基于环糊精-金刚烷主客体作用构筑低聚表面活性剂的聚集行为研究

Surfactant is an important part of the main branch of fine chemical industry and the national economy. In recent years, the exploration and synthesized of oligomeric surfactant with high surface activity and rich morphology aggregate has been an interesting problem. According to the problem that it’s difficult to synthesis oligomeric surfactant with high multimer, which has been limiting its development, β-cyclodextrin (β-CD) and adamantane as the host - guest recognition molecule will be introduced to the synthesis of oligomeric surfactant with the idea of constructing supramolecular surfactants by using non covalent interactions. Studies on building oligomeric surfactant system with high multimer and exploring its preparation method will be carried on using host-guest inclusion complex between oligomeric surfactant based on adamantane and oligomeric β-CD. Systematic research on the surface activity and aggregation behavior of oligomeric surfactant will reveal the relationship of structures and properties of oligomeric surfactant. And the general rules and methods for the construction of oligomeric surfactant by host-guest interaction are presented. What’s more, Dissipative particle dynamics simulation method (DPD) will be used to investigate aggregation behavior of the surfactant which can explain the mechanism of the formation of aggregates from the micro level based on the experimental results and it also will provide technical support and guidance for the application of surfactant based on adamantane and cyclodextrin in the fields of colloid and interface chemistry, food, medicine and etc.

表面活性剂是精细化工的主要分支和国民经济重要组成部分，近年来探索并合成具有高表面活性、聚集体形态丰富的低聚表面活性剂一直是人们感兴趣的课题。本项目针对高聚合度的低聚表面活性剂合成困难而限制其发展的问题，利用超分子间非共价键相互作用来构筑超分子表面活性剂的思想，将β-环糊精与金刚烷这对主客体识别分子引入到低聚表面活性剂的合成中，利用金刚烷基表面活性剂多聚体与β-CD多聚体进行主客体包合，构筑聚合度倍增的低聚表面活性剂体系，探索制备高聚合度低聚表面活性剂的新方法。对低聚表面活性剂的表面活性和聚集行为进行系统性研究，揭示低聚表面活性剂的结构与性能构效关系，提出主客体作用构筑低聚表面活性剂的一般规则和方法。并利用耗散颗粒动力学模拟方法（DPD）研究表面活性剂的聚集行为，结合实验结果从微观层次阐明聚集体形成的机制，为环糊精-金刚烷构筑表面活性剂在胶体与界面化学、食品、药物等领域提供技术支撑和指导。

表面活性剂广泛应用于日常生产生活及高新技术领域，是重要的精细化工产品。近年来非共价键构筑的超分子表面活性剂逐渐成研究热点。本项目利用超分子间非共价键相互作用来构筑超分子表面活性剂的思想，将β-环糊精与金刚烷这对主客体识别分子引入到表面活性剂的合成中。我们设计并合成了两种β-CD二聚体（bisβ-CD 和sti bisβ-CD）“主体”分子，还合成并鉴定了三种金刚烷基二聚型表面活性剂（Ad-bis12、Ad-ph-bis12和Ad-pame-bis12）和四种金刚烷基单链表面活性剂（Ad-12、AdP-12、C11AD和AD-C11im）“客体”分子。基于环糊精与金刚烷基表面活性剂C11AD、金刚烷基离子液体AD-C11im主客体作用，构筑了两种类型的Bola型表面活性剂和超分子凝胶，研究了环糊精-金刚烷主客体作用对C11AD和AD-C11im聚集行为的影响。通过氢谱、2D ROESY氢谱和直观的泡沫性能研究环糊精与金刚烷基表面活性剂的主客体相互作用情况，采用表面张力法和电导率法、TEM、Cryo-TEM、SEM和DLS等方法研究了β-环糊精对C11AD和AD-C11im在主客体相互作用下的聚集形态转变的行为。此外，利用环糊精二聚体bisβ-CD“主体”与金刚烷基表面活性剂AdP-12“客体”、与金刚烷基二聚表面活性剂Ad-bis12“客体”，按照主客体相应的摩尔比1:2进行溶液配置，分别构筑出二聚、四聚表面活性剂的溶液体系。研究发现，构筑的二聚、四聚表面活性剂均比原“客体”具有更低的临界胶束浓度CMC值，符合低聚表面活性剂的特性。随着浓度的变化，二聚体系bisβ-CD@2AdP-12在水溶液中可以聚集形成规整的分散性球形囊泡和不规则的中空纳米管状结构。四聚体系bisβ-CD@2Ad-bis12在水溶液中聚集形成蠕虫状胶束和球形囊泡，显示出低聚表面活性剂具有丰富的聚集形态和优异的自组装能力，本研究所得结果为金刚烷-环糊精构筑表面活性剂在胶体与界面化学、食品、药物等领域提供技术支撑和指导。相关研究成果已发表学术论文9篇（其中SCI收录论文8篇），申请国家发明专利5项。