School of Physics, Beijing Institute of Technology, Beijing 100081, China.
CAS Key Laboratory of Standardization and Measurement for Nanotechnology, National Center for Nanoscience and Technology, Beijing 100190, China.
ACS Nano. 2021 Dec 28;15(12):19535-19545. doi: 10.1021/acsnano.1c06467. Epub 2021 Nov 19.
Molecular chirality recognition plays a pivotal role in chiral generation and transfer in living systems and makes important contribution to the development of diverse applications spanning from chiral separation to soft nanorobots. To detect chirality recognition, most of the molecular sensors described to date are based on the design and preparation of the host-guest complexation with chromophore or fluorophore at the reporter unit. Nevertheless, the involved tedious procedures and complicated chemical syntheses hamper their practical applications. Here, we report the plasmonically chiroptical detection of molecular chirality recognition without the need for a chromophore or fluorophore unit. This facile methodology is based on plasmonic nanotransducers that can convert molecular chirality recognitions occurring at nanoscale interfaces into asymmetrically amplified plasmonic circular dichroism readouts, enabling enantiospecific recognition and quantitative determination of the enantiomeric excess of small amino acids. Importantly, such a plasmon-based chirality sensing shows 10-10 amplification in the plasmonic circular dichroism signals from the detections of racemate and near-racemate of molecular analysts, demonstrating an extraordinary sensitivity to the host-guest enantioselective interactions. Furthermore, with advantages of easy-processing, cost-effective, and specific to interfacial molecular chirality, our chiroptical sensing scheme could hold considerable promise toward applications of enantioselective high-throughput screening in biology, stereochemistry, and pharmaceutics.
分子手性识别在生命系统中的手性产生和传递中起着关键作用，为从手性分离到软纳米机器人等多种应用的发展做出了重要贡献。为了检测手性识别，迄今为止描述的大多数分子传感器都是基于在报告单元中设计和制备带有生色团或荧光团的主体-客体络合作用。然而，所涉及的繁琐程序和复杂的化学合成阻碍了它们的实际应用。在这里，我们报告了无需生色团或荧光团单元即可进行手性识别的等离子体手性检测。这种简便的方法基于等离子体纳米换能器，它可以将纳米尺度界面上发生的分子手性识别转化为不对称放大的等离子体圆二色性读出，从而实现对小氨基酸对映体选择性的识别和对映过量的定量测定。重要的是，这种基于等离子体的手性传感在手性分析物的外消旋体和近外消旋体检测中，在等离子体圆二色信号中表现出 10-10 的放大，对手-客体对映选择性相互作用具有极高的灵敏度。此外，由于具有易于处理、成本效益高以及对界面分子手性特异性的优点，我们的手性传感方案在手性生物、立体化学和药物学中的对映体高通量筛选应用方面具有很大的应用前景。
