Reaction-Modulated Surface-Enhanced Raman Scattering Strategy for Stereoselective Differentiation and Identification of Amino Acids,Analytical Chemistry

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Reaction-Modulated Surface-Enhanced Raman Scattering Strategy for Stereoselective Differentiation and Identification of Amino Acids
Analytical Chemistry ( IF 6.7 ) Pub Date : 2024-09-05 , DOI: 10.1021/acs.analchem.4c01519
Ruiqi Peng ₁ , Lei Guo ₁ , Lu Chen ₁ , Lulu Liu ₁ , Wei Deng ₁ , Dan Li ₁

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Surface-enhanced Raman scattering (SERS) sensing of racemates is a remarkably fascinating yet very sophisticated objective because of similar physicochemical features of enantiomers. Inspired by the enantiomeric selectivity of nucleophilic addition reaction (NAR) toward amino acids, we herein propose highly effective, robust SERS discrimination of d- and l-valine by synergizing asymmetric gold nanorods-embedded ZIF-8 nanoparticles (AGNZ) with NAR to engender stereoselective molecular fingerprint. Experimental and chemometric analyses disclose that enantioselectivity lies in dual aspects: (i) abundant interfacial cavities and 3D hot-spots in AGNZ offer necessary confined asymmetrical surroundings to trigger enantiospecific molecular adsorption and interaction affinity, and (ii) the specified NAR drags the racemates adjacent to the interfacial area of AGNZ for maximum analytes–substrate interaction. This strategy is universal and can be utilized for the recognition of different amino acid enantiomers. Importantly, multiple quantifications of the racemic ratio can be realized with superior prognostic performances. This synergizing strategy therefore provides a significant paradigm shift from traditional methods to realize highly effective SERS discrimination of racemates.

中文翻译：

用于氨基酸立体选择性分化和鉴定的反应调制表面增强拉曼散射策略

由于对映体具有相似的物理化学特征，外消旋体的表面增强拉曼散射（SERS）传感是一个非常令人着迷但非常复杂的目标。受亲核加成反应 (NAR) 对氨基酸的对映体选择性的启发，我们在此提出通过协同不对称金纳米棒嵌入的 ZIF-8 纳米颗粒 (AGNZ) 与 NAR 产生对d-和l-缬氨酸的高效、稳健的 SERS 区分，以产生立体选择性分子指纹。实验和化学计量分析表明，对映选择性存在于两个方面：(i) AGNZ 中丰富的界面空腔和 3D 热点提供了必要的受限不对称环境，以触发对映特异性分子吸附和相互作用亲和力，以及 (ii) 指定的 NAR 拖动相邻的外消旋物到 AGNZ 的界面区域，以实现最大程度的分析物-底物相互作用。该策略是通用的，可用于识别不同的氨基酸对映体。重要的是，可以实现外消旋比例的多重量化，并具有优异的预后性能。因此，这种协同策略提供了从传统方法到实现高效 SERS 外消旋体区分的重大范式转变。

更新日期：2024-09-05

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