Catriona M. McGilvery

DNA tunneling detector embedded in a nanopore.

We report on the fabrication and characterization of a DNA nanopore detector with integrated tunneling electrodes. Functional tunneling devices were identified by tunneling spectroscopy in different solvents and then used in proof-of-principle experiments demonstrating, for the first time, concurrent tunneling detection and ionic current detection of DNA molecules in a nanopore platform. This is an important step toward ultrafast DNA sequencing by tunneling.

Evidence for supercurrent connectivity in conglomerate particles in NdFeAsO1−δ

Here we report the use of global and local magnetometry and Hall probe imaging to investigate the electromagnetic connectivity of the superconducting current path in the oxygen-deficient fluorine-free Nd-based oxypnictides. High resolution transmission electron microscopy and scanning electron microscopy show strongly layered crystallites, evidence for a ~5?nm amorphous oxide around individual particles, and second phase neodymium oxide which may contribute to the large paramagnetic background at high field and at high temperatures. From global magnetometry and electrical transport measurements it is clear that there is a small supercurrent flowing on macroscopic sample dimensions (mm), with a lower bound for the average (over this length scale) critical current density of the order of 103?A?cm?2. From magnetometry of powder samples and local Hall probe imaging of a single large conglomerate particle ~120??m it is clear that, on smaller scales, there is better current connectivity with a critical current density of the order of 5 ? 104?A?cm?2. We find enhanced flux creep around the second peak anomaly in the magnetization curve and an irreversibility line significantly below Hc2(T) as determined by ac calorimetry.

Micro-to nano-scale characterisation of polyamide structures of the SW30HR RO membrane using advanced electron microscopy and stain tracers

The development of new reverse osmosis (RO) membranes with enhanced performance would benefit from a detailed knowledge of the membrane structures which participate in the filtration process. Here, we examined the hierarchical structures of the polyamide (PA) active layer of the SW30HR RO membrane. Scanning electron microscopy combined with focused ion beam milling (FIB-SEM) was used to obtain the 3-D reconstructions of membrane morphology with 5 nm cross-sectional resolution (comparable with the resolution of low magnification TEM imaging in 2D) and 30 nm slice thickness. The complex folding of the PA layer was examined in 3 dimensions, enabling the quantification of key structural properties of the PA layer, including the local thickness, volume, surface area and their derivatives. The PA layer was found to exhibit a much higher and convoluted surface area than that estimated via atomic force microscopy (AFM). Cross-sectional scanning transmission electron microscopy (STEM) was used to observe the distribution of a tracer stain under various conditions. The behaviour of stain in dry and wet PA indicated that the permeation pathways have a dynamic nature and are activated by water. High resolution STEM imaging of the stained PA nano-films revealed the presence of <1 nm pore-like structures with a size compatible with free volume estimations by positron annihilation lifetime spectroscopy (PALS). This study presents a comprehensive map of the active PA layer across different length scales (from micro- to sub-nanometre) and mechanistic insight into their role in the permeation process.

The effect of columnar defects on the pinning properties of NdFeAsO0.85 conglomerate particles

Oxypnictide superconductor NdFeAsO0.85 sample was irradiated with 2 GeV Ta ions at a fluence of 5x10^10 ions/cm2. High resolution transmission electron microscopy study revealed that the irradiation produced columnar-like defects. The effect of these defects on the irreversible magnetisation in polycrystalline randomly oriented fragments was studied as a function of field angle and field sweep rate. We find that the critical current density is enhanced at fields below the matching field (~1 Tesla) but only marginally. The pinning enhancement is anisotropic and maximum along the defect direction at high temperatures but the pinning then becomes more isotropic at low temperatures. The creep rate is suppressed at high temperatures and at fields below the matching field, indicating the columnar defects are efficient pinning sites at these H and T conditions.

Mechanistic link between diesel exhaust particles and respiratory reflexes

Background: Diesel exhaust particles (DEPs) are a major component of particulate matter in Europes largest cities, and epidemiologic evidence links exposure with respiratory symptoms and asthma exacerbations. Respiratory reflexes are responsible for symptoms and are regulated by vagal afferent nerves, which innervate the airway. It is not known how DEP exposure activates airway afferents to elicit symptoms, such as cough and bronchospasm. Objective: We sought to identify the mechanisms involved in activation of airway sensory afferents by DEPs. Methods: In this study we use in vitro and in vivo electrophysiologic techniques, including a unique model that assesses depolarization (a marker of sensory nerve activation) of human vagus. Results: We demonstrate a direct interaction between DEP and airway C‐fiber afferents. In anesthetized guinea pigs intratracheal administration of DEPs activated airway C‐fibers. The organic extract (DEP‐OE) and not the cleaned particles evoked depolarization of guinea pig and human vagus, and this was inhibited by a transient receptor potential ankyrin‐1 antagonist and the antioxidant N‐acetyl cysteine. Polycyclic aromatic hydrocarbons, major constituents of DEPs, were implicated in this process through activation of the aryl hydrocarbon receptor and subsequent mitochondrial reactive oxygen species production, which is known to activate transient receptor potential ankyrin‐1 on nociceptive C‐fibers. Conclusions: This study provides the first mechanistic insights into how exposure to urban air pollution leads to activation of guinea pig and human sensory nerves, which are responsible for respiratory symptoms. Mechanistic information will enable the development of appropriate therapeutic interventions and mitigation strategies for those susceptible subjects who are most at risk.

Contamination of holey/lacey carbon films in STEM.

