Synthesis of Fluorescent Dibenzofuran α-Amino Acids: Conformationally Rigid Analogues of Tyrosine.

We report two synthetic strategies for the preparation of dibenzofuran α-amino acids, expanding the structural toolbox of fluorescent probes. The strategies involved dibenzofuran synthesis via a Pd(II)-catalyzed C-O cyclization, alongside an efficient Negishi coupling approach for faster access to analogues. These rigid tyrosine mimics possess enhanced fluorescent properties compared to proteinogenic amino acids as demonstrated by application of the lead compound as a FRET donor for monitoring peptide hydrolysis by a serine protease.

Electromagnetic Enantiomer: Chiral Nanophotonic Cavities for Inducing Chemical Asymmetry.

Chiral molecules, a cornerstone of chemical sciences with applications ranging from pharmaceuticals to molecular electronics, come in mirror-image pairs called enantiomers. However, their synthesis often requires complex control of their molecular geometry. We propose a strategy called "electromagnetic enantiomers" for inducing chirality in molecules located within engineered nanocavities using light, eliminating the need for intricate molecular design.

Spatial Control of 2D Nanomaterial Electronic Properties Using Chiral Light Beams.

Single-layer two-dimensional (2D) nanomaterials exhibit physical and chemical properties which can be dynamically modulated through out-of-plane deformations. Existing methods rely on intricate micromechanical manipulations (., poking, bending, rumpling), hindering their widespread technological implementation.

Ultrasensitive Raman Detection of Biomolecular Conformation at the Attomole Scale using Chiral Nanophotonics.

Understanding the function of a biomolecule hinges on its 3D conformation or secondary structure. Chirally sensitive, optically active techniques based on the differential absorption of UV-vis circularly polarized light excel at rapid characterisation of secondary structures. However, Raman spectroscopy, a powerful method for determining the structure of simple molecules, has limited capacity for structural analysis of biomolecules because of intrinsically weak optical activity, necessitating millimolar (mM) sample quantities.

Evaluating the native oxide of titanium as an electrocatalyst for oxalic acid reduction.

Herein, we show that unmodified titanium electrodes bearing the naturally-forming native TiO coating display superior activity for the electroreduction of oxalic acid to glyoxylic acid and glycolic acid compared to Ti-based electrodes that have been deliberately modified for this purpose, in terms of both oxalic acid conversion and overall yields of reduced products.

Fluorescent carbazole-derived α-amino acids: structural mimics of tryptophan.

Fluorescent tags are commonly used for imaging of proteins and peptides during biological events; however, the large size of dyes can disrupt protein structure and function, and typically require the use of a chemical spacer. Herein, we report the synthesis of a new class of fluorescent unnatural α-amino acid, containing carbazole side-chains designed to mimic l-tryptophan and thus, readily incorporated into peptides. The amino acids were constructed using a Negishi cross-coupling reaction as the key step and exhibited strong fluorescent emission, with high quantum yields in both organic solvents and water.

Tuning dipolar and multipolar resonances of chiral silicon nanostructures for control of near field superchirality.

Chiral materials display a property called optical activity, which is the capability to interact differentially with left and right circularly polarised light. This leads to the ability to manipulate the polarisation state of light, which has a broad range of applications spanning from energy efficient displays to quantum technologies. Both synthesised and engineered chiral nanomaterials are exploited in such devices.

Multiplexed Biosensing of Proteins and Virions with Disposable Plasmonic Assays.

Our growing ability to tailor healthcare to the needs of individuals has the potential to transform clinical treatment. However, the measurement of multiple biomarkers to inform clinical decisions requires rapid, effective, and affordable diagnostics. Chronic diseases and rapidly evolving pathogens in a larger population have also escalated the need for improved diagnostic capabilities.

Coupling of plasmonic hot spots with shurikens for superchiral SERS-based enantiomer recognition.

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.

Near-Field Probing of Optical Superchirality with Plasmonic Circularly Polarized Luminescence for Enhanced Bio-Detection.

