金属有机骨架结构诱导及双光子细胞成像应用

Metal - organic frameworks (MOFs) are a class of hybrid materials with the properties of gas adsorption, catalysis, etc. The infinite tunability of MOFs are resulted from the limitless choice of metals and organic bridging ligands. It is a novel method to adjust the structures of MOFs with the constant metals and ligands by applying the structural induction agents (SIAs) presented by our team. SIAs exist in the synthetic system and have important roles to form structures of the aimed compounds, while they have neither coordination actions with the metal ions nor stay in the cavities/channels of the resultant frameworks. The SIAs are not removed from the frameworks for application, which is different from templates and structural direct agents (SDAs) and beneficial for the stability of the frameworks. In the other hand, Compared with one-photon microscopy (OPM), two-photon microscopy (TPM) offers several advantages, including the capability of imaging deep inside a tissue, higher spacial resolution, and longer observation time. While, the luminescence of nanoscale metalorganic frameworks (NMOFs) is not ideal for biomedical imaging applications due to its low quantum yields. This project based on inductive effect of zwitterion pyridiniumolate derivatives, is aimed at constructing novel metal - organic frameworks with high quantum yields of two - photon luminescence. The project, in order to reveal the synthesis law, found the relationship between structures and properties, set up and improve the theoretical foundations for molecular functional materials, and guide the syntheses for the metal - organic hybrid materials, is required to do research on designing, synthesis, adjusting, structure and property.

金属有机骨架化合物是具有吸附、催化等性能的重要复合材料。当前，其结构调控过度依赖金属及配体。本课题组发现在金属及配体恒定情况下，结构诱导剂可诱导新型金属有机骨架结构。不同于结构指向法、模板法，结构诱导是一种全新结构调控手段。双光子细胞成像具有深穿透、低毒性等优点。有机无机复合纳米粒子因低荧光量子产率限制了其细胞成像应用。本项目拟应用两性吡啶盐衍生物作为结构诱导剂，诱导调控新型金属有机骨架结构，研究结构诱导调控及结构与性能关系，为材料设计合成提供新方法；调控材料尺度及荧光性能，制备具有高量子产率双光子荧光纳米金属有机骨架化合物，并应用于细胞成像，研究其与细胞组成动态作用及机理，拓展材料应用。通过研究此类材料设计、合成、调控、结构及性能，揭示合成规律，深入认识构效关系物理本质，建立并完善分子基材料理论基础，为金属有机复合材料制备及应用提供理论指导。

当前，金属有机骨架化合物(Metal-Organic Frameworks，MOFs)结构调控过度依赖金属及有机连接体。温度、酸度等合成条件不变，应用相同金属离子、有机连接体进行自组装，金属有机骨架结构难以变化。本项目通过客体分子、分子间作用力、配体构型等调变金属有机骨架结构，进而调控材料光学性能，研究其构效关系，并在非线性光学，生物成像等领域拓展金属有机骨架材料的应用。四年内，项目从微观原子层次对相变展开研究，为相变提供结构支持，为材料性能突变提供理论支持；研究了四苯基乙烯随温度的构象运动轨迹，为聚集诱导发光（AIE）物理机制提供物理观测支持；研究配位聚合物材料设计构筑及构效关系，为寻找新材料提供方法学指导。本基金支持下，在Inorg. Chem.、Sci. China Mater.、J. Mater. Chem. B、Chem. Eur. J.、CrystEngComm、Dalton Trans.、J. Phys. Chem. C、J. Mater. Chem. C、Mater. Chem. Front.等知名期刊上，发表了标注本基金号的SCI论文34篇，远超初期6-14篇目标。其中主持人为第一作者/第一通讯作者SCI论文有26篇，国家自然科学基金为第一标注SCI论文有30篇。