Optical spectroscopic methods do not routinely provide information on higher order hierarchical structure (tertiary/quaternary) of biological macromolecules and assemblies. This necessitates the use of time-consuming and material intensive techniques, such as protein crystallography, NMR, and electron microscopy. Here we demonstrate a spectroscopic phenomenon, superchiral polarimetry, which can rapidly characterize ligand-induced changes in protein higher order (tertiary/quaternary) structure at the picogram level, which is undetectable using conventional CD spectroscopy. This is achieved by utilizing the enhanced sensitivity of superchiral evanescent fields to mesoscale chiral structure.

Development of low‐cost disposable plasmonic substrates is vital for the applicability of plasmonic sensing. Such devices can be made using injection‐molded templates to create plasmonic films. The elements of these plasmonic films are hybrid nanostructures composed of inverse and solid structures. Tuning the modal coupling between the two allows optimization of the optical properties for nanophotonic applications.

The structural order of biopolymers, such as proteins, at interfaces defines the physical and chemical interactions of biological systems with their surroundings, and is hence a critical parameter in a range of biological problems. Known spectroscopic methods for routine rapid monitoring of structural order in biolayers are generally only applied to model single component systems that possess a spectral fingerprint which is highly sensitive to orientation. This spectroscopic behaviour is not a generic property and may require the addition of a label. Importantly, such techniques cannot readily be applied to real multicomponent biolayers, have ill-defined, or unknown compositions, and have complex spectroscopic signatures with many overlapping bands. Here we demonstrate the sensitivity of plasmonic fields with enhanced chirality, a property referred to as superchirality, to global orientational order within both simple model and “real” complex protein layers. The sensitivity to structural order is derived from the capability of superchiral fields to detect the anisotropic nature of electric dipole-magnetic dipole response of the layer; this is validated by numerical simulations. As a model study, the evolution of orientational order with increasing surface density in layers of the antibody immunoglobulin G (IgG) was monitored. As an exemplar of greater complexity, superchiral fields are demonstrated, without knowledge of exact composition, to be able to monitor how qualitative changes in composition alter the structural order of protein layers formed from blood serum, thereby establishing the efficacy of the phenomenon as a tool for studying complex biological interfaces.

The refractive index sensitivity of plasmonic fields has been exploited for over 20 years in analytical technologies. While this sensitivity can be used to achieve attomole detection levels, they are in essence binary measurements that sense the presence/absence of a predetermined analyte. Using plasmonic fields, not to sense effective refractive indices but to provide more “granular” information about the structural characteristics of a medium, provides a more information rich output, which affords opportunities to create new powerful and flexible sensing technologies not limited by the need to synthesize chemical recognition elements. Here we report a new plasmonic phenomenon that is sensitive to the biomacromolecular structure without relying on measuring effective refractive indices. Chiral biomaterials mediate the hybridization of electric and magnetic modes of a chiral solid-inverse plasmonic structure, resulting in a measurable change in both reflectivity and chiroptical properties. The phenomenon originates from the electric-dipole–magnetic-dipole response of the biomaterial and is hence sensitive to biomacromolecular secondary structure providing unique fingerprints of α-helical, β-sheet, and disordered motifs. The phenomenon can be observed for subchiral plasmonic fields (i.e., fields with a lower chiral asymmetry than circularly polarized light) hence lifting constraints to engineer structures that produce fields with enhanced chirality, thus providing greater flexibility in nanostructure design. To demonstrate the efficacy of the phenomenon, we have detected and characterized picogram quantities of simple model helical biopolymers and more complex real proteins.

The advent of metamaterials has heralded a period of unprecedented control of light. The optical responses of metamaterials are determined by the properties of constituent nanostructures. The current design philosophy for tailoring metamaterial functionality is to use geometry to control the nearfield coupling of the elements of the nanostructures. A drawback of this geometry-focused strategy is that the functionality of a metamaterial is predetermined and cannot be manipulated easily postfabrication. Here we present a new design paradigm for metamaterials, in which the coupling between chiral elements of a nanostructure is controlled by the chiral asymmetries of the nearfield, which can be externally manipulated. We call this mechanism dichroic coupling. This phenomenon is used to control the electromagnetic induced transparency displayed by a chiral metamaterial by tuning the chirality of the near fields. This “non-geometric” paradigm for controlling optical properties offers the opportunity to optimally design chiral metamaterials for applications in the polarization state control and for ultrasensitive analysis of biomaterials and soft matter.