Department of Chemistry, The University of Tokyo, Tokyo, Japan.
Institute for Quantum Life Science, National Institute for Quantum and Radiological Science and Technology, Chiba, Japan.
Nat Commun. 2021 May 24;12(1):3062. doi: 10.1038/s41467-021-23364-w.
Raman optical activity (ROA) is effective for studying the conformational structure and behavior of chiral molecules in aqueous solutions and is advantageous over X-ray crystallography and nuclear magnetic resonance spectroscopy in sample preparation and cost performance. However, ROA signals are inherently minuscule; 3-5 orders of magnitude weaker than spontaneous Raman scattering due to the weak chiral light-matter interaction. Localized surface plasmon resonance on metallic nanoparticles has been employed to enhance ROA signals, but suffers from detrimental spectral artifacts due to its photothermal heat generation and inability to efficiently transfer and enhance optical chirality from the far field to the near field. Here we demonstrate all-dielectric chiral-field-enhanced ROA by devising a silicon nanodisk array and exploiting its dark mode to overcome these limitations. Specifically, we use it with pairs of chemical and biological enantiomers to show >100x enhanced chiral light-molecule interaction with negligible artifacts for ROA measurements.
拉曼光学活性(ROA)可有效用于研究水溶液中手性分子的构象结构和行为,在样品制备和性价比方面优于 X 射线晶体学和核磁共振波谱学。然而,ROA 信号本质上非常微弱,由于手性光物质相互作用较弱,其强度比自发拉曼散射弱 3-5 个数量级。金属纳米粒子的局域表面等离激元共振已被用于增强 ROA 信号,但由于其光热产生和无法有效地将光学手性从远场转移和增强到近场,因此会产生有害的光谱伪影。在这里,我们通过设计硅纳米盘阵列并利用其暗模式来克服这些限制,展示了全介质手性场增强 ROA。具体来说,我们使用它与 pairs of chemical and biological enantiomers 一对化学和生物对映体一起使用,显示出 >100x 的增强的手性光分子相互作用,同时对于 ROA 测量几乎没有伪影。