Symmetry Reduction and Shape Effects in Concave Chiral Plasmonic Structures

Chiral metamaterials have shown a number of interesting properties which result from the interaction of the chiral near-field they produce with light and matter. We investigate the influence of structural imperfections on the plasmonic properties of a chiral gold “gammadion”, using electron energy loss spectroscopy to directly inform simulations of realistic, imperfect structures. Unlike structures of simple convex geometry, the lowest energy modes of the ideal concave gammadion have a quadrupole and dipole character, with the mode energies determined by the nature of electrostatic coupling between the gammadion arms. These modes are strongly affected by structural imperfections that are inherent to the material properties and lithographic patterning. Even subwavelength-scale imperfections reduce the symmetry, lift mode degeneracies convert dark modes into bright ones and significantly alter the mode energy, its near-field strength, and chirality. Such effects will be common to a number of multitipped concave structures currently being investigated for the chiral fields they support

Symmetry Reduction and Shape Effects in Concave Chiral Plasmonic Structures

Chiral metamaterials have shown a number of interesting properties which result from the interaction of the chiral near-field they produce with light and matter. We investigate the influence of structural imperfections on the plasmonic properties of a chiral gold “gammadion”, using electron energy loss spectroscopy to directly inform simulations of realistic, imperfect structures. Unlike structures of simple convex geometry, the lowest energy modes of the ideal concave gammadion have a quadrupole and dipole character, with the mode energies determined by the nature of electrostatic coupling between the gammadion arms. These modes are strongly affected by structural imperfections that are inherent to the material properties and lithographic patterning. Even subwavelength-scale imperfections reduce the symmetry, lift mode degeneracies convert dark modes into bright ones and significantly alter the mode energy, its near-field strength, and chirality. Such effects will be common to a number of multitipped concave structures currently being investigated for the chiral fields they support

Controlling Metamaterial Transparency with Superchiral Fields

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

Induced Chirality through Electromagnetic Coupling between Chiral Molecular Layers and Plasmonic Nanostructures

We report a new approach for creating chiral plasmonic nanomaterials. A previously unconsidered, far-field mechanism is utilized which enables chirality to be conveyed from a surrounding chiral molecular material to a plasmonic resonance of an achiral metallic nanostructure. Our observations break a currently held preconception that optical properties of plasmonic particles can most effectively be manipulated by molecular materials through near-field effects. We show that far-field electromagnetic coupling between a localized plasmon of a nonchiral nanostructure and a surrounding chiral molecular layer can induce plasmonic chirality much more effectively (by a factor of 10³) than previously reported near-field phenomena. We gain insight into the mechanism by comparing our experimental results to a simple electromagnetic model which incorporates a plasmonic object coupled with a chiral molecular medium. Our work offers a new direction for the creation of hybrid molecular plasmonic nanomaterials that display significant chiroptical properties in the visible spectral region

Chiral Plasmonic Fields Probe Structural Order of Biointerfaces

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 behavior 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 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

Superchiral Plasmonic Phase Sensitivity for Fingerprinting of Protein Interface Structure

The structure adopted by biomaterials, such as proteins, at interfaces is a crucial parameter in a range of important biological problems. It is a critical property in defining the functionality of cell/bacterial membranes and biofilms (<i>i.e.</i>, in antibiotic-resistant infections) and the exploitation of immobilized enzymes in biocatalysis. The intrinsically small quantities of materials at interfaces precludes the application of conventional spectroscopic phenomena routinely used for (bio)­structural analysis due to a lack of sensitivity. We show that the interaction of proteins with superchiral fields induces asymmetric changes in retardation phase effects of excited bright and dark modes of a chiral plasmonic nanostructure. Phase retardations are obtained by a simple procedure, which involves fitting the line shape of resonances in the reflectance spectra. These interference effects provide fingerprints that are an incisive probe of the structure of interfacial biomolecules. Using these fingerprints, layers composed of structurally related proteins with differing geometries can be discriminated. Thus, we demonstrate a powerful tool for the bioanalytical toolbox