基于烷氧基胺键的多重响应型聚合物囊泡制备及其结构与性能

Responsive polymersomes have become a burgeoning field in the past decades due to their applications in biomaterials, micro/nano reactors, catalysts, coatings, composite materials, fillers, etc. Many interesting results have been achieved so far, but the incorporation of responsive chemical bonds is usually complicated. In this project, we will try to use silica particles as templates and "living" polymerization to control the compositions and structures of polymers to synthesize a series of alkoxyamine bond based polymersomes with various compositions, molecular segments, thicknesses, crosslinking density, sizes of cavum. After crosslinked by nitroxide radical coupling, alkoxyamine bonds can be incorporated. Because alkoxyamine bonds can be decomposed by base, oxygen, vitamin C and high temperature, thus, the novel responsive polymersomes based on alkoxyamine bonds are easily synthesized. After comprehensively investigating the effects of the composition and structure of polymersomes as well as environments on the responsive decomposing mechanism of molecular chains and the controllable releasing behavior of guest molecules, we expect to reveal the relationship between composition-structure-property of polymersomes and its controllable laws, and to finally develop novel and feasible strategies for fabrication of responsive polymersomes. It is anticipated that more than 15 SCI papers will be published in journals at impact factor over3.0, and 1 paper in top journals of chemistry or materialss. 1 or 2 patents might be conceivable.

响应型聚合物囊泡在载体与可控释放、微反应容器、复合材料等方面具有许多重要应用，但现有聚合物囊泡中响应断裂化学键大多引入过程复杂，甚至有毒。本项目拟采用二氧化硅微球为模板，通过活性聚合控制聚合物分子链组成和结构，以氮氧稳定自由基偶合交联引入烷氧基胺键，从而可以方便引入可在碱性、氧气、维生素C、高温下等环境条件下发生响应断裂的基于烷氧基胺键的新型响应型聚合物囊泡。深入系统研究这种新型聚合物囊泡的组成、结构、环境条件等对分子链响应断裂机制、客体分子的可控释放行为的影响，揭示其组成-结构-性能的相关性及其调控规律，发展简便、无毒的新型响应型聚合物囊泡的制备路线，并进一步探索其可能的应用途径，既有理论研究价值又具实际意义。预期共发表SCI论文15篇以上，其中IF3.0以上论文不少于8篇，至少1篇发表在化学或材料领域顶级学术期刊上论文；申请国家发明专利1-2项。

响应型聚合物囊泡在载体与可控释放、微反应容器、复合材料等方面具有许多重要应用，但现有聚合物囊泡中响应断裂化学键大多引入过程复杂，甚至有毒。本项目通过表面引发原子转移自由基聚合和表面转移氮氧自由基偶合反应，成功合成了以交联的聚甲基丙烯酸羟乙酯（PHEMA）和聚苯乙烯（PS）为单元的新型响应型聚合物微球；将天然聚合物氧化海藻酸钠（ADA）的水溶液与FF的六氟异丙醇溶液混合，同时加入HAuCl4稀溶液，首次报道了具有pH与谷胱甘肽（GSH）双重响应的基于二苯基丙氨酸（FF）自组装的纳米药物载体；以硅烷偶联剂改性的SiO2和TiO2 纳米颗粒共同稳定乳液，通过Pickering乳液聚合制备了UV刺激响应性有机/无机杂化微胶囊并用于水性自修复超疏水涂层；报道了一种相对简便和实用的方法来制备负载两种客体物质且具有可控顺序释放的双响应杂化微胶囊。两种客体物质被独立地封装在不同的存储空间里，这样，得到的微胶囊可以实现预程序化的在某种刺激下独立释放某一种客体物质，并且释放顺序可调。4年共发表标注本项目基金号的SCI论文28篇，其中IF3.0以上论文25篇，包括Sci. Adv.（1篇）、Chem. Soc. Rev.（1篇）、Angew. Chem. Int. Ed. （1篇）、ACS Nano（4）Adv. Funct. Mater.（2篇）、Chem. Mater.（3篇）、Small（3篇）、Macromolecules（2篇）等。申请国家发明专利3项。圆满完成了本项目规定的考核任务。