Enantioselective Surface‐Enhanced Raman Scattering by Chiral Au Nanocrystals with Finely Modulated Chiral Fields and Internal Standards

Abstract The chiral discrimination of enantiomers is crucial for drug screening and agricultural production. Surface‐enhanced Raman scattering (SERS) is proposed for discriminating enantiomers benefiting from chiral plasmonic materials. However, the mechanism of enantioselective SERS is unclear, and fluctuating SERS intensities may result in errors. Herein, this work demonstrates a reliable SERS substrate using chiral Au nanocrystals with finely modulated chiral fields and internal standards. Chiral electromagnetic fields are enhanced after modulation, which is conducive to increasing the difference in the enantiomeric SERS intensity, as evidenced by the experimental and simulation results. Furthermore, the SERS stability is improved by the corrective effect of the internal standards, and the relative standard deviation is significantly reduced. Using finely modulated chiral fields and internal standards, L‐ and D‐phenylalanine exhibit a stable six times difference in SERS ratio. Theoretical simulations reveal that linearly polarized light can also excite the chiral fields of chiral Au nanocrystals, indicating non‐chiral far‐field light is converted into chiral near‐field sources by chiral Au nanocrystals. Thus, the mechanism of enantioselective SERS can be elucidated by the scattering difference of chiral molecules in chiral near fields. This study will pave the way for the development of enantioselective SERS and related chiroptical technologies.