杯[4]芳烃基超分子凝胶创制中的主客体作用

Calixarenes, as the third generation of supramolecular host, possesshydrophobic cavities and could interact with various anions, cations and neutral molecules. The molecular recognition and assembly of calixareneshave become one of hot topics in thesupramolecular gel field. In recent years, novel stimuli-response supramolecular gels based on the calixarenehost have been developed and brought new life to the study of supramolecular gels. The studies will mainly be focused on: 1) design and synthesis of a series of novel supramolecular gels based on gelators with calix[4]arene and pyrene, ferrocene as the main components; 2) investigations of the host-guest interaction of the derivatives of calixareneswith some guest anions, cations and neutral molecules, as well as the stimuli-responsiviness of the supramolecular gels and the viscous solutions based on the gelators as created. It is believed that the introduction of pyrene and calix[4]arene will greatly affect the dissolution and assembly of the compounds as created, and thereby makes the host-guest interaction, the stimuli-responsiveness and visicosity control possible.Based on the results as expected, development of new effective extraction/separation systems will be highly possible. No doubt, the research as planned will provide a deeper understanding of in the host-guest chemistry of calixarene, and promote the practical applications of calix[4]arene.

杯芳烃作为第三代超分子主体拥有可调节的疏水空腔，可和多种离子、中性分子发生主客体作用，杯芳烃的分子识别和组装研究成为超分子领域的热点之一。本项目拟以杯[4]芳烃与芘、二茂铁的主客体作用制备新型超分子凝胶为目标，设计、合成特定结构新型含芘，二茂铁杯[4]芳烃衍生物；研究新型含芘、二茂铁的杯[4]芳烃衍生物的分子间主客体作用、溶液行为；构建新型含芘、二茂铁杯[4]芳烃衍生物的刺激响应性物理凝胶和粘度可控体系等。预期芘、二茂铁和杯[4]芳烃的引入将会极大地影响胶凝剂的溶解性和聚集行为，为杯[4]芳烃主客体作用创造机会，从而为刺激响应性凝胶材料，特别是剪切响应性凝胶材料和粘度可控体系的构建提供可能，为新的高效萃取分离体系创制奠定基础，为揭示杯芳烃类凝胶形成机制积累素材。毫无疑问，本项目的开展不仅可以深化对杯[4]芳烃主客体化学的认识，丰富杯[4]芳烃主客体化学内容，还可推进杯[4]芳烃的实际应用。

杯芳烃作为第三代超分子主体拥有可调节的疏水空腔，与多种离子、中性分子发生主客体作用，杯芳烃的分子识别和组装研究成为超分子领域的热点之一。本项目以杯[4]芳烃、芘、胆固醇单元为主要片段合成了含芘、二氨基、苯丙胺、三氮唑的新型杯[4]芳烃衍生物并进行了核磁和质谱的结构检测；研究新物质的溶液行为：含芘、二氨基、胆固醇的杯[4]芳烃衍生物和不同手性的苯丙胺三氮唑新型杯[4]芳烃胆固醇衍生物在常温不能胶凝任何一种常用溶剂。D-苯丙胺的三氮唑新型杯[4]芳烃胆固醇衍生物的丁醇溶液比较粘稠，在体系中加入四丁基磷酸二氢铵，浓度大于1.5%(w/v)，温度为42-48°C，超声作用下形成稳定可逆的超分子凝胶。核磁研究表明磷酸二氢根离子与杯[4]芳烃下沿的氢及氧作用有效调整了D-苯丙胺的三氮唑新型杯[4]芳烃胆固醇衍生物的构象结构，释放出了多个超分子作用位点，有效促进构建了新型杯[4]芳烃衍生物的刺激响应性软物质和粘度可控体系。不同浓度的流变学研究表明凝胶的机械强度随着胶凝剂浓度的增大而增强；干凝胶形貌研究表明D-苯丙胺的三氮唑新型杯[4]芳烃胆固醇衍生物首先形成线状组装体，随着浓度增加线状组装体肩并肩形成粗的聚集体，聚集体搭建成网络结构；在D-苯丙胺的三氮唑新型杯[4]芳烃胆固醇衍生物/丁醇四丁基磷酸二氢铵的凝胶体系中四丁基铵根阳离子和呋喃噻咪唑阴离子形成了新药物共晶体，与两种物质在丁醇溶液中对比有效提高了药物晶体生长浓度。总之，本项目的开展研究了有效构建了杯[4]芳烃衍生物的可控超分子凝胶体系，为新的高效萃取分离体系的创制奠定了基础，为呋喃噻咪唑的新型晶体生长提供了新的介质，优化药物晶体生长的条件，推进了杯[4]芳烃及超分子凝胶的实际应用。