An Analysis of Semicircular Channel Backscattering Interferometry through Ray Tracing Simulations.

Recent backscattering interferometry studies utilise a single channel microfluidic system, typically approximately semicircular in cross-section. Here, we present a complete ray tracing model for on-chip backscattering interferometry with a semicircular cross-section, including the dependence upon polarisation and angle of incidence. The full model is validated and utilised to calculate the expected fringe patterns and sensitivities observed under both normal and oblique angles of incidence. Comparison with experimental data from approximately semicircular channels using the parameters stated shows that they cannot be explained using a semicircular geometry. The disagreement does not impact on the validity of the experimental data, but highlights that the optical mechanisms behind the various modalities of backscattering interferometry would benefit from clarification. From the analysis presented here, we conclude that for reasons of ease of analysis, data quality, and sensitivity for a given radius, capillary-based backscattering interferometry affords numerous benefits over on-chip backscattering interferometry.

Smooth Sidewalls on Crystalline Gold through Facet-Selective Anisotropic Reactive Ion Etching: Toward Low-Loss Plasmonic Devices.

Quantum plasmonics aims to harness the deeply subwavelength confinement provided by plasmonic devices to engineer more efficient interfaces to quantum systems in particular single emitters. Realizing this vision is hampered by the roughness-induced scattering and loss inherent in most nanofabricated devices. In this work, we show evidence of a reactive ion etching process to selectively etch gold along select crystalline facets. Since the etch is facet selective, the sidewalls of fabricated devices are smoother than the lithography induced line-edge roughness with the prospect of achieving atomic smoothness by further optimization of the etch chemistry. This opens up a route toward fabricating integrated plasmonic circuits that can achieve loss metrics close to fundamental bounds.

Determining nanorod dimensions in dispersion with size anisotropy nanoparticle tracking analysis.

Control over nanorod dimensions is critical to their application, requiring fast, robust characterisation of their volume and aspect ratio whilst in their working medium. Here, we present an extension of Nanoparticle Tracking Analysis which determines the aspect ratio of nanoparticles from the polarisation state of scattered light in addition to a hydrodynamic diameter from Brownian motion. These data, in principle, permit the determination of nanorod dimensions of any composition using Nanoparticle Tracking Analysis. The results are compared with transmission electron microscopy and show that this technique can additionally determine the aggregation state of the nanorod dispersion if single nanorod dimensions are determined with a complementary technique. We also show it is possible to differentiate nanoparticles of similar hydrodynamic diameter by their depolarised scattering. Finally, we assess the ability of the technique to output nanorod dimensions and suggest ways to further improve the approach. This technique will enable rapid characterisation of nanorods in suspension, which are important tools for nanotechnology.

Measuring the refractive index and sub-nanometre surface functionalisation of nanoparticles in suspension.

Direct measurements to determine the degree of surface coverage of nanoparticles by functional moieties are rare, with current strategies requiring a high level of expertise and expensive equipment. Here, a practical method to determine the ratio of the volume of the functionalisation layer to the particle volume based on measuring the refractive index of nanoparticles in suspension is proposed. As a proof of concept, this technique is applied to poly(methyl methacrylate) (PMMA) nanoparticles and semicrystalline carbon dots functionalised with different surface moieties, yielding refractive indices that are commensurate to those from previous literature and Mie theory. In doing so, it is demonstrated that this technique is able to optically detect differences in surface functionalisation or composition of nanometre-sized particles. This non-destructive and rapid method is well-suited for in situ industrial particle characterisation and biological applications.

Shedding Light on Capillary-Based Backscattering Interferometry.

Capillary-based backscattering interferometry has been used extensively as a tool to measure molecular binding via interferometric refractive index sensing. Previous studies have analysed the fringe patterns created in the backscatter direction. However, polarisation effects, spatial chirps in the fringe pattern and the practical impact of various approximations, and assumptions in existing models are yet to be fully explored. Here, two independent ray tracing approaches are applied, analysed, contrasted, compared to experimental data, and improved upon by introducing explicit polarisation dependence. In doing so, the significance of the inner diameter, outer diameter, and material of the capillary to the resulting fringe pattern and subsequent analysis are elucidated for the first time. The inner diameter is shown to dictate the fringe pattern seen, and therefore, the effectiveness of any dechirping algorithm, demonstrating that current dechirping methods are only valid for a subset of capillary dimensions. Potential improvements are suggested in order to guide further research, increase sensitivity, and promote wider applicability.

