与金属配位导向的杂臂星形聚合物自组装及其药控性研究

A miktoarm star polymer is one that combines different polymer arms into a molecule through a single core. As a result, the arms could exhibit good independence with regard to structure and function. Therefore, miktoarm star polymers are able to exhibit unique self-assembly behaviors and have potential applications in some fields like nano-medicine. However, at present self-assembly of miktoarm star polymers lacks high directionality. Therefore, to explore self-assemblies with novel morphologies and functions, in the project coordination-directed self-assembly of miktoarm star polymers with metal ions will be proposed. For this purpose, several kinds of functional amphiphilic miktoarm star polymers containing ligand moieties are designed and synthesized, where the ligand groups are also emanated from the cores. Then, the self-assemblies with multi-microenvironments will be constructed through hierarchical self-assembly such as metal-ligand coordination-driven self-assembly followed by further self-assembly induced by changes in environmental conditions. The influences of the structures of the miktoarm star polymers, metal ion species and changes in environmental factors on architectures and morphologies of the self-assemblies will be investigated. And the application of the self-assemblies in drug delivery will be explored. Finally, the structure-properties relationship of the self-assemblies of miktoarm star polymers with metal ions will be elaborated.

杂臂星形聚合物分子中不同臂链仅通过连接点关联，因而它们保持了结构与功能的相对独立性。因此，这类聚合物具有独特的自组装特性，并且在纳米药物等领域有潜在的应用价值，但杂臂星形聚合物自组装缺乏定向性。本项目提出并构筑与金属配位导向杂臂星形聚合物自组装，并实施多级自组装策略，以探索新颖形态与功能的自组装体。首先通过结构与功能设计合成几种含配体基团的两亲性功能杂臂星形聚合物,其配体基团也是从杂臂的中心连接点辐射出。然后由金属-有机配位键驱动杂臂星形聚合物初级自组装,由环境变化诱导其臂链发生溶解性转变驱动进一步自组装，以构筑出含多种功能性微环境的自组装体。深入研究杂臂星形聚合物单元结构、金属离子种类及环境因素等对自组装体结构、形态、形态转变与性能的影响。探索杂臂星形聚合物单元/金属离子自组装体系在药物控释方面的应用。通过研究，较系统地阐述杂臂星形聚合物/金属离子超分子自组装体系的结构与性能关系。

杂臂星形共聚物分子中不同臂链仅通过连接点关联，因而它们保持了结构与功能的相对独立性。因此，这类共聚物具有独特的自组装特性，并且在纳米药物等领域有潜在的应用价值，但杂臂星形共聚物自组装缺乏定向性。本项目提出并构筑了与金属配位导向杂臂星形共聚物自组装，并实施多级自组装策略，以探索具有新颖形态与功能的自组装体。首先通过结构与功能设计合成出了几类含三联吡啶配体基团的两亲性功能性杂臂星形共聚物，配体基团也连在臂链的连接处。合成含配体基团杂臂星形共聚物涉及多步反应，并应用了多种反应技术，尤其是将光引发的大分子巯基-烯自由基偶联反应应用到合成中，探索并优化出了在含氨基聚合物链存在下的高效偶联反应条件，实现了目标杂臂星形共聚物的精准合成。然后，由金属离子-配体配位键驱动杂臂星形共聚物初级自组装制备出了金属化超分子配位复合物，研究了杂臂星形共聚物单元结构对其与金属离子(如钌离子)配位性的影响。最后，研究了配位复合物在水溶液中的自组装特性，及环境因素变化对自组装体结构与形态的影响，构筑出几种多功能自组装体。另外，初步探索了自组装体对客体分子的包载与释放。通过研究，明确了杂臂星形共聚物及其金属化超分子配位复合物的高效合成方法，表征了金属化超分子配位复合物自组装体系的结构。