Resonant Plasmonic–Biomolecular Chiral Interactions in the Far-Ultraviolet: Enantiomeric Discrimination of sub-10 nm Amino Acid Films

Resonant plasmonic–molecular chiral interactions are a promising route to enhanced biosensing. However, biomolecular optical activity primarily exists in the far-ultraviolet regime, posing significant challenges for spectral overlap with current nano-optical platforms. We demonstrate experimentally and computationally the enhanced chiral sensing of a resonant plasmonic–biomolecular system operating in the far-UV. We develop a full-wave model of biomolecular films on Al gammadion arrays using experimentally derived chirality parameters. Our calculations show that detectable enhancements in the chiroptical signals from small amounts of biomolecules are possible only when tight spectral overlap exists between the plasmonic and biomolecular chiral responses. We support this conclusion experimentally by using Al gammadion arrays to enantiomerically discriminate ultrathin (<10 nm thick) films of tyrosine. Notably, the chiroptical signals of the bare films were within instrumental noise. Our results demonstrate the importance of using far-UV active metasurfaces for enhancing natural optical activity.