基于超分子作用的手性翻转精准调控

Presice control over chairility conversion of optical mateirals remains a significant chanllenge. This project starts from chiral molecules that are abundent in nature to create chariality conversion in bulk materials of hydrogel and liquid crystal with the help of host-guest chemistry and coordination chemistry. By employment the host-guest chemisty of cyclodextrins that display guest position dependent chirality, we are able to achieve the chirality conversion in self-assembled liquid crystal based on the host-guest supramolecules by controlling the exchanging dynamics between the guest in and out the cavity of cyclodextrins; which can be further made into enzyme and photo responsive chirality conversion owing to the enzyme and light triggered change of molar ratio between the guest conversion . We are also able to control the chirality conversion in hydrogels by using the metal coordination interaction, which triggers the conformational change of the coordinating molecule. Since both the host-guest formation and the coordination triggered molecular conformation can be theoritically calculated either with Molecular Dynamics or quatum chemsitry calculation, we expect to achieve precise control over the chirality of the macroscopic liquid crystal and hydrogel based on the chirality conversion at molecular level.

手性翻转的精准控制是手性材料研究领域面临的重要挑战。本项目拟从经典的环糊精及来源丰富的手性配位分子出发，通过主客体化学与配位化学精准调控超分子手性翻转，获得可宏量制备的手性凝胶、液晶等手性组装材料。利用客体分子在环糊精空腔内的嵌入深度不同对手性的影响，通过控制客体分子链的长短、客体分子交换动力学实现主客体系手性的精准控制；通过淀粉酶引起环糊精水解、光照导致客体异构等调控客体交换动力学，实现主客体系手性的动态控制；以及利用不同金属离子的配位场差异导致配体分子远程构型翻转，控制配位超分子凝胶体系的手性。分别通过分子动力学模拟及量子化学计算理论预测客体在环糊精空腔的结合位置以及配位引起的分子远程构象变化，在理论的指导下实现源于分子层次手性翻转的介观组装及宏观材料手性的精确控制。

"基于超分子作用的手性翻转精准调控"重大研究计划培育项目面向智能手性材料研究的前沿和挑战，从空间图像清晰的经典主客作用与配位作用出发，利用环糊精主客动力学、配位化学的空间效应，发展能够在外界刺激下发生手性翻转、信号响应的液晶、薄膜、凝胶等智能手性材料。3年来，项目严格按照计划执行，围绕既定研究目标开展工作。利用主客动力学实现了结晶自组装的手性翻转；利用配位化学的空间效应实现了介观自组装手性翻转；结合主客体动力学与配位组装，实现了主客动力学催化的配位组装对称性破缺和手性翻转控制，获得了具有先进防伪、显示功能的多模态手性可控圆偏振发光液晶、凝胶材料，并拓展了利用电荷密度匹配/失配变化调控静电组装薄膜材料的手性，首次在理论的指导下实现了自组装材料手性的理性控制。在Nature Communications, JACS Au, Angew. Chem. Int. Ed., ACS Nano等期刊发表研究论文14篇，申请中国发明专利一项。该研究建立了手性材料合成的新方法和新策略 ，实现了基于廉价易得工业原料的手性材料合成，为手性功能材料的规模化生产提供变革性技术，全面完成了研究目标。