新型温度响应型智能蠕虫状胶束体系构筑的相化学和热化学研究

Construction of new intelligent micelles is a hot field in self-assembly chemistry by the amphiphilic molecules with specific functions and properties.In this project, we intend to synthesize a series of hydroxyl-functionalized cationic surfactants. Binary/ternary phase diagram of the surfactant-water/surfactant-water-additive systems will be obtained by phase equilibrium research, which can be regarded as guidance to fabricate temperature- switchable intelligent micellar structures through multiple weak interactions. Online calorimetric curves for formation of wormlike micelles, micellar structure transformation and temperature-switchable processes of intelligent mecellar systems will be determined by utilizing microcalorimetry, and thermodynamic and kinetic parameters for the processes will be obtained by data process of the calorimetric data according to thermodynamic and kinetic equations. Structure-activity relationship between the aggregate structures and the important factors, including molecular structures of surfactants, countra-ion and additives, are to be systemically investigated by combining the thermodynamic and kinetic properties with the rheological,electron microscopic and light scattering technologies.The micellar formation mechanism, the microstructure of the intelligent micelles, the rule of micellar structure transition induced by temperature, and the effects of additives on the structure formation will be explored. These research works can reveal the interaction mechanism between the molecules in the process of intelligent micelle formation, and the synergistic interactions of various non-covalent forces from the point of view at molecular level, establish the new supramolecular structures and widen the type of and the function of assembly and deepen the understanding about the basic issues and related laws in the supramolecular chemistry and self-assembly field, which is quite useful and of great importance.

以具备特定功能和性质的两亲分子构筑新的智能胶束是聚集体化学研究的热点之一。本项目拟合成系列羟基功能化的阳离子表面活性剂，通过表面活性剂-水和表面活性剂-水-添加剂相平衡研究，得到二元和三元相图，在相图指导下利用分子间多重弱相互作用构筑温度调控的智能型蠕虫状胶束体系。以微量热为主要研究手段，测定智能型蠕虫状胶束形成、结构转化及温度调控过程的在线量热曲线，通过热动力学方程得到过程的热力学和动力学参数。结合流变、核磁、电镜、光散射等技术，系统考查温度调控下智能胶束的构筑与表面活性剂分子结构、反离子以及添加剂之间的构效关系；探索智能胶束的构建机制、微观结构、温度诱导的结构演变及添加剂对胶束形成的影响规律。这对从分子水平揭示智能胶束形成过程中分子间相互作用机理及不同非共价键力的协同效应，对建立新型超分子结构、拓宽组装体类型和功能，加深对超分子化学和自组装领域中基本问题和有关规律的了解具有重要意义。

合成了五类价格低廉、毒性较低、性能优良的含有温敏性基团（烷氧羟丙基）的单、双链季铵盐阳离子表面活性剂并进行了结构表征。系统开展了系列温敏性蠕虫状胶束体系（TSWMS）的构筑及性能研究。首先用不同表面活性剂分别与不同添加剂组分组成多元体系并绘制二元(表面活性剂/水或三元（表面活性剂/水/添加剂）相图，确定了温敏型胶束存在的组成区域。在相图指导下构筑了温度调控的多系列智能温敏型蠕虫状胶束体系。以量热为主要研究手段结合流变性能测试、低温透射电子显微镜、核磁共振光谱、小角X衍射以及紫外、荧光光谱等微观结构探测技术，参考表面活性剂分子聚集体的晶体结构数据，系统考查温度、主要组分浓度以及不同添加剂对此类体系热力学和动力学性质的影响规律。根据热化学基本原理和相关的计算公式，得到TSWMS在不同条件下形成、解离以及不同结构之间转化过程的热力学参数和微观数据信息，深入探讨了表面活性剂分子中功能基团、共存分子、反离子属性与TSWMS结构形成规律的内在联系。从微观角度诠释了TSWMS的形成和解离规律、胶束－胶束之间、胶束－凝胶之间的转化驱动力、分子间各种非共价键作用的协同机理以及外部条件对温度调控的影响，结合部分体系的分子动力学模拟，判断和预测TSWMS的形成趋势。该课题为丰富TSWMS研究内容、拓展TSWMS在药物控释，物相分离，生物高分子材料的掺杂、化妆品增稠以及油田增产等领域，实现低成本、高效率、低污染和能源利用最佳化提供了理论基础和实验数据。