不对称结构两亲分子有序聚集体的构筑与功能研究

Controlled assembling of organized molecular aggregates with asymmetric hierarchical structures in solution or at interface from the small amphiphilic building blocks is not only significant both from the theoretical and practical point of view, but also rich in challenge and opportunity as a research project. Motivated by the preliminary results we have tried, the research work now will be concentrated on the design and preparation of various covalent and supramolecular amphiphilic building blocks and the possibility to fabricate asymmetric hierarchical organized aggregate structures in different solvents or at interfaces. Various structural factors of the amphiphilic building blocks and their intermolecular interactions will be systematically studied using different assembling techniques to find their influences on the aggregate morphology. The tuning effects of environmental physical modulations on the aggregate structure and their synergetic properties will also be investigated. Efforts will be focused on seeking an effective way to produce asymmetric hierarchical organized aggregates and their reversible transitions. New characterization methods for such asymmetric aggregates will be explored. Meanwhile, the functionalities of fabricated aggregates and their enhancements on building block properties would be studied. The establishment and launching of this project is not only hopeful to find a novel method or path to effectively assemble the asymmetric hierarchical organized aggregates in a controlled manner, but also beneficial for better understanding on certain basic questions and rules in chemistry, life science and material field. The obtained results could provide more valuable information on the design and production of novel supramolecular materials.

利用小分子两亲基元在溶液或界面上可控组装具有不对称分级有序结构聚集体具有重要的理论意义和应用价值，是一项富有挑战性的研究课题。受前期初步研究结果启示，本项目拟通过共价和超分子两亲基元的设计与构建，在不同溶剂和界面上探求其形成不对称分级有序聚集结构的可能性。系统考察两亲基元分子结构内在因素、分子间相互作用及组装方式对聚集体形态的影响，以及外界环境因素对有序聚集结构及表观协同性能的调控作用。寻求有效构筑不对称聚集体的方法与途径，以及不对称聚集结构的有效表征手段，并考察不对称聚集体自身功能性和对单体两亲基元功能性的改进。本项目的设立与开展，不仅有望建立出可控制备不对称分级有序聚集结构的新方法和途径，而且可以加深对化学、生命科学、材料科学等领域基本问题和有关规律的更高层次的认识和理解，为新型超分子聚集材料的设计与构建提供有价值的信息。

不对称/分级有序聚集体的可控组装是新型超分子聚集材料设计与构建的重要途径，在化学、生命科学和材料科学等领域有重要的理论和实际意义。本研究借助环糊精包结、静电相互作用、动态亚胺键、氢键、金属配位和疏溶剂等非共价相互作用，选取甾醇分子、季铵盐类Gemini表面活性剂、脱氧胆酸钠、双尾链阴离子表面活性剂(AOT)、以及修饰有金刚烷/偶氮苯/二茂铁的两亲分子等为构筑基元，在水、离子液体和有机溶剂中，构建了各种结构与功能独特的分级有序聚集体。利用小角X射线散射、偏光显微镜、红外光谱、核磁共振、荧光光谱、扫描或透射电镜、原子力显微镜、激光共聚焦显微镜以及分子模拟等技术，探索了各种内外因素对聚集体结构形成的影响。研究发现，设计和构建不对称两亲基元，通过分子结构不对称信息的传递，可有效构筑分级结构有序聚集体。考察疏溶剂效应和氢键等在双相分级有序聚集体形成过程中的作用发现，保持各种组装驱动力之间的微细平衡起着非常关键的作用；而利用各种非共价相互作用力的多级简单组装，也是分级有序聚集体形成的重要途径。构筑基元及溶剂的结构微调也会对有序聚集体的相行为产生很大的影响，形成独特的聚集体结构。初步尝试将稀土化合物引入到溶致结晶中，液晶的聚集结构对稀土化合物产生的束缚作用加强了稀土离子配位层的不对称性，进而有效地改善了其荧光特性。本研究所得结果对有效、可控制备不对称分级有序聚集体及功能材料具有较大的参考价值。相关研究成果已发表SCI收录论文22篇，其中影响因子大于3.0 的论文13篇。