杯芳烃衍生物分析及其色谱保留机理的量子化学研究

【作者】 李勇波；

【导师】 张书胜； 刘红霞；

【作者基本信息】 郑州大学 ， 分析化学， 2007， 硕士

【摘要】 杯芳烃作为第三代主体分子，与环糊精和冠醚相比，更容易进行化学修饰，可广泛的应用于主-客体化学的研究与应用领域。利用主体分子的分子识别功能提高分离选择性是色谱分离材料研究的重要课题，杯芳烃在色谱分析领域的应用主要为流动相或背景电解液的添加剂和色谱固定相的制备。本论文主要包括苯甲酰基杯芳烃的合成、杯芳烃混合物的色谱分离研究和杯[4]芳烃键合硅胶色谱柱上色谱分离行为的量子化学研究等三部分内容：1．合成了苯甲酰基杯[4，6，8]芳烃，并通过红外光谱、核磁共振、质谱和液相色谱验证了其结构和纯度。2．分别在C18柱、CN RP柱、NH₂柱和LC-318柱上，对杯芳烃及其衍生物的色谱行为进行了比较研究。杯[4，6，8]芳烃在C18柱上10 min可达到基线分离；25-乙氧基杯[4]芳烃、杯[4]芳烃、对叔丁基杯[4]芳烃在C18柱上，采用甲醇-水梯度洗脱可达到基线分离；对叔丁基杯[4，6，8]芳烃在C18柱和LC-318柱上，使用乙腈／氯仿流动相，可以达到基线分离。3．采用量子化学方法对多种物质在DBS4柱上的色谱行为进行了研究，发现DBS4固定相与被分离物之间的作用力不但有π-π作用、包结作用、疏水作用和范德华力，还存在与溶质体积相关的阻力，流动相对溶质的溶解作用也是影响色谱分离的重要因素。更多还原

【Abstract】 As a typical representative of the third generation of supramolecules, calixarenes are more easily to be chemically modified than CDs and crowns. Calixarenes have being widely studied and applied in host-guest chemistry because their interactions between calixarenes and guests exist based on many kinds of modes and mechanisms. It is an important task to improve the separation selectivity of calixarene materials using the host molecule’s recognition functions. In separation science, it has been widely used as the mobile phase additive, bonded stationary and capillary inner-wall modifier. This paper systemically introduced the synthesis of benzoyl hexahydroxy calixarene, the separation of calixarene derivatives and the quantum chemistry study of the separation behavior of the solutes on the calix[4]arene-bonded silica stationary phase. The summary of the thesis is as follows:1. para-Benzoyl hexahydroxy clixarenes synthesized and characterized by IR, NMR and MS methods. The purity was determined with more than 98% by HPLC.2. The separations of calixarene derivatives have been investigated using C18 column, CN RP column, NH₂ column and LC-318 column respectively. With C18 column and MeOH mobile phase, calix[4-8]arenes could be well baseline separated within 10min. Using C18 column, with a mobile phase of MeOH/H₂0, 25-ethoxycalix[4]arene, calix[4]arene and p-tert-butylcalix[4]arene could be baseline separated with gradient elution. Using NH₂ column and MeCN mobile phase, p-tert-butylcalix[4-8]arenes were baseline separated within 10 min at 0.8 ml/min.3. The quantumn chemistry study of the separation behavior of the analytes in the DBS4 has carried out. The results display that the interactions between DBS4 and solutes not only includeπ-πinteraction, inclusion interaction, hydrophobic interaction and van der waals forces, but also include the hindrance hindrance related to the volume size of solute molecules. The mobile phase solvent can affect chromatography separation through the analytes’ solubility.更多还原