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. A breakthrough is presented for utilising Raman spectroscopy in ultrasensitive biomolecular conformation detection, surpassing conventional Raman optical activity by 15 orders of magnitude. This strategy combines chiral plasmonic metasurfaces with achiral molecular Raman reporters and enables the detection of different conformations (α-helix and random coil) of a model peptide (poly-L/D-lysine) at the ≤attomole level (monolayer). This exceptional sensitivity stems from the ability to detect local, molecular-scale changes in the electromagnetic (EM) environment of a chiral nanocavity induced by the presence of biomolecules using molecular Raman reporters. Further signal enhancement is achieved by incorporating achiral Au nanoparticles. The introduction of the nanoparticles creates highly localized regions of extreme optical chirality. This approach, which exploits Raman, a generic phenomenon, paves the way for next-generation technologies for the ultrasensitive detection of diverse biomolecular structures.

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 TixOy 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.

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. Here, we exploit an intriguing phenomenon, plasmonic circularly polarized luminescence (PCPL), which is an incisive local probe of near field chirality. This allows the chiral detection of monolayer quantities of a de novo designed peptide, which is not achieved with a far field response. Our work demonstrates that by leveraging the capabilities of nanophotonic platforms with the near field sensitivity of PCPL, optimal biomolecular detection performance can be achieved, opening new avenues for nanometrology.

Determination of the preferred reaction pathway of acetophenone on Si(001) using photoelectron diffraction.

The adsorption configurations of a technologically relevant model organic adsorbate on the silicon (001) surface were studied using energy scanned x-ray photoelectron diffraction (PhD). Previous work has established the existence of an interesting vertically-aligned ('flagpole') configuration, where the acetophenone attaches to Si(001) via the acetyl group carbon and oxygen atoms. Density functional theory calculations have predicted two energetically similar variants of this structure, where the phenyl ring is orientated parallel or perpendicular to the rows of silicon dimers on this reconstructed surface. However, previously published experimental measurements, including scanning tunnelling microscopy, x-ray photoelectron spectroscopy, and near-edge x-ray absorption fine structure investigations were unable to distinguish between these two configurations. Here, we apply the unique experimental capabilities of the PhD technique to this system and demonstrate that the dominant adsorption configuration has the phenyl ring parallel to the dimer rows (the end-bridge structure). This information in turn facilitates the determination of the dominant reaction pathway for acetophenone on Si(001), which has remained elusive until now. Information about subtle preferences in reaction pathways that affect the alignment and orientation of organic adsorbates such as acetophenone on technologically-relevant semiconductor surfaces such as Si(001) is critical for the fabrication of future atomically-precise atomic and molecular-scale electronic devices utilising the organic-silicon interface, and this work demonstrates the unique and complementary capabilities of PhD for providing this information.