Ultra-fastin vivodirectional dark-field x-ray imaging for visualising magnetic control of particles for airway gene delivery.

Objective.Magnetic nanoparticles can be used as a targeted delivery vehicle for genetic therapies. Understanding how they can be manipulated within the complex environment of live airways is key to their application to cystic fibrosis and other respiratory diseases.Approach.Dark-field x-ray imaging provides sensitivity to scattering information, and allows the presence of structures smaller than the detector pixel size to be detected. In this study, ultra-fast directional dark-field synchrotron x-ray imaging was utlilised to understand how magnetic nanoparticles move within a live, anaesthetised, rat airway under the influence of static and moving magnetic fields.Main results.Magnetic nanoparticles emerging from an indwelling tracheal cannula were detectable during delivery, with dark-field imaging increasing the signal-to-noise ratio of this event by 3.5 times compared to the x-ray transmission signal. Particle movement as well as particle retention was evident. Dynamic magnetic fields could manipulate the magnetic particlesin situ. Significance.This is the first evidence of the effectiveness ofin vivodark-field imaging operating at these spatial and temporal resolutions, used to detect magnetic nanoparticles. These findings provide the basis for further development toward the effective use of magnetic nanoparticles, and advance their potential as an effective delivery vehicle for genetic agents in the airways of live organisms.

Effect of elexacaftor-tezacaftor-ivacaftor on nasal potential difference and lung function in Phe508del rats.

Introduction: Phe508del is the most common cystic fibrosis transmembrane conductance regulator (CFTR) gene variant that results in the recessive genetic disorder cystic fibrosis (CF). The recent development of highly effective CFTR modulator therapies has led to significant health improvements in individuals with this mutation. While numerous animal models of CF exist, few have a CFTR mutation that is amenable to the triple combination therapy elexacaftor-tezacaftor-ivacaftor (ETI). Methods: To determine the responsiveness of Phe508del rats to ETI, a baseline nasal potential difference was measured. Subsequently, they received ETI daily for 14 days, after which post-treatment nasal potential difference, lung mechanics (via flexiVent) and lung ventilation (via X-ray Velocimetry) were assessed. Results: Chloride ion transport in nasal airways was restored in Phe508del rats treated with ETI, but neither lung mechanics nor ventilation were significantly altered. Discussion: These findings validate the usefulness of this rat model for future investigations of modulator therapy in CF.

High-speed processing of X-ray wavefront marking data with the Unified Modulated Pattern Analysis (UMPA) model.

Wavefront-marking X-ray imaging techniques use e.g., sandpaper or a grating to generate intensity fluctuations, and analyze their distortion by the sample in order to retrieve attenuation, phase-contrast, and dark-field information. Phase contrast yields an improved visibility of soft-tissue specimens, while dark-field reveals small-angle scatter from sub-resolution structures. Both have found many biomedical and engineering applications. The previously developed Unified Modulated Pattern Analysis (UMPA) model extracts these modalities from wavefront-marking data. We here present a new UMPA implementation, capable of rapidly processing large datasets and featuring capabilities to greatly extend the field of view. We also discuss possible artifacts and additional new features.

X-ray directional dark-field imaging using Unified Modulated Pattern Analysis.

X-ray directional dark-field imaging is a recent technique that can reveal a sample's small-scale structural properties which are otherwise invisible in a conventional imaging system. In particular, directional dark-field can detect and quantify the orientation of anisotropic structures. Here, we present an algorithm that allows for the extraction of a directional dark-field signal from X-ray speckle-based imaging data. The experimental setup is simple, as it requires only the addition of a diffuser to a full-field microscope setup. Sandpaper is an appropriate diffuser material in the hard x-ray regime. We propose an approach to extract the mean scattering width, directionality, and orientation from the recorded speckle images acquired with the technique. We demonstrate that our method can detect and quantify the orientation of fibres inside a carbon fibre reinforced polymer (CFRP) sample within one degree of accuracy and show how the accuracy depends on the number of included measurements. We show that the reconstruction parameters can be tuned to increase or decrease accuracy at the expense of spatial resolution.

Mechanochromic and Thermochromic Sensors Based on Graphene Infused Polymer Opals.

