Tashiro Shohei, Nakata Kosuke, Hayashi Ryunosuke, Shionoya Mitsuhiko
Department of Chemistry, Graduate School of Science, The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033 Japan
Research Institute for Science and Technology, Tokyo University of Science 2641 Yamazaki, Noda Chiba 278-8510 Japan
Chem Sci. 2025 Jun 2. doi: 10.1039/d5sc00795j.
The arrangement of amino acids within crystalline porous materials represents a unique approach to enhance their functionalities such as catalysis, separation and sensing. In particular, the simultaneous arrangement of distinct residues in crystalline frameworks, , shape sorting, remains one of the most important challenges. Here, we demonstrate the shape sorting of two distinct amino acid residues, tryptophan and serine, within porous metal-macrocycle framework-1 precise molecular recognition at multiple binding sites on the pore surface. Single-crystal X-ray diffraction analysis showed that the indole ring of an N-protected tryptophan molecule was effectively encapsulated within a binding pocket located at the bottom corners of the nanochannel, forming multipoint hydrogen bonds and CH-π interactions. In addition to tryptophan, N-protected serine was adsorbed onto the ceiling sites multipoint hydrogen bonds. Moreover, modifying their protecting groups allowed us to control the relative positions of the two residues in the nanochannel. We further tested the co-adsorption of both residues in selective separation experiments. The results suggest that designing porous crystals with multiple binding sites is an effective strategy for precise heteroleptic arrangement of amino acid residues, resulting in enhanced functionalization of porous materials.
氨基酸在晶体多孔材料中的排列是增强其催化、分离和传感等功能的独特方法。特别是，在晶体框架中同时排列不同的残基，即形状筛选，仍然是最重要的挑战之一。在这里，我们展示了在多孔金属大环框架-1中两种不同氨基酸残基色氨酸和丝氨酸的形状筛选，即在孔表面的多个结合位点上实现精确的分子识别。单晶X射线衍射分析表明，N-保护色氨酸分子的吲哚环有效地封装在位于纳米通道底角的一个结合口袋内，形成多点氢键和CH-π相互作用。除了色氨酸，N-保护丝氨酸通过多点氢键吸附在顶部位点上。此外，修饰它们的保护基团使我们能够控制纳米通道中两个残基的相对位置。我们在选择性分离实验中进一步测试了两种残基的共吸附。结果表明，设计具有多个结合位点的多孔晶体是实现氨基酸残基精确杂配排列的有效策略，从而增强了多孔材料的功能化。
