Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science, Ministry of Education, Advanced Technology Research Institute (Jinan), Frontiers Science Center for High Energy Material, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China.
J Am Chem Soc. 2022 Mar 23;144(11):5145-5154. doi: 10.1021/jacs.2c00584. Epub 2022 Mar 8.
The pore apertures dictate the guest accessibilities of the pores, imparting diverse functions to porous materials. It is highly desired to construct crystalline porous polymers with predesignable and uniform mesopores that can allow large organic, inorganic, and biological molecules to enter. However, due to the ease of the formation of interpenetrated and/or fragile structures, the largest pore aperture reported in the metal-organic frameworks is 8.5 nm, and the value for covalent organic frameworks (COFs) is only 5.8 nm. Herein, we construct a series of COFs with record pore aperture values from 7.7 to 10.0 nm by designing building blocks with large conformational rigidness, planarity, and suitable local polarity. All of the obtained COFs possess eclipsed stacking structures, high crystallinity, permanent porosity, and high stability. As a proof of concept, we successfully employed these COFs to separate pepsin that is ∼7 nm in size from its crudes and to protect tyrosinase from heat-induced deactivation.
孔径决定了孔的客体可及性，赋予多孔材料多样化的功能。人们非常希望构建具有预定和均匀介孔的结晶多孔聚合物，使大有机、无机和生物分子能够进入。然而，由于易于形成互穿和/或脆弱的结构，金属-有机骨架中报道的最大孔径为 8.5nm，共价有机骨架（COFs）的值仅为 5.8nm。在此，我们通过设计具有大构象刚性、平面性和适当局部极性的构筑块，构建了一系列具有 7.7 至 10.0nm 孔径记录值的 COFs。所得到的 COFs 均具有重叠堆积结构、高结晶度、永久孔隙率和高稳定性。作为概念验证，我们成功地将这些 COFs 用于从粗品中分离大小约为 7nm 的胃蛋白酶，并保护酪氨酸酶免受热诱导失活。
