中山大学苏成勇团队报道了包含12适应性口袋的高阶客体结合超越仿生学动态金属超分子笼。相关研究成果发表在2023年10月16日出版的《美国化学会杂志》。

分子识别是生物功能的核心，这激发了对人工宿主合成的持久研究，以模拟能够识别、处理和运输具有最高复杂性的分子的生物分子。然而，为多个客人（≥4）设计人工宿主的原理和量化方法仍然是一项艰巨的任务。

该文中，研究人员报道了两个菱形十二面体笼[（Zn/Fe）8Pd6-MOC-16]，它们包含12个用于多客体结合的自适应口袋，具有金属中心不稳定性所固有的不同构象动力学，并且能够捕获4–24个客体，以表现出惊人的结合场景的复杂性。特殊的高阶和分级封装现象表明了广泛的主客体动态拟合，使构象调整和适应超越了蛋白质相互作用中诱导拟合和构象选择的双重性。通过NMR和ESI–MS光谱对溶液中的宿主-客体结合事件进行了关键检查，强调了从不同技术中获得可靠结合库的重要性，以及通过过于简化的方法量化增殖客体的结合亲和力的不确定性。

附：英文原文

Title: Dynamic Metallosupramolecular Cages Containing 12 Adaptable Pockets for High-Order Guest Binding Beyond Biomimicry

Author: Yin-Hui Huang, Yu-Lin Lu, Jia Ruan, Shao-Ping Zheng, Xiao-Dong Zhang, Chen-Hui Liu, Yu-Han Qin, Zhong-Min Cao, Zhiwei Jiao, Hai-Sen Xu, Cheng-Yong Su

Issue&Volume: October 16, 2023

Abstract: Molecular recognition lies at the heart of biological functions, which inspires lasting research in artificial host syntheses to mimic biomolecules that can recognize, process, and transport molecules with the highest level of complexity; nonetheless, the design principle and quantifying methodology of artificial hosts for multiple guests (≥4) remain a formidable task. Herein, we report two rhombic dodecahedral cages [(Zn/Fe)8Pd6-MOC-16], which embrace 12 adaptive pockets for multiguest binding with distinct conformational dynamics inherent in metal-center lability and are able to capture 4–24 guests to manifest a surprising complexity of binding scenarios. The exceptional high-order and hierarchical encapsulation phenomena suggest a wide host–guest dynamic–fit, enabling conformational adjustment and adaptation beyond the duality of induced–fit and conformational selection in protein interactions. A critical inspection of the host–guest binding events in solution has been performed by NMR and ESI–MS spectra, highlighting the importance of acquiring a reliable binding repertoire from different techniques and the uncertainty of quantifying the binding affinities of multiplying guests by an oversimplified method.

DOI: 10.1021/jacs.3c09491

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c09491