光に応答するミクロ孔を利用した異方的能動輸送膜の開発

今年的这个研究项目源于一个偶然的发现。利用原位光学显微镜观察发现了卟啉基核壳样微观结构（PorMOF）的拓扑缺陷导向成核和生长。重点总结如下：1。在64°c的石英池（1 mm × 10 mm）中，在DMF / EtOH （v / v = 3:1）中一锅合成了六水硝酸锌、4,4′-偶氮吡啶（AzoPy）和4,4′，4′，4′-（卟啉-5,10,15,20-四烷基）四苯甲酸（2hor），发现了一种独特的具有核壳结构的卟啉基晶体微观结构的结晶途径。通过扫描电子显微镜、透射电子显微镜、原子力显微镜和x射线衍射分析表征了该晶体微观结构的形貌和结构。这种晶体微观结构的形成机制是基于原位光学显微镜观察建立的，即由于较低的能垒，固定在壳晶中心的拓扑缺陷指导并触发了新晶相的成核和生长。这种晶体微观结构表现出独特的光物理性质，壳部分对位于壳中心的相应核心部分的荧光发射产生显著影响。更具体地说，壳层可以熄灭核的荧光；当核心晶体从壳层部分释放时，观察到各向异性荧光发射。

This research project in this year is originated from a serendipitous discovery. A topological defect-directed nucleation and growth of a porphyrin-based core-shell-like microstructure (PorMOF) is discovered with the aid of in situ optical microscopic observations. The key points are summarized as follows:1.A unique crystallization pathway of a porphyrin-based crystalline microstructure with a core-shell morphology is discovered in one-pot synthesis of zinc nitrate hexahydrate, 4,4’-azopyridine (AzoPy) and 4,4’,4’’,4’’’-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid) (2HPor) in DMF / EtOH (v / v = 3:1) in a quartz cell (1 mm × 10 mm) at 64°C.2.The morphologies and structures of this crystalline microstructure are characterized by scanning electron microscopy, transmission electron microscopy and atomic force microscopy and X-ray diffraction analysis.3.The mechanism of this crystalline microstructure formation is established based on in situ optical microscopic observations that a topological defects pinned at the center of shell crystals directs and triggers the nucleation and growth of a new crystalline phase because of a lower energy barrier.4.Such a crystalline microstructure exhibits unique photophysical properties that the shell part imposes a remarkable impact on the fluorescence emission of the corresponding core part that locates in the center of the shell. More specifically, the shell can quench the fluorescence of the core; and if the core crystal is released from the shell part, anisotropic fluorescence emission is observed.