Coupling of Plasmonic Hot Spots with Shurikens for Superchiral SERS-based Enantiomer Recognition

Detection of enantiomers is a challenging problem in drug development as well as environmental and food quality monitoring where traditional optical detection methods suffer from low signals and sensitivity. Application of surface enhanced Raman scattering (SERS) for enantiomeric discrimination is a powerful approach for the analysis of optically active small organic or large biomolecules. In this work, for enantio-selective sensing we proposed the coupling of disposable chiral plasmonic shurikens supporting the chiral near-field distribution with SERS active silver nanoclusters. As a result of the plasmonic coupling significant difference in SERS response of optically active analytes is observed. This is hypothesized and confirmed by numerical simulations to be a consequence of the silver particles being excited by superchiral fields generated at the surface or the probe molecules achieving additional polarization. The plasmon coupling phenomena was found to be extremely sensitive to slight variations in shuriken geometry, silver nanostructured layer parameters, and SERS excitation wavelength(s). Designed structures were able to discriminate cysteine enantiomers at concentrations in the nanomolar range and probe biomolecular chirality, using a common Raman spectrometer within several minutes. The combination of disposable plasmonic substrates with specific near-field polarization can make the SERS enantiomer discrimination a commonly available technique using standard Raman spectrometers.