Lee Sung Gun, Kwak Sungjun, Son Won-Ki, Kim Seonung, Nam Ki Tae, Lee Ho-Young, Jeong Dae Hong
Department of Chemistry Education, College of Education, Seoul National University, Seoul 08826, Republic of Korea.
Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Republic of Korea.
Anal Chem. 2024 Jun 18;96(24):9894-9900. doi: 10.1021/acs.analchem.4c00772. Epub 2024 Jun 4.
Surface-enhanced Raman optical activity (SEROA) is a promising method for analyzing chiral molecules' molecular chirality and structural changes. However, conventional SEROA measurements face challenges related to substrate stability, signal uniformity, and interference from electronic circular dichroism (ECD). Therefore, in this study, we present a uniform and stable substrate for SEROA measurements by utilizing Au nanoparticles on the Au nanofilm structure to confine hotspots to the film-particle junctions and minimize ECD interference. This method also uses the induction of chirality from chiral molecules to achiral molecules to overcome the limitation of chiral molecules in SEROA measurements, specifically their lower signal efficiency. Successful chirality transfer is demonstrated through distinguishable SEROA signals when the l/d-alanine mixture is present. Enantiomeric discrimination of different l/d-alanine ratios was achieved with linear responses in the circular intensity difference (CID). Altogether, the proposed chiral-induced SEROA on the AuNP_on_AuNF substrate shows promising potential for detecting and characterizing structural changes in biomolecules, thus making it a valuable tool for various research applications.
表面增强拉曼光学活性（SEROA）是一种用于分析手性分子的分子手性和结构变化的很有前景的方法。然而，传统的SEROA测量面临与底物稳定性、信号均匀性以及来自电子圆二色性（ECD）的干扰相关的挑战。因此，在本研究中，我们通过在金纳米膜结构上利用金纳米颗粒将热点限制在膜 - 颗粒结处并最小化ECD干扰，提出了一种用于SEROA测量的均匀且稳定的底物。该方法还利用手性分子向非手性分子的手性诱导来克服SEROA测量中手性分子的局限性，特别是其较低的信号效率。当存在l/d - 丙氨酸混合物时，通过可区分的SEROA信号证明了成功的手性转移。通过圆强度差（CID）中的线性响应实现了不同l/d - 丙氨酸比例的对映体鉴别。总之，所提出的在AuNP_on_AuNF底物上的手性诱导SEROA在检测和表征生物分子的结构变化方面显示出有前景的潜力，因此使其成为各种研究应用的有价值工具。
