Sun Bo, Kim Yongju, Wang Yanqiu, Wang Huaxin, Kim Jehan, Liu Xin, Lee Myongsoo
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, China.
Pohang Accelerator Laboratory, Postech, Pohang, Gyeongbuk, Korea.
Nat Mater. 2018 Jul;17(7):599-604. doi: 10.1038/s41563-018-0107-4. Epub 2018 Jun 11.
Protein pores are highly specific in binding to chiral substrates and in catalysing stereospecific reactions, because their active pockets are asymmetric and stereoselective. Chiral binding materials from molecular-level pores with high specificity have not been achieved because of problems with pore deformation and blocking . A promising solution is the self-assembly of single sheets where all pores are exposed to the environment, for example as metal-organic frameworks , polymers or non-covalent aromatic networks, but, typically, the pores are distant from the internal cavities with chirality. Here, we report the synthesis of homochiral porous nanosheets achieved by the 2D self-assembly of non-chiral macrocycles, with open/closed pore switching. Pore chirality is spontaneously induced by a twisted stack of dimeric macrocycles. The porous 2D structures can serve as enantiomer sieving membranes that exclusively capture a single enantiomer in a racemic mixture solution, with uptake capacity greater than 96%. Moreover, the entrapped guests inside the pores can be pumped out by pore closing triggered by external stimuli. This strategy could provide new opportunities for controlled molecule release, as well as for artificial cells.
蛋白质孔在与手性底物结合以及催化立体特异性反应方面具有高度特异性,因为它们的活性口袋是不对称且具有立体选择性的。由于孔变形和堵塞问题,尚未实现具有高特异性的分子级孔的手性结合材料。一个有前景的解决方案是单层自组装,其中所有孔都暴露于环境中,例如作为金属有机框架、聚合物或非共价芳香网络,但通常情况下,孔与具有手性的内腔距离较远。在此,我们报告了通过非手性大环化合物的二维自组装实现的同手性多孔纳米片的合成,具有开/关孔切换功能。孔的手性由二聚大环化合物的扭曲堆叠自发诱导。这种多孔二维结构可作为对映体筛分膜,在消旋混合物溶液中专门捕获单一对映体,摄取容量大于96%。此外,孔内捕获的客体可以通过外部刺激触发的孔关闭而被泵出。这种策略可为可控分子释放以及人工细胞提供新的机会。