Hu Weilin, Li Mingyao, Xiong Wan, Zhou Shuyao, Zou Qi, Lü Jing-Tao, Tian He, Guo Xuefeng
Beijing National Laboratory for Molecular Sciences, National Biomedical Imaging Center, College of Chemistry and Molecular Engineering, Peking University, 292 Chengfu Road, Haidian District, Beijing 100871, P. R. China.
School of Physics, Institute for Quantum Science and Engineering and Wuhan National High Magnetic Field Center, Huazhong University of Science and Technology, 1037 Luoyu Road, Hongshan District, Wuhan 430074, P. R. China.
J Am Chem Soc. 2024 Jul 3;146(26):17765-17772. doi: 10.1021/jacs.4c03071. Epub 2024 Jun 20.
Chirality, a fundamental attribute of nature, significantly influences a wide range of phenomena related to physical properties, chemical reactions, biological pharmacology, and so on. As a pivotal aspect of chirality research, chirality recognition contributes to the synthesis of complex chiral products from simple chiral compounds and exhibits intricate interplay between chiral materials. However, macroscopic detection technologies cannot unveil the dynamic process and intrinsic mechanisms of single-molecule chirality recognition. Herein, we present a single-molecule detection platform based on graphene-molecule-graphene single-molecule junctions to measure the chirality recognition involving interactions between amines and chiral alcohols. This approach leads to the realization of in situ and real-time direct observation of chirality recognition at the single-molecule level, demonstrating that chiral alcohols exhibit compelling potential to induce the formation of the corresponding chiral configuration of molecules. The amalgamation of theoretical analyses with experimental findings reveals a synergistic action between electrostatic interactions and steric hindrance effects in the chirality recognition process, thus substantiating the microscopic mechanism governing the chiral structure-activity relationship. These studies open up a pathway for exploring novel chiral phenomena from the fundamental limits of chemistry, such as chiral origin and chiral amplification, and offer important insights into the precise synthesis of chiral materials.
手性作为自然界的一种基本属性，对与物理性质、化学反应、生物药理学等相关的广泛现象有着重大影响。作为手性研究的一个关键方面，手性识别有助于从简单的手性化合物合成复杂的手性产物，并在手性材料之间展现出复杂的相互作用。然而，宏观检测技术无法揭示单分子手性识别的动态过程和内在机制。在此，我们提出了一种基于石墨烯 - 分子 - 石墨烯单分子结的单分子检测平台，用于测量涉及胺与手性醇之间相互作用的手性识别。这种方法实现了在单分子水平上对手性识别的原位实时直接观察，表明手性醇在诱导分子形成相应手性构型方面具有显著潜力。理论分析与实验结果的结合揭示了手性识别过程中静电相互作用和空间位阻效应之间的协同作用，从而证实了控制手性结构 - 活性关系的微观机制。这些研究为从化学的基本极限探索新型手性现象（如手性起源和手性放大）开辟了一条途径，并为手性材料的精确合成提供了重要见解。
