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.
Optical spectroscopy can be used to quickly characterise the structural properties of individual molecules. However, it cannot be applied to biological assemblies because light is generally blind to ...the spatial distribution of the component molecules. This insensitivity arises from the mismatch in length scales between the assemblies (a few tens of nm) and the wavelength of light required to excite chromophores (≥150 nm). Consequently, with conventional spectroscopy, ordered assemblies, such as the icosahedral capsids of viruses, appear to be indistinguishable isotropic spherical objects. This limits potential routes to rapid high-throughput portable detection appropriate for point-of-care diagnostics. Here, we demonstrate that chiral electromagnetic (EM) near fields, which have both enhanced chiral asymmetry (referred to as superchirality) and subwavelength spatial localisation (∼10 nm), can detect the icosahedral structure of virus capsids. Thus, they can detect both the presence and relative orientation of a bound virus capsid. To illustrate the potential uses of the exquisite structural sensitivity of subwavelength superchiral fields, we have used them to successfully detect virus particles in the complex milieu of blood serum.
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.
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.e., 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.
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.
Abstract
Manipulating symmetry environments of metal ions to control functional properties is a fundamental concept of chemistry. For example, lattice strain enables control of symmetry in solids ...through a change in the nuclear positions surrounding a metal centre. Light–matter interactions can also induce strain but providing dynamic symmetry control is restricted to specific materials under intense laser illumination. Here, we show how effective chemical symmetry can be tuned by creating a symmetry-breaking rotational bulk polarisation in the electronic charge distribution surrounding a metal centre, which we term a meta-crystal field. The effect arises from an interface-mediated transfer of optical spin from a chiral light beam to produce an electronic torque that replicates the effect of strain created by high pressures. Since the phenomenon does not rely on a physical rearrangement of nuclear positions, material constraints are lifted, thus providing a generic and fully reversible method of manipulating effective symmetry in solids.
Optimal performance of nanophotonic devices, including sensors and solar cells, requires maximizing the interaction between light and matter. This efficiency is optimized when active moieties are ...localized in areas where electromagnetic (EM) fields are confined. Confinement of matter in these 'hotspots' has previously been accomplished through inefficient 'top-down' methods. Here we report a rapid 'bottom-up' approach to functionalize selective regions of plasmonic nanostructures that uses nano-localized heating of the surrounding water induced by pulsed laser irradiation. This localized heating is exploited in a chemical protection/deprotection strategy to allow selective regions of a nanostructure to be chemically modified. As an exemplar, we use the strategy to enhance the biosensing capabilities of a chiral plasmonic substrate. This novel spatially selective functionalization strategy provides new opportunities for efficient high-throughput control of chemistry on the nanoscale over macroscopic areas for device fabrication.
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.
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 modeling and experimental measurements on an antibody–antigen exemplar system, important factors that influence the efficacy of chiral sensing are illustrated. It is demonstrated that localized and lattice chiral resonances display enantiomeric sensitivity. However, only the localized resonances show a 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, it is highlighted that surface morphology/defects may amplify sensing capabilities of localized chiral plasmonic modes by mediating inductive coupling.
Using chiral plasmonic structures provides a strategy for enhanced detection of chiral biological and pharmaceutical molecules. Herein, the factors that influence the effectiveness of chiral sensing with plasmonic structures are explored.
Transition metal oxides exhibit a rich collection of electronic properties and have many practical applications in areas such as catalysis and ultra-high-density magnetic data storage. Therefore the ...development of switchable molecular transition metal oxides has potential for the engineering of single-molecule devices and nanoscale electronics. At present, the electronic properties of transition metal oxides can only be tailored through the irreversible introduction of dopant ions, modifying the electronic structure by either injecting electrons or core holes. Here we show that a molybdenum(VI) oxide 'polyoxometalate' molecular nanocluster containing two embedded redox agents is activated by a metallic surface and can reversibly interconvert between two electronic states. Upon thermal activation two electrons are ejected from the active sulphite anions and delocalized over the metal oxide cluster cage, switching it from a fully oxidized state to a two-electron reduced state along with the concomitant formation of an S-S bonding interaction between the two sulphur centres inside the cluster shell.
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