Wang Guangtong, Feng Yu, Ye Xingyao, Li Zhongping, Tao Shanshan, Jiang Donglin
School of Medicine and Health, Harbin Institute of Technology, Harbin 150080, China.
School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China.
J Am Chem Soc. 2024 Apr 17;146(15):10953-10962. doi: 10.1021/jacs.4c02164. Epub 2024 Apr 2.
We report light gating in synthetic one-dimensional nanochannels of stable crystalline porous covalent organic frameworks. The frameworks consist of 2D hexagonal skeletons that are extended over the - plane and stacked along the -direction to create dense yet aligned 1D mesoporous channels. The pores are designed to be photoadaptable by covalently integrating tetrafluoro-substituted azobenzene units onto edges, which protrude from walls and offer light-gating machinery confined in the channels. The implanted tetrafluoroazobenzene units are thermally stable yet highly sensitive to visible light to induce photoisomerization between the and forms. Remarkably, photoisomerization induces drastic changes in intrapore polarity as well as pore shape and size, which exert profound effects on the molecular adsorption of a broad spectrum of compounds, ranging from inorganic iodine to organic dyes, drugs, and enzymes. Unexpectedly, the systems respond rapidly to visible lights to gate the molecular release of drugs and enzymes. Photoadaptable covalent organic frameworks with reversibly convertible pores offer a platform for constructing light-gating porous materials and tailorable delivery systems, remotely controlled by visible lights.
我们报道了在稳定的晶体多孔共价有机框架的合成一维纳米通道中的光控门控现象。这些框架由二维六边形骨架组成，这些骨架在xy平面上延伸并沿z方向堆叠，以形成密集且排列整齐的一维介孔通道。通过将四氟取代的偶氮苯单元共价整合到从壁上突出的边缘上，使孔具有光适应性，这些边缘提供了限制在通道内的光控机制。植入的四氟偶氮苯单元热稳定，但对可见光高度敏感，可诱导反式和顺式异构体之间的光异构化。值得注意的是，光异构化会引起孔内极性以及孔的形状和尺寸的剧烈变化，这对从无机碘到有机染料、药物和酶等多种化合物的分子吸附产生深远影响。出乎意料的是，该系统对可见光反应迅速，可控制药物和酶的分子释放。具有可逆转换孔的光适应性共价有机框架为构建由可见光远程控制的光控多孔材料和可定制的递送系统提供了一个平台。
