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Abstract: The ability to manipulate the composition of semiconductor alloys on-demand and at nanometer-scale resolutions is a powerful tool that could be exploited to tune key properties such as the electronic bandgap, mobility, and refractive index. However, existing methods to modify the composition involve altering the stoichiometry by temporal or spatial modulation of the process parameters during material growth, limiting the scalability and flexibility for device fabrication. Here, we report a laser processing method for localized tailoring of the composition in amorphous silicon-germanium (a-SiGe) nanoscale thin films on silicon substrates, post-deposition, by controlling phase segregation through the scan speed of the laser-induced molten zone. Laser-driven phase segregation at speeds adjustable from 0.1 to 100 mm s-1 allows access to previously unexplored solidification dynamics. The steady-state spatial distribution of the alloy constituents can be tuned directly by setting the constant laser scan speed to achieve indefinitely long Si1-xGex microstructures exhibiting the full range of compositions (0

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Abstract: The use of solar energy to activate chemical pathways in a sustainable manner drives the development in photocatalysis. While catalyst optimisation is a major theme in this pursuit, the development of novel photocatalytic reactors to enhance productivity is also imperative. In this work we combine, for the first time, microstructured optical fibre technology with photocatalysis, creating a photocatalytic microreactor coated with titania decorated with palladium nanoparticles. By doing so, we can create a system capable of effectively combining photons, liquids and gases within a monolithic, highly confined, transparent silica geometry. We utilise a range of characterisation techniques to selectively focus on the photocatalyst that resides exclusively within the internal capillaries of this system. In doing so we validate our design approach, and demonstrate the ability to simultaneously control both nanoparticle size and metal content. Further, we justify our unique design, showing its activity in photocatalytic hydrogen generation from water. In doing so highlighting the importance in developing light propagation properties from optical fibres, and the significant potential of this technology in the expansive photocatalysis landscape.

Open Access

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Abstract: Microcalcifications are important diagnostic indicators of disease in breast tissue. Tissue microenvironments differ in many aspects between normal and cancerous cells, notably extracellular pH and glycolytic respiration. Hydroxyapatite microcalcification microstructure is also found to differ between tissue pathologies, including differential ion substitutions and the presence of additional crystallographic phases. Distinguishing between tissue pathologies at an early stage is essential to improve patient experience and diagnostic accuracy, leading to better disease outcome. This study explores the hypothesis that microenvironment features may become immortalised within calcification crystallite characteristics thus becoming indicators of tissue pathology. In total, 55 breast calcifications incorporating 3 tissue pathologies (benign – B2, ductal carcinoma in-situ - B5a and invasive malignancy - B5b) from archive formalin-fixed paraffin-embedded core needle breast biopsies were analysed using X-ray diffraction. Crystallite size and strain were determined from 548 diffractograms using Williamson-Hall analysis. There was an increased crystallinity of hydroxyapatite with tissue malignancy compared to benign tissue. Coherence length was significantly correlated with pathology grade in all basis crystallographic directions (P < 0.01), with a greater difference between benign and in situ disease compared to in-situ disease and invasive malignancy. Crystallite size and non-uniform strain contributed to peak broadening in all three pathologies. Furthermore, crystallite size and non-uniform strain normal to the basal planes increased significantly with malignancy (P < 0.05). Our findings support the view that tissue microenvironments can influence differing formation mechanisms of hydroxyapatite through acidic precursors, leading to differential substitution of carbonate into the hydroxide and phosphate sites, causing significant changes in crystallite size and non-uniform strain.

Open Access

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Abstract: Microglia and astrocytes can quench metal toxicity to maintain tissue homeostasis, but with age, increasing glial dystrophy alongside metal dyshomeostasis may predispose the aged brain to acquire neurodegenerative diseases. The aim of the present study was to investigate age-related changes in brain metal deposition along with glial distribution in normal C57Bl/6J mice aged 2-, 6-, 19- and 27-months (n = 4/age). Using synchrotron-based X-ray fluorescence elemental mapping, we demonstrated age-related increases in iron, copper, and zinc in the basal ganglia (p < 0.05). Qualitative assessments revealed age-associated increases in iron, particularly in the basal ganglia and zinc in the white matter tracts, while copper showed overt enrichment in the choroid plexus/ventricles. Immunohistochemical staining showed augmented numbers of microglia and astrocytes, as a function of aging, in the basal ganglia (p < 0.05). Moreover, qualitative analysis of the glial immunostaining at the level of the fimbria and ventral commissure, revealed increments in the number of microglia but decrements in astroglia, in older aged mice. Upon morphological evaluation, aged microglia and astroglia displayed enlarged soma and thickened processes, reminiscent of dystrophy. Since glial cells have major roles in metal metabolism, we performed linear regression analysis and found a positive association between iron (R2 = 0.57, p = 0.0008), copper (R2 = 0.43, p = 0.0057), and zinc (R2 = 0.37, p = 0.0132) with microglia in the basal ganglia. Also, higher levels of iron (R2 = 0.49, p = 0.0025) and zinc (R2 = 0.27, p = 0.040) were correlated to higher astroglia numbers. Aging was accompanied by a dissociation between metal and glial levels, as we found through the formulation of metal to glia ratios, with regions of basal ganglia being differentially affected. For example, iron to astroglia ratio showed age-related increases in the substantia nigra and globus pallidus, while the ratio was decreased in the striatum. Meanwhile, copper and zinc to astroglia ratios showed a similar regional decline. Our findings suggest that inflammation at the choroid plexus, part of the blood-cerebrospinal-fluid barrier, prompts accumulation of, particularly, copper and iron in the ventricles, implying a compromised barrier system. Moreover, age-related glial dystrophy/senescence appears to disrupt metal homeostasis, likely due to induced oxidative stress, and hence increase the risk of neurodegenerative diseases.

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Abstract: Determining the oxidation state of Fe through parameterization of X-ray absorption near-edge structure (XANES) spectral features is highly dependent on accurate and repeatable energy calibration between spectra. Small errors in energy calibration can lead to vastly different interpretations. While simultaneous measurement of a reference foil is often undertaken on X-ray spectroscopy beamlines, other beamlines measure XANES spectra without a reference foil and therefore lack a method for correcting energy drift. Here a method is proposed that combines two measures of Fe oxidation state taken from different parts of the spectrum to iteratively correct for an unknown energy offset between spectra, showing successful iterative self-calibration not only during individual beam time but also across different beamlines.