In many cases, the key to obtaining good TEM results is in the sample preparation itself. Even once a thin specimen is achieved, other factors determine how well the sample will behave in the microscope. One of the main hindrances to TEM and STEM-EELS analysis is the build up of carbon contamination on the sample under the electron beam. This process may occur due to the nature of the sample itself or the support grids or films on which the sample sits. Here, we investigate contamination on holey and lacey carbon films from three different suppliers. We find that all grids have a large amount of mobile hydrocarbon contamination on them, as well as other larger contaminant species on the surface. Even after a variety of cleaning routines, none of the films are clean enough for STEM-EELS experiments requiring long acquisition times.

Light-triggered enzymatic reactions in nested vesicle reactors

Cell-sized vesicles have tremendous potential both as miniaturised pL reaction vessels and in bottom-up synthetic biology as chassis for artificial cells. In both these areas the introduction of light-responsive modules affords increased functionality, for example, to initiate enzymatic reactions in the vesicle interior with spatiotemporal control. Here we report a system composed of nested vesicles where the inner compartments act as phototransducers, responding to ultraviolet irradiation through diacetylene polymerisation-induced pore formation to initiate enzymatic reactions. The controlled release and hydrolysis of a fluorogenic β-galactosidase substrate in the external compartment is demonstrated, where the rate of reaction can be modulated by varying ultraviolet exposure time. Such cell-like nested microreactor structures could be utilised in fields from biocatalysis through to drug delivery.Matryoshka doll-like, nested vesicles, each containing a different ingredient to a chemical reaction, can serve as microreactors. Here, the authors developed a system in which mixing of the ingredients can be induced by irradiation with ultraviolet light.

Template-Free Synthesis of Highly Porous Boron Nitride: Insights into Pore Network Design and Impact on Gas Sorption

Production of biocompatible and stable porous materials, e.g., boron nitride, exhibiting tunable and enhanced porosity is a prerequisite if they are to be employed to address challenges such as drug delivery, molecular separations, or catalysis. However, there is currently very limited understanding of the formation mechanisms of porous boron nitride and the parameters controlling its porosity, which ultimately prevents exploiting the materials full potential. Herein, we produce boron nitride with high and tunable surface area and micro/mesoporosity via a facile template-free method using multiple readily available N-containing precursors with different thermal decomposition patterns. The gases are gradually released, creating hierarchical pores, high surface areas (>1900 m2/g), and micropore volumes. We use 3D tomography techniques to reconstruct the pore structure, allowing direct visualization of the mesopore network. Additional imaging and analytical tools are employed to characterize the materials from the micro- down to the nanoscale. The CO2 uptake of the materials rivals or surpasses those of commercial benchmarks or other boron nitride materials reported to date (up to 4 times higher), even after pelletizing. Overall, the approach provides a scalable route to porous boron nitride production as well as fundamental insights into the materials formation, which can be used to design a variety of boron nitride structures.

Inactivation, Clearance, and Functional Effects of Lung-Instilled Short and Long Silver Nanowires in Rats

There is a potential for silver nanowires (AgNWs) to be inhaled, but there is little information on their health effects and their chemical transformation inside the lungs in vivo. We studied the effects of short (S-AgNWs; 1.5 μm) and long (L-AgNWs; 10 μm) nanowires instilled into the lungs of Sprague–Dawley rats. S- and L-AgNWs were phagocytosed and degraded by macrophages; there was no frustrated phagocytosis. Interestingly, both AgNWs were internalized in alveolar epithelial cells, with precipitation of Ag2S on their surface as secondary Ag2S nanoparticles. Quantitative serial block face three-dimensional scanning electron microscopy showed a small, but significant, reduction of NW lengths inside alveolar epithelial cells. AgNWs were also present in the lung subpleural space where L-AgNWs exposure resulted in more Ag+ve macrophages situated within the pleura and subpleural alveoli, compared with the S-AgNWs exposure. For both AgNWs, there was lung inflammation at day 1, disappearing by day 21, but in bronchoalveolar lavage fluid (BALF), L-AgNWs caused a delayed neutrophilic and macrophagic inflammation, while S-AgNWs caused only acute transient neutrophilia. Surfactant protein D (SP-D) levels in BALF increased after S- and L-AgNWs exposure at day 7. L-AgNWs induced MIP-1α and S-AgNWs induced IL-18 at day 1. Large airway bronchial responsiveness to acetylcholine increased following L-AgNWs, but not S-AgNWs, exposure. The attenuated response to AgNW instillation may be due to silver inactivation after precipitation of Ag2S with limited dissolution. Our findings have important consequences for the safety of silver-based technologies to human health.

A comprehensive systematic study on thermoresponsive gels: beyond the common architectures of linear terpolymers

In this study, seven thermoresponsive methacrylate terpolymers with the same molar mass (MM) and composition but various architectures were successfully synthesized using group transfer polymerization (GTP). These terpolymers were based on tri(ethylene glycol) methyl ether methacrylate (TEGMA, A unit), n-butyl methacrylate (BuMA, B unit), and 2-(dimethylamino)ethyl methacrylate (DMAEMA, C unit). Along with the more common ABC, ACB, BAC, and statistical architectures, three diblock terpolymers were also synthesized and investigated for the first time, namely (AB)C, A(BC), and B(AC); where the units in the brackets are randomly copolymerized. Two BC diblock copolymers were also synthesized for comparison. Their hydrodynamic diameters and their effective pKas were determined by dynamic light scattering (DLS) and hydrogen ion titrations, respectively. The self-assembly behavior of the copolymers was also visualized by transmission electron microscopy (TEM). Both dilute and concentrated aqueous copolymer solutions were extensively studied by visual tests and their cloud points (CP) and gel points were determined. It is proven that the aqueous solution properties of the copolymers, with specific interest in their thermoresponsive properties, are influenced by the architecture, with the ABC and A(BC) ones to show clear sol-gel transition.