含手性基元的液晶聚合物的合成及自组装研究

Living organisms derive from the chiral substances, which determine their biological activities and functions. The study of polymers with chiral structures and their self-assembly is of great importance in understanding life phenomena and developing new functional materials. However, the related research in polymer science is rare, and the relationship between the chiral structures and self-assembly behaviors still need to be investigated. Introduction of chiral induction into the controlled self-assembly processes of polymers (e.g. CDSA, LCDSA) will provide a new way to explore the self-assembly behaviors of polymers in complex conditions, and lead to a further development of new polymers based chiral materials with the biomimetic functions. In this proposal, we intend to design and synthesize a series of liquid crystal polymers containing chiral units (e.g. amino acids or peptides), and explore the effect of chiral induction and liquid-crystallization on the self-assembly of the polymers. In order to understand the relationship of cooperation-competition between the multiple driving forces, the chemical structures, chiral characters, polymer topologies, the assembled chiral structures of the polymers as well as their biomimetic functions will be systematically investigated. It is anticipated that the obtained results will provide not only a new method to develop the liquid crystal polymers with additional chiral groups, but also a novel controlled self-assembly strategy driven by liquid crystallization with a chiral induction. This research could be useful for understanding the life phenomena and provide new chiral polymer materials utilized as chiral targeting carriers, bio-recognition or protein purification materials in the fields of biomedicine, targeted therapy and etc.

生命体源自手性物质，特定的手性结构决定着生命物质的功能。研究手性组装结构与性能的关系对了解生命现象和发展新型仿生功能材料具有十分重要的意义。然而，目前关于聚合物基手性组装的系统研究较少，其手性自组装机理尚不明确，仍需深入探索。将手性诱导作用引入聚合物精准自组装体系，会为发展聚合物基手性组装结构和仿生功能材料提供一条全新思路。本申请拟合成含有手性基团的液晶聚合物体系，通过研究拓扑结构、化学结构和环境条件等对其自组装行为的影响，揭示复杂作用力下的自组装规律的同时，制备具有手性结构的聚合物自组装体，以探索手性结构的形成机理和生物功能。该项目的成功实施，不仅能提供具有手性特征液晶聚合物的合成新途径，并且可发展出一种基于手性诱导-液晶驱动协同作用下的精准自组装策略。为加深对生命体手性现象的认识和理解，开发具有手性结构的新型聚合物纳米材料，并扩展其在生物医药等领域的应用提供重要的指导作用。

本项目结合液晶驱动-手性诱导协同作用的自组装理念，开展一系列含有手性氨基酸基团的液晶聚合物体系溶液自组装研究。系统探索了液晶相有序排列与手性诱导协同作用下的聚合物组装机理，评估了具有手性特征的聚合物纳米组装体的细胞毒性等相关性质。具体研究内容如下，结合刚性液晶基元与多种氨基酸柔性链接构建成功合成了具有手性特征的二嵌段聚合物聚合物体系以及二嵌段三组分聚合物体系；系统研究溶液体系中手性基元诱导下的聚合物液晶驱动自组装行为，探索液晶共聚物的手性基元结构、化学组成和组装条件等因素与组装结构的关系；发现了液晶驱动与手性诱导两种作用的竞争规律，并构建多种具有特定手性特征及结构可控的聚合物组装体。在此基础上，初步发展了一种通过手性大分子与液晶嵌段聚合物共混自组装方式，构建具有手性特征的新型组装结构的新策略。结果表明，液晶驱动与手性基元诱导两种作用可通过共混的方式实现协同作用的规律，大分子体系手性可在共混组装过程中实现传递与放大并诱导产生新型的手性组装结构。希望本项目研究结果可进一步对扩展聚合物手性自组装结构类型，发展组装行为调控新策略，为理解手性结构与功能之间的规律提供一定程度的支撑。