重氮偶合反应诱导自组装构筑刺激响应性纳/微米聚集体

In recent years, azobenzene containing polymeric aggregates have attracted much attention for their interesting stimulus responsive properties. The typical procedure for the fabrication of azobenzene polymeric aggregates is by self-assembly block copolymers in selected solvents, which is usually performed in dilute solutions and the large-scale preparation is hard to achieve. This procedure involves multi-steps and is time-consuming. On the other hand, due to the similar solubility of the azobenzene monomer and its polymer, the polymerization-induced self-assembly of azobenzene containing polymers has not been reported yet. As we know, the water insoluble azobenzene is usually prepared by azo coupling reaction between diazonium salts and derivatives of aniline or phenol in water. This provides the possibility to obtain the self-assembly aggregates induced by azo coupling reaction in aqueous solution. In this project, we will develop a novel one-pot strategy to prepare polymeric aggregates via the azo coupling reaction induced macromolecular self-assembly in aqueous solution, which efficiently combined the chemical reaction and self-assembly in one pot. Furthermore, it was very easy to introduce more functionality to the self-assembly aggregates.

偶氮苯作为刺激响应基团中的明星分子近年来受到了广泛关注，尤其是随着大分子自组装研究的发展，将偶氮苯基元引入大分子自组装体系，为自组装体系带来了诸如光、酶等刺激响应功能，从而在生命科学和材料科学等领域有着广泛的应用前景。在传统的选择性溶剂自组装法效率低，聚合诱导自组装又不适用的情况下，亟需发展其它行之有效的刺激响应性偶氮聚合物自组装体的制备新方法。本项目正是以此为目标，发展重氮偶合反应诱导聚合物自组装制备纳微米聚集体的新方法，并探索此过程中的规律。重氮偶合反应生成偶氮苯基团的同时，又实现了反应诱导聚合物自组装，这样就将反应与组装有机的结合到了一起。在此基础上，我们进一步研究上述体系的光、酶及化学还原剂的刺激响应行为，探索上述相关材料在传感器、可控释放以及荧光可控成像等方面的应用。

将偶氮苯基元引入大分子自组装体系，为自组装体系带来了诸如光、酶等刺激响应功能，从而在生命科学和材料科学等领域有着广泛的应用前景。在传统的选择性溶剂自组装法效率低，聚合诱导自组装又不适用的情况下，亟需发展其它行之有效的刺激响应性偶氮聚合物自组装体的制备新方法。 本项目正是以此为目标，发展重氮偶合反应诱导聚合物自组装制备纳微米聚集体的新方法，并探索此过程中的规律。重氮偶合反应生成偶氮苯基团的同时，又实现了反应诱导聚合物自组装，这样就将反应与组装有机的结合到了一起。我们设计并利用活性聚合合成得到多种结构新颖的嵌段聚合物，包括大分子重氮盐、大分子苯胺以及双亲水性偶氮苯类聚合物等；以大分子重氮盐及大分子苯胺为前体，系统研究了重氮偶合反应诱导自组装的组装条件及组装规律；通过引入AIE基团，拓展了组装聚集体的酶响应还原特性及相关应用；制备了兼具胶体稳定性及反应活性的大分子重氮盐纳米聚集体；基于具有自降解特性且含有AIEgens的偶氮苯类聚合物，构建了酶解反应自组装体系，探索了该类聚合物在生物成像等方面的初步应用。