| The functional modified of calixarene has been playing an important role in the research process of calixarene chemistry. In this dissertation, we have synthesized ten kinds of new calix[4]arene derivatives and thiacalix[4]arene derivatives containing thiadiazole functional groups at lower rims, and confirmed the structures and the conformers of them. At the same time, the synthesized calix[4]arene derivative were modified on the electrode surface by the Langmuir-Blodgett(LB) film techniques as a new type of voltammetric sensor. The electrochemical properties and the recognizing mechanism of the film for silver ion were researched. A new stripping voltammetric method for determining of Ag～+ was erected. The main work and results are summarized as following:1. Synthesis and Characterization of p-tert-Butylcalix[4]arene Derivatives Containning Thiadiazole Functional Groups at Lower RimsThe p-tert-butylcalix[4]arene (compound 1) was firstly alkylated with 1,2-dibromoethane and 1,3-dibromopropane to get two kinds calix[4]arene derivatives (compound 2 and 3) in the presence of potassium carbonate, respectively. Six p-tert-butylcalix[4]arene derivatives (compound 4a～4c, 5a～5c) which append thiadiazolidinyl groups at the lower rims were easily synthesized with good yields by the reaction of compounds 2 or 3 with 2-mercaptothiadiazole. All new compounds were characterized by 1H NMR, 13C NMR, IR, MS spectra and elemental analysis.2. Synthesis and Structure of p-tert-Butylthiacalix[4]arene Derivatives Containning Thiadiazole Functional Groups at Lower RimsThe p-tert-butylthiacalix[4]arene (compound 6) was firstly alkylated with methyl iodide to obtain thiacalix[4]arene derivatives (compound 7), and which reacted with 1,2-dibromoethane and 1,3-dibromopropane to get two kinds thiacalix[4]arene derivatives (compound 8 and 9) in the presence of potassium carbonate, respectively. Four p-tert-butylthiacalix[4]arene derivatives (compound 10a～10b,11a～11b) which append thiadiazolidinyl groups at the lower rims were easily synthesized with good yields by the reaction of dibromoalkoxythiacalix[4]arene intermediates 8 or 9 with 2-mercaptothiadiazole in the presence of potassium carbonate. All new compounds were characterized by 1H NMR, 13C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene derivatives 8 and 10a were identified by X-ray analysis.3. Electrochemical Properties of Electrode Modified with Langmuir-Blodgett Film of p-tert-Butylcalix [4]arene Derivatives and Its Application in Determining of SilverThe glassy carbon electrode modified with Langmuir-Blodgett film of 5, 11, 17, 23 -tetra -tert-butyl-25, 27-di(3-thiadiazole -propanoxy)-26, 28-dihydroxycalix[4]arene (LBTZCA-GCE) was prepared. As a new type of voltammetric sensor, the electrochemical properties of LBTZCA-GCE were researched in detail and its recognizing mechanism for silver ion in aqueous solution was discussed. Using this voltammetric sensor, a new stripping voltammetric method for determining of Ag+ was erected. In 0.1 M HNO3 solution, the LBTZCA-GCE shows linear voltammetric response for silver ion in the range of 2×10-8～1×10-6 M. The detection limit is 8×10-9 M at accumulation time of 180s. By this method, real samples (lake water, tap water and synthesis sample) were analyzed and the results obtained were well satisfactory. |
