基于发光铂(II)配合物的杂化高分子：合成、自组装结构转变与光物理性质研究

项目名称： 基于发光铂(II)配合物的杂化高分子：合成、自组装结构转变与光物理性质研究

项目编号： No.21474044

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 卜伟锋

作者单位： 兰州大学

项目金额： 86万元

中文摘要： 超分子化学的一个主要研究方向是利用非生物分子模拟生物过程，以促进人们对生物体系的理解。本项目旨在利用基于发光铂(II)配合物的杂化高分子囊泡作为模型体系来模拟生物膜融合：一、合成一系列端基为平面型铂(II)配合物的杂化聚苯乙烯，其中铂(II)配合物和聚苯乙烯是通过静电或共价连接的，结构上类似于（超分子）平面-线两嵌段共聚物；二、研究杂化高分子在固态、溶液、薄膜中的自组装结构及其转变、光物理性质，揭示杂化高分子的分子结构、自组装结构与光物理性质三者间的内在联系；三、发现杂化高分子在改变溶剂质量的混合溶剂（氯仿/甲醇，甲苯/甲醇等）中所形成的囊泡和在小时级时间范围内的囊泡融合现象，通过透射电镜清晰地捕捉到囊泡融合过程中的一系列结构转变中间体：相互靠近的囊泡、囊泡外膜突起、类茎秆、半融合中间体和融合孔，阐明该类囊泡及其融合的形成机理，构建模拟生物膜融合的一种非生物高分子/配合物杂化模型体系。

中文关键词： 超分子组装；囊泡融合中间体；铂(II)配合物；光物理性质；溶剂质量

英文摘要： A main topic in the field of supramolecular chemistry is to mimic biological processes by using nonbiological molecules, which provides mechanistic insights for understanding living biological systems. In this proposal, a vesicle model fabricated by solution-based self-assembly of luminescence synthetic polymer/platinum(II) hybrids is used to mimic biomembrane fusion processes. (i) A series of platinum(II) complex terminated polystyrenes are synthesized and characterized in detail.The platinum(II) complexes are connected with polystyrenes by electrostatic interaction or covalent force. These polymeric hybrids are conceptually regarded as (supramolecular) planar-coil diblock copolymers. (ii) The self-assembled structures, structural transitions and photophysical properties of the hybrids are then investigated at the solid, solution, and thin-film states. And therefore, we will build a substantial relationship among molecular structures, self-assembled structures, and photophysical properties. (iii) The hybrids can self-assemble into vesicular aggregates in solvents of variable quality such as chloroform/methanol, toluene/methanol or other mixture solvents, which further show a spontaneous fusion into larger vesicles with an hour-scale fusion time. With this much longer fusion process, the vesicle fusion intermediates for structural evolution, such as docking vesicles, arrow-like protrusion, stalk intermediate, hemifusion diaphragm, and fusion pore are clearly captured by transmission electron microscopy. The mechanisms for the presence of both vesicle and vesicle fusion are clarified.The present concept concerning luminescence metal complexes with solution-based self-assembly of polymers will open a new avenue to mimic the biomembranes and their fusion processes.

英文关键词： Supramolecular Assembly;Vesicle Fusion Intermediates;Platinum(II) Complexes;Photophysical Properties;Solvent Quality