基于环糊精超分子交联剂的大形变、自修复水凝胶

Supramolecular hydrogels based on inclusion complexation interactions are very important for the experimental and therotical studies on drug/gene loading and tissue engineering materials. The main objective of this project is to construct a divinyl functionalized host-guest pair，using monovinyl functionalized β-cyclodextrin monomer(β-CD-m)as host molecule and adamantane monomer (Ada-m) as gust molecule,based on the inclusion complexation interaction between β -CD and Adamantane.This host-guest pair can be further used as a supramolecular cross-linker instead of normal chemical cross-linkers due to the polymerizable vinyl groups attached on the host and guest molecules.Thus,a series of transparent supramolecular hydrogels can be obtained by compolymerization of this divinyl functionalized host-guest pair with many normal water soluble monomers through simple free-radicl copolymerization.Due to the dynamic revisible inclusion complexation interaction between Ada and β-CD and the relative slippage between the polymer chains cross-linked by supramolecular interactions, the obtained supramolecular hysrogels will have self-healing and highly stretchable properties. Additionally, because β-CD/Ada pair has competitive host(guest) stimuli responsive complexation-decomplexation behavior,and so the obtained supramolecular hydrogel are also expected to have competitive host(guest) stiumli responsive gel-sol transiton properties.

基于环糊精包结作用的超分子水凝胶对药物/基因载体及组织工程用材料研究 具有重要的理论和实际意义。本项目旨在以双键单取代的β-环糊精（β-CD-m）为主体分子， 以金刚烷单体(Ada-m)为客体分子，通过二者间的包结络合作用,构建双键功能化的双官能度主-客体作用对-β-CD-m/Ada-m。进而以β-CD-m/Ada-m 为超分子交联剂,通过简单的自由基共聚合反应，实现基于常见水溶性单体的透明超分子水凝胶的制备。利用β-CD/Ada 间的动态可逆包结络合作用及超分子相互作用力交联的聚合物链间的相对滑移,实现所制超分子水凝胶的自修复和良好的拉伸性能。同时，由于β-CD/Ada 包合物具有对竞争主(客)体的刺激响应性络合-解络合特性，预期所制超分子水凝胶也将具有竞争主（客）体的响应性凝胶-溶胶转变行为。

本项研究按照原计划书设计理念，以β-环糊精（βCD）为主体分子，以金刚烷单体为客体分子，通过二者间的包结络合作用来构筑新型超分子交联剂。进而通过简单的自由基聚合，制备抗拉伸、自修复的功能性超分子水凝胶。这里，我们通过β-环糊精单体的自由基聚合反应，制备了线型主体高分子pAOI-β-CD，进而以金刚烷单体（A-TG-Ada）为客体分子，通过与丙烯酰胺的简单自由基聚合反应，制备出了可超长拉伸、耐刺穿且具有抗缺口不敏感性和自修复功能的超分子水凝胶。提出了利用络合有客体分子单体的主体分子均聚物的在聚合前后的模版效应和动态可逆多价超分子交联剂的协同效应，制备功能性、高性能主客体超分子水凝胶的新思路。与此同时还以β-CD单体与端氨基修饰的PEG-PPG-PEG中PPG链段选择性包结络合作用，通过简单的扩链后的自由基聚合反应，制备出了一种新型的具有优良的拉伸增强和形变恢复性能的新型滑轮水凝胶。这些研究结果为高性能、功能性超分子软物质材料的分子设计和制备及应用研究提供了一定的支撑，对基于其它超分子相互作用的新型功能性软物质材料的研究也有一定的借鉴意义。