High quality opal-like photonic crystals containing graphene are fabricated using evaporation-driven self-assembly of soft polymer colloids. A miniscule amount of pristine graphene within a colloidal crystal lattice results in the formation of colloidal crystals with a strong angle-dependent structural color and a stop band that can be reversibly shifted across the visible spectrum. The crystals can be mechanically deformed or can reversibly change color as a function of their temperature, hence their sensitive mechanochromic and thermochromic response make them attractive candidates for a wide range of visual sensing applications. In particular, it is shown that the crystals are excellent candidates for visual strain sensors or integrated time-temperature indicators which act over large temperature windows. Given the versatility of these crystals, this method represents a simple, inexpensive, and scalable approach to produce multifunctional graphene infused synthetic opals and opens up exciting applications for novel solution-processable nanomaterial based photonics.

Spectroscopic metrics allow in situ measurement of mean size and thickness of liquid-exfoliated few-layer graphene nanosheets.

Liquid phase exfoliation is a powerful and scalable technique to produce defect-free mono- and few-layer graphene. However, samples are typically polydisperse and control over size and thickness is challenging. Notably, high throughput techniques to measure size and thickness are lacking. In this work, we have measured the extinction, absorption, scattering and Raman spectra for liquid phase exfoliated graphene nanosheets of various lateral sizes (90 ≤ 〈L〉 ≤ 810 nm) and thicknesses (2.7 ≤ 〈N〉 ≤ 10.4). We found all spectra to show well-defined dependences on nanosheet dimensions. Measurements of extinction and absorption spectra of nanosheet dispersions showed both peak position and spectral shape to vary with nanosheet thickness in a manner consistent with theoretical calculations. This allows the development of empirical metrics to extract the mean thickness of liquid dispersed nanosheets from an extinction (or absorption) spectrum. While the scattering spectra depended on nanosheet length, poor signal to noise ratios made the resultant length metric unreliable. By analyzing Raman spectra measured on graphene nanosheet networks, we found both the D/G intensity ratio and the width of the G-band to scale with mean nanosheet length allowing us to establish quantitative relationships. In addition, we elucidate the variation of 2D/G band intensities and 2D-band shape with the mean nanosheet thickness, allowing us to establish quantitative metrics for mean nanosheet thickness from Raman spectra.

Preparation of Liquid-exfoliated Transition Metal Dichalcogenide Nanosheets with Controlled Size and Thickness: A State of the Art Protocol.

We summarize recent advances in the production of liquid-exfoliated transition metal dichalcogenide (TMD) nanosheets with controlled size and thickness. Layered crystals of molybdenum disulphide (MoS2) and tungsten disulphide (WS2) are exfoliated in aqueous surfactant solution by sonication. This yields highly polydisperse mixtures containing nanosheets with broad size and thickness distributions. However, for most purposes, specific sizes (in terms of both lateral dimension and thickness) are required. For example, large and thin nanosheets are desired for (opto) electronic applications, while laterally small nanosheets are interesting for catalytic applications. Therefore, post-exfoliation size selection is an important step that we address here. We provide a detailed protocol on the efficient size selection in large quantities by liquid cascade centrifugation and the size and thickness quantification by statistical microscopic analysis (atomic force microscopy and transmission electron microscopy). The comparison of MoS2 and WS2 shows that both materials are size-selected in a similar way by the same procedure. Importantly, the dispersions of size-selected nanosheets show systematic changes in their optical extinction spectra with size due to edge and confinement effects. We show how these optical changes are related quantitatively to the nanosheets dimensions and describe how mean nanosheets length and layer number can be extracted reliably from the extinction spectra. The exfoliation and size selection protocol can be applied to a broad range of layered crystals as we have previously demonstrated for graphene, gallium sulphide (GaS) and black phosphorus.

Edge and confinement effects allow in situ measurement of size and thickness of liquid-exfoliated nanosheets.

