A Charge-Transfer-Induced Strategy for Enantioselective Discrimination by Potential-Regulated Surface-Enhanced Raman Scattering Spectroscopy.

Abstract

A simple and efficient enantioselective discrimination method, especially the chirality-label-free discrimination method, for the recognition of chiral small molecules with high resolution and wide applicability has been urgently desired. Herein, achiral Au/p-aminothiophenol (PATP) substrates were prepared to link the enantiomers via coupling reactions for constructing the enantioselective discrimination system. The resultant Au/PATP/enantiomer systems displayed charge-transfer (CT)-induced surface-enhanced Raman scattering (SERS) spectra that offered distinguishable information for the systems with different chirality. The differentiated spectral signal can be amplified by regulating the applied electrode potential, leading to great enantioselective discrimination performance. Moreover, the relationship between the discrimination performance and the potential-regulated CT process was revealed by SERS, which enabled an accurate and effective enantiomeric determination for various chiral molecules, including aromatic and aliphatic small molecules. The aliphatic molecule with the shorter chain was discriminated with a higher resolution, since the longer-chain molecule in the discrimination system may cause a change in the molecular electronic structure of the PATP. In addition, the aromatic chiral molecule can be distinguished easier than the aliphatic molecules, which means that the generation of the conjugation of electrons in the aromatic molecule-involved enantiomeric systems facilitates CT-induced SERS discrimination. Our work provides guidance for the design and development of an effective enantioselective discrimination strategy with high discrimination performance in diverse application fields.