功能性自组装体的制备研究.docVIP

功能性自组装体的制备研究 　　摘 要：新型组装基元的构筑和组装体的功能是自组装研究的两个核心问题。该研究分别在这两个方面取得了一些进展。各向异性组装基元的出现极大地丰富了自组装的研究内容，并为制备高度有序和复杂的组装体提供了新工具，但目前已报道的各向异性组装基元一般限于微观和亚微观尺寸。该研究制备了分子水平的各向异性粒子，并发现其具有独特的自组装行为。比如：合成了分别具有一个环糊精基团和一个偶氮苯基团的超支化聚合物，然后通过环糊精和偶氮苯之间的主客体复合，偶联得到了Janus型超支化聚合物，且该各向异性聚合物可以进一步自组装形成均一的纳米囊泡，而且所制备的囊泡可以进一步组装形成类似胶子晶体的多级结构。这种高度均一的囊泡组装体是十分罕见的。该课题还在组装体的功能化方面开展研究。例如：长期以来仿细胞模型体系一般只限于对细胞膜结构的仿生，但实际上细胞在发生结构转变时往往伴随着功能的表达。最近，我们制备了具有pH响应的聚合物囊泡，该囊泡可以在pH触发下实现可逆的收缩和膨胀，最为重要的是在这个形变过程中，同时伴随着囊泡荧光的增强和淬灭。整个过程和绿色荧光水母的呼吸过程有些相似。这是目前已报道的为数不多的结构和功能同时表达的一个人工模型膜体系。 　　关键词：自组装 各向异性粒子 超支化聚合物 囊泡 细胞模拟 　　Abstract： It is centrally important for self-assembly research to construct new building blocks and attain new functionalities. We made some progress in these two topics in 2013. Anisotropic particles are new building blocks for self-assembly， which greatly enrich the scope of self-assembly and provide a new toolbox to construct highly ordered and complex self-assemblies. However， most of the reported anisotropic particles are limited in microscopic or submicroscopic scale. Recently， we have extended it into the molecular level， and found new self-assembly behaviors can be realized from these building blocks. For instance， we constructed a Janus hyperbranched polymer by the noncovalent coupling between a hydrophobic hyperbranched poly（3-ethyl-3-oxetanemethanol） with an apex of an azobenzene （AZO）group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin （CD） group through the specific AZO/CD host？guest interactions. This amphiphilic supramolecular polymer can further self-assemble into unilamellar bilayer vesicles with narrow size distribution， which could further aggregate into colloidal crystal-like close-packed arrays under freeze-drying conditions. Such a well-defined and uniform vesicle structure has seldom been observed. Besides， we also focused on the functionalities of self-assemblies. For example， in cytomimetic chemistry， most of the works are concentrated on the structure mim