Two-dimensional nanomaterials such as MoS2 are of great interest both because of their novel physical properties and their applications potential. Liquid exfoliation, an important production method, is limited by our inability to quickly and easily measure nanosheet size, thickness or concentration. Here we demonstrate a method to simultaneously determine mean values of these properties from an optical extinction spectrum measured on a liquid dispersion of MoS2 nanosheets. The concentration measurement is based on the size-independence of the low-wavelength extinction coefficient, while the size and thickness measurements rely on the effect of edges and quantum confinement on the optical spectra. The resultant controllability of concentration, size and thickness facilitates the preparation of dispersions with pre-determined properties such as high monolayer-content, leading to first measurement of A-exciton MoS2 luminescence in liquid suspensions. These techniques are general and can be applied to a range of two-dimensional materials including WS2, MoSe2 and WSe2.

Turbulence-assisted shear exfoliation of graphene using household detergent and a kitchen blender.

To facilitate progression from the lab to commercial applications, it will be necessary to develop simple, scalable methods to produce high quality graphene. Here we demonstrate the production of large quantities of defect-free graphene using a kitchen blender and household detergent. We have characterised the scaling of both graphene concentration and production rate with the mixing parameters: mixing time, initial graphite concentration, rotor speed and liquid volume. We find the production rate to be invariant with mixing time and to increase strongly with mixing volume, results which are important for scale-up. Even in this simple system, concentrations of up to 1 mg ml(-1) and graphene masses of >500 mg can be achieved after a few hours mixing. The maximum production rate was ∼0.15 g h(-1), much higher than for standard sonication-based exfoliation methods. We demonstrate that graphene production occurs because the mean turbulent shear rate in the blender exceeds the critical shear rate for exfoliation.

Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids.

To progress from the laboratory to commercial applications, it will be necessary to develop industrially scalable methods to produce large quantities of defect-free graphene. Here we show that high-shear mixing of graphite in suitable stabilizing liquids results in large-scale exfoliation to give dispersions of graphene nanosheets. X-ray photoelectron spectroscopy and Raman spectroscopy show the exfoliated flakes to be unoxidized and free of basal-plane defects. We have developed a simple model that shows exfoliation to occur once the local shear rate exceeds 10(4) s(-1). By fully characterizing the scaling behaviour of the graphene production rate, we show that exfoliation can be achieved in liquid volumes from hundreds of millilitres up to hundreds of litres and beyond. The graphene produced by this method performs well in applications from composites to conductive coatings. This method can be applied to exfoliate BN, MoS2 and a range of other layered crystals.

Two-dimensional nanosheets produced by liquid exfoliation of layered materials.

If they could be easily exfoliated, layered materials would become a diverse source of two-dimensional crystals whose properties would be useful in applications ranging from electronics to energy storage. We show that layered compounds such as MoS(2), WS(2), MoSe(2), MoTe(2), TaSe(2), NbSe(2), NiTe(2), BN, and Bi(2)Te(3) can be efficiently dispersed in common solvents and can be deposited as individual flakes or formed into films. Electron microscopy strongly suggests that the material is exfoliated into individual layers. By blending this material with suspensions of other nanomaterials or polymer solutions, we can prepare hybrid dispersions or composites, which can be cast into films. We show that WS(2) and MoS(2) effectively reinforce polymers, whereas WS(2)/carbon nanotube hybrid films have high conductivity, leading to promising thermoelectric properties.

Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions.

We have demonstrated a method to disperse and exfoliate graphite to give graphene suspended in water-surfactant solutions. Optical characterization of these suspensions allowed the partial optimization of the dispersion process. Transmission electron microscopy showed the dispersed phase to consist of small graphitic flakes. More than 40% of these flakes had <5 layers with approximately 3% of flakes consisting of monolayers. Atomic resolution transmission electron microscopy shows the monolayers to be generally free of defects. The dispersed graphitic flakes are stabilized against reaggregation by Coulomb repulsion due to the adsorbed surfactant. We use DLVO and Hamaker theory to describe this stabilization. However, the larger flakes tend to sediment out over approximately 6 weeks, leaving only small flakes dispersed. It is possible to form thin films by vacuum filtration of these dispersions. Raman and IR spectroscopic analysis of these films suggests the flakes to be largely free of defects and oxides, although X-ray photoelectron spectroscopy shows evidence of a small oxide population. Individual graphene flakes can be deposited onto mica by spray coating, allowing statistical analysis of flake size and thickness. Vacuum filtered films are reasonably conductive and are semitransparent. Further improvements may result in the development of cheap transparent conductors.