【作者】 王璐；

【导师】 冶保献； 赵邦屯；

【作者基本信息】 郑州大学 ， 分析化学， 2007， 硕士

【摘要】 杯芳烃的功能化修饰是目前杯芳烃化学研究的热点之一。本论文将含有氮、硫杂原子的2-巯基-1，3，4-噻二唑引入到母体杯[4]芳烃及硫桥杯[4]芳烃中，合成了10种新的杯[4]芳烃衍生物。对合成的新化合物用多种手段进行了表征，确定了其分子结构和构象。同时，将所合成的杯[4]芳烃衍生物以整齐、有序的LB膜形式修饰到电极表面，制作了新的杯芳烃LB膜修饰电极。作为一种伏安传感器，研究了其本身的电化学性质和对Ag⁺离子的选择性识别，建立了测定痕量Ag⁺的电化学阳极溶出伏安分析方法。论文具体包括以下几个方面的内容：1．含噻二唑基的对叔丁基杯[4]芳烃衍生物的合成与表征以对叔丁基杯[4]芳烃（化合物1）为原料，分别与1，2-二溴乙烷、1，3-二溴丙烷在碳酸钾的存在下进行选择性烷基化反应，得到了两种杯[4]芳烃衍生物（化合物2和3）。在氢氧化钠存在下，化合物2和3与过量的含不同官能团的2-巯基噻二唑反应，合成了六种下缘含噻二唑基的杯[4]芳烃衍生物（化合物4a～4c，5a～5c），其结构用¹H NMR，¹³C NMR，IR，MS和元素分析等表征手段进行了确证。2．含噻二唑基的对叔丁基硫桥杯[4]芳烃衍生物的合成及结构以对叔丁基硫桥杯[4]芳烃（化合物6）为原料，在碳酸钾存在下与碘甲烷反应，生成1，3二取代硫桥杯[4]芳烃（化合物7），其分别与1，2-二溴乙烷、1，3-二溴丙烷在碳酸钾的存在下进行烷基化反应，得到两种硫桥杯[4]芳烃衍生物（化合物8和9）。在碳酸钾存在下，8和9分别与过量的含不同官能团的2-巯基噻二唑反应，合成出了四种下缘含噻二唑基的硫桥杯[4]芳烃衍生物（化合物10a～10b、11a～11b），并通过了¹H NMR，¹³C NMR，IR，MS和元素分析等方法对目标化合物进行了确证。同时，X-射线分析确定了硫桥杯[4]芳烃衍生物8和10a的晶体结构。3．含噻二唑基的对叔丁基杯[4]芳烃衍生物LB膜修饰电极的电化学性质及对银离子的识别应用利用自己合成的硫桥杯[4]芳烃衍生物—25，27-二（3-噻二唑基硫代丙氧基）-26，28-二羟基-5，11，17，23-四叔丁基杯[4]芳烃（TZCA）和LB膜技术，制作了新的杯芳烃LB膜修饰玻碳电极。作为一种新型的电化学伏安传感器，详细研究了该化学修饰电极的电化学性质和它在水溶液中对银离子的识别以及分析应用。建立了一种新的识别银离子的溶出伏安分析方法。在0.1 M HNO₃支持介质中和富集时间为180s下，银离子响应的线性范围为2×10^-8～1×10^-6 M，检测限达8×10^-9 M。我们用这种方法分析了实际水样（湖水，自来水和合成水样），得到了令人满意的结果。更多还原

【Abstract】 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 (LB_TZCA-GCE) was prepared. As a new type of voltammetric sensor, the electrochemical properties of LB_TZCA-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 LB_TZCA-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.更多还原