Nanophotonic platforms in theory uniquely enable < femtomoles of chiral biological and pharmaceutical molecules to be detected, through the highly localized changes in the chiral asymmetries of the near fields that they induce. However, current chiral nanophotonic based strategies are intrinsically limited because they rely on far field optical measurements that are sensitive to a much larger near field volume, than that influenced by the chiral molecules. Consequently, they depend on detecting small changes in far field optical response restricting detection sensitivities.

Chiral Quantum Metamaterial for Hypersensitive Biomolecule Detection.

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.

Superchiral near fields detect virus structure.

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).

Controlling the symmetry of inorganic ionic nanofilms with optical chirality.

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.

Probing Specificity of Protein-Protein Interactions with Chiral Plasmonic Nanostructures.

Protein-protein interactions (PPIs) play a pivotal role in many biological processes. Discriminating functionally important well-defined protein-protein complexes formed by specific interactions from random aggregates produced by nonspecific interactions is therefore a critical capability. While there are many techniques which enable rapid screening of binding affinities in PPIs, there is no generic spectroscopic phenomenon which provides rapid characterization of the structure of protein-protein complexes.

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.

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.e.

Biomacromolecular Stereostructure Mediates Mode Hybridization in Chiral Plasmonic Nanostructures.

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.

Spatial control of chemical processes on nanostructures through nano-localized water heating.

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.

Disposable Plasmonics: Plastic Templated Plasmonic Metamaterials with Tunable Chirality.

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.

"Superchiral" Spectroscopy: Detection of Protein Higher Order Hierarchical Structure with Chiral Plasmonic Nanostructures.

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.

The origin of off-resonance non-linear optical activity of a gold chiral nanomaterial.

We demonstrate that engineered artificial gold chiral nanostructures display significant levels of non-linear optical activity even without plasmonic enhancement. Our work suggests that although plasmonic excitation enhances the intensity of second harmonic emission it is not a prerequisite for significant non-linear (second harmonic) optical activity. It is also shown that the non-linear optical activities of both the chiral nanostructures and simple chiral molecules on surfaces have a common origin, namely pure electric dipole excitation.

Chiral electromagnetic fields generated by arrays of nanoslits.

Using a modal matching theory, we demonstrate the generation of short-range, chiral electromagnetic fields via the excitation of arrays of staggered nanoslits that are chiral in two dimensions. The electromagnetic near fields, which exhibit a chiral density greater than that of circularly polarized light, can enhance the chiroptical interactions in the vicinity of the nanoslits. We discuss the features of nanostructure symmetry required to obtain the chiral fields and explicitly show how these structures can give rise to detection and characterization of materials with chiral symmetry.

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.

Probing the chemical and electronic properties of the core-shell architecture of transition metal trisulfide nanoribbons.

Ultraviolet and X-ray photoelectron spectroscopies are used to probe the chemical and electronic structure of an amorphous, 2-20 nm-thick shell that encases the crystalline core in core-shell nanoribbons of TaS(3). The shell is chemically heterogeneous, containing elemental sulfur and a with a notable (S(2))(2-) deficiency over the crystalline TaS(3) core. We find nanoribbon stability to be substrate-dependent; whilst the ribbons are stable on the native oxide of a silicon surface, mass transport of sulfur species between the amorphous shell and a gold substrate leads to a significant change in the electronic properties of the nanomaterials.

Ultrasensitive detection and characterization of biomolecules using superchiral fields.

The spectroscopic analysis of large biomolecules is important in applications such as biomedical diagnostics and pathogen detection, and spectroscopic techniques can detect such molecules at the nanogram level or lower. However, spectroscopic techniques have not been able to probe the structure of large biomolecules with similar levels of sensitivity. Here, we show that superchiral electromagnetic fields, generated by the optical excitation of plasmonic planar chiral metamaterials, are highly sensitive probes of chiral supramolecular structure.