Zhang Zhipeng, Li Xiaoxing, Cheng Yujun, Yao Yao, Li Ruili, Liu Qi, Yang Hua, Chen Xiaoqing
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China.
Xiangjiang Laboratory, Changsha 410205, China.
Anal Chem. 2024 Dec 10;96(49):19632-19640. doi: 10.1021/acs.analchem.4c04726. Epub 2024 Nov 26.
To address the challenge of chiral recognition in terms of efficiency and generality, we propose a novel fluorescence sensing approach by rationally designing metal-ion-responsive chiral molecular tweezers. The flexible and adaptable molecular tweezers enable facile recognition of 31 structurally varied chiral primary amine compounds, including amino acids, amino acid esters, and chiral amines. Notably, upon stimulation by zinc ions, the chiral molecular tweezers demonstrate a higher enantioselective fluorescence response. Combined density functional theory calculations reveal that the chiral sensing mechanism relies on differential reaction rates and potential hydrogen-bonding interactions between the two enantiomers and the chiral receptor, which results in one of the enantiomers forming a more abundant, stable, and structurally rigid complex with the receptor, resulting in a significant increase in the fluorescence intensity and enantioselectivity. The stimuli-responsive molecular tweezers approach provides a novel strategy for precise stereocontrol and universality of chiral recognition, offering a promising tool for applications in various fields.
为了应对手性识别在效率和通用性方面的挑战，我们通过合理设计金属离子响应性手性分子镊子，提出了一种新颖的荧光传感方法。这种灵活且适应性强的分子镊子能够轻松识别31种结构各异的手性伯胺化合物，包括氨基酸、氨基酸酯和手性胺。值得注意的是，在手性分子镊子受到锌离子刺激后，表现出更高的对映选择性荧光响应。结合密度泛函理论计算表明，手性传感机制依赖于两种对映体与手性受体之间不同的反应速率和潜在的氢键相互作用，这导致其中一种对映体与受体形成更丰富、稳定且结构刚性的复合物，从而使荧光强度和对映选择性显著增加。这种刺激响应性分子镊子方法为手性识别的精确立体控制和通用性提供了一种新颖策略，为在各个领域的应用提供了一个有前景的工具。
