlorate (TBAP,0.2 mol/L) with chloroform as the organic solvents. In the potential range of 0.6～1.6V, the electrochemical properties of five CAs are similar. They all have two oxidative peaks with peak potentials of about 1.4 V and 0.8 V respectively and a reductive peak with peak potential of about 0.4 V. The dynamics parameters of oxidative peaks with peak potentials of about 1.4 V were investigated by cyclic voltammetry (CV). The properties of forming LB film of five new calix[4]arene derivatives were investigated and the effect of different heterocycle functional groups on forming LB film were discussed.3. The glassy carbon electrode (GCE) modified with LB film of CA(LBCA-GCE) was prepared. Theπ-A isotherms of the LB films suggested that the monolayer of CA can coordinate with Ag+ at the air-water surface. Using the LBCA-GCE as a new voltammetric sensor, a new stripping voltammetric method for determining of Ag+ was erected. The LBCA-GCE shows linear voltammetric response for Ag+ in the range of 1×10-8～6×10-6 mol/L and the detection limit is 1×10-10 mol/L. In addition, the recognition mechanism for Ag+ was discussed. From the analysis of real samples (lake water, tap water and synthesis sample), the results obtained were satisfactory.