二氧化碳刺激响应高分子体系的构筑与功能研究

This project aims at the study of the controlled synthesis, morphology-tuning and function-tuning of block copolymer and comb copolymer with carbon dioxide stimuli-responsive block by using carbon dioxide. We design and develop biomimetic polymersomes, polymer membrane, and polymer hydrogel,which can reversibly respond to carbon dioxide and nitrogen, and perform a distinctive breathing function. It is expected that the carbon dioxide responsive polymersomes would open a door to mimic the cytomembrane and understand cellular biofunction. By regulating carbon dioxide stimulation time to induce the growth of these polymersomes, polymer membrane, and polymer hydrogel, tunable permeability could be introduced in the membrane. Utilizing such a controlled semi-permeability, we could enable the polymersomes or polymer membrane to realize the hierarchical cargo release and the selective separation of guest molecules according to their size differences. Furthermore, we will use the vesicle or membrane as nanoreactor to divide different enzymatic catalytic reactions in spatial and temporal scale by simply modulating the carbon dioxide treatment levels. The project will develop a new stimuli-responsive mode, that is gas stimuli. We will clarify the regularity of the responsive time and responsive degree of amine, amidine and guanidine on carbon dioxide. We will pay attention to the high sensitivity and high efficiency of response, and the simple and practical synthesis. Through the gas control, the separation, release and reaction of different size nanoparticles, protein, and functional molecules could be realized. The control method is simple, control process is clean and fast. This project will build the effective method for carbon dioxide stimuli-response polymer system.The project has important scientific significance and broad application prospect.

本项目致力于含二氧化碳刺激响应链段的嵌段共聚物、梳形共聚物的可控合成、组装形貌调控与功能调控研究。包括构筑多种二氧化碳响应的聚合物组装体，研究其在二氧化碳氛围内的形貌转变，进行生物模拟，探索仿生组装体形貌转变规律，运用气体可逆调控聚合物形貌；使用二氧化碳气体驱动高分子膜透过率改变，模拟细胞体行为和功能，构筑具有二氧化碳响应的仿生大分子纳米分离器和纳米反应器；构筑具有二氧化碳响应纳米通道的膜材料；构筑通过二氧化碳进行尺寸调控和功能材料释放的水凝胶。 开拓较新的刺激响应调控方式- - 气体调控，阐明胺、脒、胍等二氧化碳刺激响应基元在响应模式、响应程度上的规律，实现刺激响应的敏感性、高效性，解决合成方法简易性、实用性问题。通过气体调控纳米粒子、蛋白、功能分子的分离、释放、参与反应，调控手段简单，控制过程清洁快速。本项目将建立构筑二氧化碳刺激响应聚合物体系的有效方法，具有重要科学意义和宽广应用前景。

刺激响应性聚合物能够随环境中微小的物理条件或化学条件的改变而引起自身性质变化。近年来这类智能材料被广泛用于构筑纳米组装体、凝胶等，进而在药物可控释放、组织工程、自修复材料等领域展示了很大的应用价值。然而对于pH值、离子、氧化还原和酶等几类传统刺激模式，实现过程中需要反复向聚合物溶液中加入刺激源，可能造成副产物的累积和对系统不必要的污染。CO2在自然界大量存在，是机体与外界环境物质和能量交换过程中的重要代谢产物，气体本身具有很好的生物相容性和膜穿透性。将CO2作为刺激源，能够特异性改变聚合物的结构和性质，同时能够被惰性气体排出体系，整个过程中不产生任何副产物的累积，大大提升了其作为一类调控手段在人体内或工业领域应用时的可操作性和相容性。本项目致力于含二氧化碳刺激响应链段的嵌段共聚物、梳形共聚物的可控合成、组装形貌调控与功能调控研究。包括构筑多种二氧化碳响应的聚合物组装体，研究其在二氧化碳氛围内的形貌转变，进行生物模拟，探索仿生组装体形貌转变规律，运用气体可逆调控聚合物形貌；使用二氧化碳气体驱动高分子膜透过率改变，模拟细胞体行为和功能，构筑具有二氧化碳响应的仿生大分子纳米分离器和纳米反应器；构筑通过二氧化碳刺激响应调控的纳米纤维膜材料；构筑通过二氧化碳进行尺寸调控和功能材料释放的水凝胶。本项目开拓了较新的刺激响应调控方式——气体调控，实现了刺激响应的敏感性、高效性，解决了合成方法简易性、实用性问题，建立了构筑二氧化碳刺激响应聚合物体系的有效方法，具有重要科学意义和宽广应用前景。本项目标注基金资助的已发表SCI收录论文22篇,包括发表在Angew. Chem. Int. Ed. 的2篇，Macromolecules上的5篇；获得授权的中国发明专利2项。培养博士生6名，硕士生4名，博士后1人。