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, we proposed the coupling of disposable chiral plasmonic shurikens supporting the chiral near-field distribution with SERS active silver nanoclusters for enantio-selective sensing. As a result of the plasmonic coupling, significant difference in SERS response of optically active analytes is observed. The observations are studied by numerical simulations and it is hypothesized that the silver particles are being excited by superchiral fields generated at the surface inducing additional polarizations in the probe molecules. 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.

Light scattering from chiral plasmonic structures can create near fields with an asymmetry greater than the equivalent circularly polarised light, a property sometimes referred to as superchirality. These near fields with enhanced chiral asymmetries can be exploited for ultrasensitive detection of chiral (bio)molecules. In this combined experimental and numerical modelling study, we demonstrate that superchiral hot-spots are created around structural heterogeneities, such has protrusions and indentations, possessed by all real metal structures. These superchiral hot-spots, have chiral asymmetries greater than what would be expected from an idealised perfect structure. Our work indicates that surface morphology could play a role in determining the efficacy of a chiral structure for sensing.

Chiral near fields possessing enhanced asymmetry (superchirality), created by the interaction of light with (chiral) nanostructures, potentially provide a route to novel sensing and metrology technologies for biophysical applications. However, the mechanisms by which these near fields lead to the detection of chiral media is still poorly understood. Using a combination of numerical modelling and experimental measurements on an antibody-antigen exemplar system we illustrate important factors that influence the efficacy of chiral sensing. We demonstrate that localised and lattice chiral resonances display enantiomeric sensitivity. However, only the localised resonances exhibit strong dependency on the structure of the chiral media detected. This can be attributed to the ability of birefringent chiral layers to strongly modify the properties of near fields by acting as a sink / source of optical chirality, and hence alter inductive coupling between nanostructure elements. In addition, we highlight how surface morphology / defects may amplify sensing capabilities of localised chiral plasmonic modes by mediating inductive coupling.

Chiral biological and pharmaceutical molecules are analyzed with phenomena that monitor their very weak differential interaction with circularly polarized light. This inherent weakness results in detection levels for chiral molecules that are inferior, by at least six orders of magnitude, to the single molecule level achieved by state-of-the-art chirally insensitive spectroscopic measurements. Here, we show a phenomenon based on chiral quantum metamaterials (CQMs) that overcomes these intrinsic limits. Specifically, the emission from a quantum emitter, a semiconductor quantum dot (QD), selectively placed in a chiral nanocavity is strongly perturbed when individual biomolecules (here, antibodies) are introduced into the cavity. The effect is extremely sensitive, with six molecules per nanocavity being easily detected. The phenomenon is attributed to the CQM being responsive to significant local changes in the optical density of states caused by the introduction of the biomolecule into the cavity. These local changes in the metamaterial electromagnetic environment, and hence the biomolecules, are invisible to "classical" light-scattering-based measurements. Given the extremely large effects reported, our work presages next generation technologies for rapid hypersensitive measurements with applications in nanometrology and biodetection.

The ability to electrically control the optical properties of metamaterials is an essential capability required for technological innovation. The creation of dynamic electrically tunable metamaterials in the visible and near infrared regions is important for a range of imaging and fiber optic technologies. However, current approaches require complex nanofabrication processes which are incompatible for low‐cost device production. Herein, a novel simple approach is reported for electrical control of optical properties which uses a flexoelectric dielectric element to electromechanically manipulate the form factor of a chiral nanostructure. By altering the dimensions of the chiral nanostructure, the polarization properties of light are allowed to be electrically controlled. The flexoelectric element is part of a composite metafilm that is templated onto a nanostructured polymer substrate. As the flexoelectric element does not require in situ high temperature annealing, it can be readily combined with polymer‐based substrates produced by high throughput methods. This is not the case for piezoelectric elements, routinely used in microelectromechanical (MEM) devices which require high temperature processing. Consequently, combining amorphous flexoelectric dielectrics and low‐cost polymer‐based materials provides a route to the high throughput production of electrically responsive disposable metadevices.

Chiral plasmonic nanostructures enable ≤pg detection and characterization of biomaterials. The sensing capabilities are associated with the chiral asymmetry of the near fields, which locally can be greater than equivalent circularly polarized light, a property referred to as superchirality. However, sensing abilities do not simply scale with the magnitude of superchirality. We show that chiral molecular sensing is correlated to the thickness of a nanostructure. This observation is reconciled with a previously unconsidered interference mechanism for the sensing phenomenon. It involves the "dissipation" of optical chirality into chiral material currents through the interference of fields generated by two spatially separated chiral modes. The presence of a chiral dielectric causes an asymmetric change in the phase difference, resulting in asymmetric changes to chiroptical properties. Thus, designing a chiral plasmonic sensor requires engineering a substrate that can sustain both superchiral fields and an interference effect.