基于双模式分子识别的微孔金属-有机骨架材料结构设计、合成及性质研究

Molecular recognition has received considerable interest due to their widely application in adsorption and separation, heterogeneous catalysis, biomimetic sensing and so on. Owing to the unique structural properties of metal-organic hybrid materials, we hereby propose to design and synthesis of novel porous metal-organic hybrid materials for dual-model molecular recognition, in which the porous materials combine the ability of both size recognition and fluorescent sensing for guest molecule. Furthermore, the relationship between the structural adjustment and the dual-model recognition will also be explored. Based on our previous research results, novel porous materials with gate-opening property will be synthesized and the ratio of gates in the pore will be tuned by the way of solid-state solution process. Based on these results, the relationship between the gate inside the pore and the dual-model recognition will be extensively investigated. Furthermore, novel porous materials with core-shell structures will also be synthesized and the relationship between the functionalized shell structures and the dual-model recognition will also be carefully investigated. The results of this proposal will profit for the comprehension of the characteristics of porous metal-organic hybrid materials and will also provide valuable theoretic and basic results for further structural design and synthesis of novel structures for molecular recognition.

具有分子识别功能的多孔材料在吸附分离、多相催化、仿生传感等众多领域有着广泛的应用前景。基于多孔金属-有机自组装材料的结构特点，本项目提出设计、合成具有尺寸和荧光双模式分子识别功能的新型多孔金属-有机自组装材料，并研究其结构调控与识别性能之间的关系。在前期已有工作基础上，采用"配体预功能化"和"固体溶液"思想，以有机柔性官能团作为分子尺度的"门"，合成"门开关"可调的多孔自组装材料，基于单晶数据，研究构-效关系，揭示主体结构的尺寸识别和荧光识别的机制；采用"晶体外延生长法"，合成核-壳结构的功能材料，研究壳层功能调控的途径及其构效关系，揭示壳层结构与双模式分子识别性能之间的关系。 本项目的完成能够为分子识别功能导向的多孔自组装材料的设计合成提供重要实验依据和有价值的基础研究数据。

本项目围绕分子识别功能的多孔金属-有机自组装材料的研究计划，开展了新结构的合成、功能集成及相关应用研究工作。具体而言，在新结构构筑方面，合成了基于不同金属结构单元对接的新型多孔网络结构（如：基于车辅式与三氮唑双核/三氮唑三核的结构），丰富了这类材料的结构类型和设计思路；在门开关调控方面，利用配体与功能化策略、固体溶液策略、后交换客体填充方法，研究了小分子吸附与门调控之间的关系，指出后交换客体填充方法不仅能够实现对小分子吸附门开关的调控，而且不影响其吸附存储量；在功能集成及应用研究方面，研究了柔性多孔材料的相变与荧光响应之间的关系，构建了荧光及尺寸识别金属阳离子或阴离子功能的新型多孔材料。探索了集磁性与孔道识别功能的多孔网络结构的构建。为拓展这类材料的应用，采用外延生长法，合成了基于金属-有机框架材料的核-壳材料，它在1μL血清样本中依靠尺寸识别能高选择性捕获441条氮基化糖肽分子。. 总体而言，本项目依据既定研究方案，完成了具有识别功能的多孔金属-有机框架材料的研究内容，构建了新型多孔网络材料，探索了在分子尺度的功能调控和集成，拓展了这类多孔材料的潜在应用前景，因此，本项目达到了预期目标。