Laser-induced convection shifts size distributions in nanoparticle tracking analysis.

This work discusses the effects of increasing laser power on the size data derived from NTA for particles of known size and scatterers in solutions of flufenamic acid in ethanol. We find that whilst a higher laser power reveals more particles as expected, their residence time changes due to laser-induced convection. This reduced residence time decreases the number of tracks available for individual particle size determination, shifting the size distribution to smaller values. This problem is overcome by using a shutter to inhibit the development of convection currents, increasing particle residence time and reducing the error on the size distribution. The detailed understanding of laser-induced convection permits more robust size characterisation of mesoscopic organic clusters, which play a key role in two-step nucleation theory.

Diameter-optimized high-order waveguide nanorods for fluorescence enhancement applied in ultrasensitive bioassays.

Development of fluorescence enhancement (FE) platforms based on ZnO nanorods (NRs) has sparked considerable interest, thanks to their well-demonstrated potential in chemical and biological detection. Among the multiple factors determining the FE performance, high-order waveguide modes are specifically promising in boosting the sensitivity and realizing selective detection. However, quantitative experimental studies on the influence of the NR diameter, substrate, and surrounding medium, on the waveguide-based FE properties remain lacking. In this work, we have designed and fabricated a FE platform based on patterned and well-defined arrays of vertical, hexagonal prism ZnO NRs with six distinct diameters. Both direct experimental evidence and theoretical simulations demonstrate that high-order waveguide modes play a crucial role in FE, and are strongly dependent on the NR diameter, substrate, and surrounding medium. Using the optimized FE platform, a significant limit of detection (LOD) of 10-16 mol L-1 for Rhodamine-6G probe detection is achieved. Especially, a LOD as low as 10-14 g mL-1 is demonstrated for a prototype biomarker of carcinoembryonic antigen, which is improved by one order compared with the best LOD ever reported using fluorescence-based detection. This work provides an efficient path to design waveguiding NRs-based biochips for ultrasensitive and highly-selective biosensing.

Formation of Hypoxanthine Tetrad by Reaction with Sodium Chloride: From Planar to Stereo.

By reacting with NaCl on Au(111), the formation of hypoxanthine (HX) tetrads is demonstrated at the atomic scale in real space. These results directly demonstrate that alternative purine tetrads can be formed in both planar and non-planar configuration, and that ionic bonding plays a crucial role for the formation and planar-to-stereo transformation of the tetrads, providing deeper insight for constructing artificial DNA/RNA quadruplexes. Moreover, both the tilted HXs and Na show strong charge transfer with the substrate in the non-planar phase. The insights gained by this work also open up new routes to tune the electrostatic nature of metal-organic interfaces and design stereo-nanostructures on surfaces.

Direct Evidence of Lack of Colocalisation of Fluorescently Labelled Gold Labels Used in Correlative Light Electron Microscopy.

Fluorescently labelled nanoparticles are routinely used in Correlative Light Electron Microscopy (CLEM) to combine the capabilities of two separate microscope platforms: fluorescent light microscopy (LM) and electron microscopy (EM). The inherent assumption is that the fluorescent label observed under LM colocalises well with the electron dense nanoparticle observed in EM. Herein we show, by combining single molecule fluorescent imaging with optical detection of the scattering from single gold nanoparticles, that for a commercially produced sample of 10 nm gold nanoparticles tagged to Alexa-633 there is in fact no colocalisation between the fluorescent signatures of Alexa-633 and the scattering associated with the gold nanoparticle. This shows that the attached gold nanoparticle quenches the fluorescent signal by ~95%, or less likely that the complex has dissociated. In either scenario, the observed fluorescent signal in fact arises from a large population of untagged fluorophores; rendering these labels potentially ineffective and misleading to the field.

On the complex point spread function in interferometric cross-polarisation microscopy.

