新型双卟啉与桥式环糊精的分子组装及其功能研究

Controllable supramolecular assemblies constructed by molecular assembly have become one of the most fascinating topics in supramolecular chemistry and material science. In this project, a series of water soluble porphyrin dimers bridged by benzene, naphthalene and azobenzene, azobenzene-bridged cyclodextrin dimers and porphyrin-bridged cyclodextrin oligomers will be designed and synthesized as building blocks, which will be fully characterized by NMR, HR-MS, etc. Taking advantage of the high binding behaviors between water soluble porphyrins and cyclodextrins, a series of novel supramolecular assemblies will be constructed from the above mentioned building blocks, and the morphologies and assembly modes of the supramoleculear assemblies will be fully characterized by several modern analytical techniques, including atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), etc. Furthermore, it will be investigated that the morphological conversion upon irradiation with different wavelengths, fluorescence sensing and energy transformational behaviors towards fluorescent dyes. Then, the structure-function relationship between the structures of building blocks and morphology/function of assemblies will be summarized. Hence, this project will provide novel building blocks, theoretical guidance and strategies for constructing functional supramolecular assemblies, which will create significant influence in the supramolecular chemistry and material science.

目前，通过分子组装可控制备功能性超分子组装体是超分子化学和纳米科学的研究热点之一。本项目拟设计合成苯、萘、偶氮苯桥联水溶性双卟啉和偶氮苯桥联环糊精、卟啉桥联多环糊精作为两种组装基元，并通过核磁、高分辨质谱等分析手段对上述化合物进行结构表征；利用环糊精与水溶性卟啉强键合能力，通过上述组装基元构筑超分子组装体，并通过紫外、荧光、原子力显微镜，扫描电子显微电镜、透射电子显微镜、X-射线粉末衍射等现代分析手段表征其在液相和固相的形貌特征及组装模式；进一步研究组装体在不同波长光照调控下的形貌转换、对染料分子的荧光传感和能量传递等方面的功能，总结组装基元的分子结构与组装体形貌和功能间的构效关系。本研究将为可控超分子体系的构筑提供新的组装基元、构筑策略和理论依据，对超分子化学和材料科学的进一步发展具有重要科学意义。

基于分子识别和分子组装可控制备功能性超分子组装体是超分子化学和材料科学的研究热点，本项目3年来以多识别位点的桥联羧基卟啉和桥式环糊精为组装基元，利用分子识别和分子组装构筑了系列新型超分子组装体并在光调控形貌转换、能量传递、富勒烯的络合等功能进行了探究。研究内容概括如下：1.设计合成了苯桥联羧基卟啉G和偶氮苯桥联环糊精H，G自身通过π-π堆积在水溶液中形成片状组装体，利用羧基卟啉与环糊精强的主客体作用和偶氮苯顺反异构体的构性差异，将H-trans和H-cis引入通过二次组装成功构筑了具有强荧光的二维纳米片和球状纳米粒子并表现出了显著的细胞成像差异；两种组装体通过不同步长光照进行可逆往复转换。该工作为构筑不同形貌和性能的超分子组装体提供了简单快捷策略。2.设计合成了平面型均三苯基苯和四苯乙烯桥联多聚环糊精，基于羧基卟啉与环糊精强的主客体作用和组装基元的多识别位点，利用上述两种环糊精与G成功构筑了两类具有笼状结构的超分子组装体，得益于笼的空腔和卟啉与富勒烯强的π-π作用，两种组装体水溶液中高效络合C60并实现了对自由基的清除，该工作为实现富勒烯的水溶性和抗衰老材料制备提供了新思路。3.设计合成了偶氮苯桥联羧基卟啉和锌卟啉桥联环糊精，通过主客体作用成功实现了两种基元分子间的高效能量传递并构筑了具有笼状结构的超分子组装体，该组装体在水溶液有效络合富勒烯且实现三组分二次能量传递。研究表明多识别位点的桥联卟啉和桥式环糊精有利于构筑二维及三维笼状组装体，丰富了构筑多维超分子组装体的构筑策略，对促进超分子化学和材料科学的发展具有重要科学意义。