The ability to characterize the Point Spread Function(PSF) is crucial in practical microscopy, but requires knowledge of the complex PSF for approaches that detect fields instead of intensities. Here we experimentally measure and theoretically model the volumetric amplitude and phase response of an Interferometric Cross-polarisation Microscope to demonstrate the technique's capability to provide confocal-like images of weakly birefringent structures in living cells. We find the axial FWHM of the amplitude PSF to be 0.70 ± 0.01 µm and 0.83 µm for model and measurement, respectively, on par with confocal microscopy. Ultimately retaining both amplitude and phase information will however enable approaches for improved localisation of objects.

Combining near-field scanning optical microscopy with spectral interferometry for local characterization of the optical electric field in photonic structures.

We show how a combination of near-field scanning optical microscopy with crossed beam spectral interferometry allows a local measurement of the spectral phase and amplitude of light propagating in photonic structures. The method only requires measurement at the single point of interest and at a reference point, to correct for the relative phase of the interferometer branches, to retrieve the dispersion properties of the sample. Furthermore, since the measurement is performed in the spectral domain, the spectral phase and amplitude could be retrieved from a single camera frame, here in 70 ms for a signal power of less than 100 pW limited by the dynamic range of the 8-bit camera. The method is substantially faster than most previous time-resolved NSOM methods that are based on time-domain interferometry, which also reduced problems with drift. We demonstrate how the method can be used to measure the refractive index and group velocity in a waveguide structure.

Identification of molecular-adsorption geometries and intermolecular hydrogen-bonding configurations by in situ STM manipulation.

Don't be dim! By combining the technique with DFT calculations, STM manipulation was extended to the probing of intermolecular hydrogen-bonding configurations in self-assembled nanostructures. It was also possible to convert one configuration into another in a controlled fashion through the careful manipulation of a particular structural unit (see picture).

A molecular conformational change induced self-assembly: from randomness to order.

From an interplay of high-resolution scanning tunneling microscopy (STM) imaging and density functional theory (DFT) calculations we reveal how a molecular conformational change induced self-assembly process can result in the conversion from a random molecular phase to the formation of two types of ordered surface nanostructures with different apparent heights.

Homochiral xanthine quintet networks self-assembled on Au(111) surfaces.

Xanthine molecule is an intermediate in nucleic acid degradation from the deamination of guanine and is also a compound present in the ancient solar system that is found in high concentrations in extraterrestrial meteorites. The self-assembly of xanthine molecules on inorganic surfaces is therefore of interest for the study of biochemical processes, and it may also be relevant to the fundamental understanding of prebiotic biosynthesis. Using a combination of high-resolution scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, two new homochiral xanthine structures have been found on Au(111) under ultrahigh vacuum conditions. Xanthine molecules are found to be self-assembled into two extended homochiral networks tiled by two types of di-pentamer units and stabilized by intermolecular double hydrogen bonding. Our findings indicate that the deamination of guanine into xanthine leads to a very different base pairing potential and the chemical properties of the base which may be of relevance to the function of the cell and potential development of human diseases. Moreover, the adsorption of xanthine molecules on inorganic surfaces leading to homochiral assemblies may be of interest for the fundamental understanding of the emerged chirality at early stages of life.

Background-free detection of single 5 nm nanoparticles through interferometric cross-polarization microscopy.

Metal nanoparticles play a key role in sensing and imaging. Here we demonstrate the detection of metal particles down to 5 nm in size with a signal-to-noise ratio of ∼7 using interferometric cross-polarization microscopy at ultralow excitation powers (∼1 µW) compatible with single molecule detection. The method is background-free and induces no heating as it operates far from plasmonic resonance. The combination of unlimited observation time and protein-sized metal nanoparticles has great potential for biophysical applications.

Self-organization of gold-containing hydrogen-bonded rosette assemblies on graphite surface.

The self-organization of supramolecular structures, in particular gold-containing hydrogen-bonded rosettes, on highly oriented pyrolytic graphite (HOPG) surfaces was investigated by tapping-mode atomic force microscopy (TM-AFM) and scanning tunneling microscopy (STM). TM-AFM and high-resolution STM results show that these hydrogen-bonded assemblies self-organize to form highly ordered domains on HOPG surfaces. We find that a subtle change in one of the building blocks induces two different orientations of the assembly with respect to the surface. These results provide information on the control over the construction of supramolecular nanoarchitectures in 2D with the potential for the manufacturing of functional materials based on structural manipulation of molecular components.