Physiological monitoring technique using unattached sensors

Electronic instrumentation for body impedance change and electrocardiographic measurements using unattached electrode

Creating clinical pharmacy capacity in Namibia: a collaboration to establish a post-graduate pharmacy degree programme

Namibia has previously relied on external training of pharmacists but began in-country training in 2011. In response to an identified need for postgraduate clinical pharmacy development and training in the country, a Master’s degree was set up at the University of Namibia in 2016. The country has a considerable health burden of HIV and TB as well as a shortage of healthcare professionals. A UK clinical diploma model was adapted to meet the specific needs of the country and wider region, ensuring students could access the course over a sparsely populated, but large geographical spread, in addition to providing work-based learning, embedding research skills for future development, and focusing on the health needs of Namibia. The course uses online learning platforms and contact sessions to cover both knowledge and skill acquisition throughout the 3 years of the course. UK and US clinical pharmacists are utilised to provide specialist input, both remotely and within student workplaces, and further support has come from collaborations, including cross-site visits, with the UK-based pharmacy school whose diploma model was adapted. Challenges have included a shortage of clinical mentors, also compounding the students’ difficulty in visualising their future roles, as well as lone practitioners finding it hard to attend all contact sessions. The initial dropout rates of earlier cohorts have since reduced with greater understanding of the programme, and enthusiasm for the course remains high. The aim for the Master’s is to train students to become competent clinical pharmacists, thus having the knowledge and skills to mentor future cohorts of the course, as well as expanding the specialty within the country

Synthesis and characterization of iodovanadinite using PdI2, an iodine source for the immobilisation of radioiodine

The synthesis of a palladium-containing iodovanadinite derivative, hypothetically “PdPb9(VO4)6I2”, was attempted using PdI2 as a source of iodine in searching for a novel waste form for radioiodine. Stoichiometric amounts of Pb3(VO4)2 and PdI2 were batched and reacted at elevated temperatures in sealed vessels. Batched material was also subjected to high-energy ball-milling (HEBM) in order to reduce reaction time and the potential for iodine volatilization during subsequent reaction at 200–500 °C. The resulting products were characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, IR spectroscopy, thermal analysis and Pd K XANES. Results showed that PdI2 can function as a sacrificial iodine source for the formation of iodovanadinite, prototypically Pb10(VO4)6I2, however, the incorporation of Pd into this phase was not definitively observed. The sacrificial reaction mechanism involved the decomposition of PdI2 to Pd metal and nascent I2, with the latter incorporated into the iodovanadinite Pb10(VO4)6I2 phase. In comparison to processing using standard solid state reaction techniques, the use of HEBM prior to high temperature reaction generates a more homogeneous end-product with better iodine retention for this system. Overall, the key novelty and importance of this work is in demonstrating a method for direct immobilisation of undissolved PdI2 from nuclear fuel reprocessing, in a composite wasteform in which I-129 is immobilised within a durable iodovandinite ceramic, encapsulating Pd metal

International validation of a urinary biomarker panel for identification of active lupus nephritis in children.

Conventional markers of juvenile-onset systemic lupus erythematosus (JSLE) disease activity fail to adequately identify lupus nephritis (LN). While individual novel urine biomarkers are good at detecting LN flares, biomarker panels may improve diagnostic accuracy. The aim of this study was to assess the performance of a biomarker panel to identify active LN in two international JSLE cohorts.Novel urinary biomarkers, namely vascular cell adhesion molecule-1 (VCAM-1), monocyte chemoattractant protein 1 (MCP-1), lipocalin-like prostaglandin D synthase (LPGDS), transferrin (TF), ceruloplasmin, alpha-1-acid glycoprotein (AGP) and neutrophil gelatinase-associated lipocalin (NGAL), were quantified in a cross-sectional study that included participants of the UK JSLE Cohort Study (Cohort 1) and validated within the Einstein Lupus Cohort (Cohort 2). Binary logistic regression modelling and receiver operating characteristic curve analysis [area under the curve (AUC)] were used to identify and assess combinations of biomarkers for diagnostic accuracy.A total of 91 JSLE patients were recruited across both cohorts, of whom 31 (34 %) had active LN and 60 (66 %) had no LN. Urinary AGP, ceruloplasmin, VCAM-1, MCP-1 and LPGDS levels were significantly higher in those patients with active LN than in non-LN patients [all corrected p values (p c) < 0.05] across both cohorts. Urinary TF also differed between patient groups in Cohort 2 (p c = 0.001). Within Cohort 1, the optimal biomarker panel included AGP, ceruloplasmin, LPGDS and TF (AUC 0.920 for active LN identification). These results were validated in Cohort 2, with the same markers resulting in the optimal urine biomarker panel (AUC 0.991).In two international JSLE cohorts, urinary AGP, ceruloplasmin, LPGDS and TF demonstrate an 'excellent' ability for accurately identifying active LN in children

Role of microstructure and surface defects on the dissolution kinetics of CeO2, a UO2 fuel analogue.

The release of radionuclides from spent fuel in a geological disposal facility is controlled by the surface mediated dissolution of UO2 in groundwater. In this study we investigate the influence of reactive surface sites on the dissolution of a synthesised CeO2 analogue for UO2 fuel. Dissolution was performed on: CeO2 annealed at high temperature, which eliminated intrinsic surface defects (point defects and dislocations); CeO2-x annealed in inert and reducing atmospheres to induce oxygen vacancy defects; and on crushed CeO2 particles of different size fractions. BET surface area measurements were used as an indicator of reactive surface site concentration. Cerium stoichiometry, determined using X-ray Photoelectron Spectroscopy (XPS) and supported by X-ray Diffraction (XRD) analysis, was used to determine oxygen vacancy concentration. Upon dissolution in nitric acid medium at 90°C, a quantifiable relationship was established between the concentration of high energy surface sites and CeO2 dissolution rate; the greater the proportion of intrinsic defects and oxygen vacancies, the higher the dissolution rate. Dissolution of oxygen vacancy-containing CeO2-x gave rise to rates that were an order of magnitude greater than for CeO2 with fewer oxygen vacancies. While enhanced solubility of Ce3+ influenced the dissolution, it was shown that replacement of vacancy sites by oxygen significantly affected the dissolution mechanism due to changes in the lattice volume and strain upon dissolution and concurrent grain boundary decohesion. These results highlight the significant influence of defect sites and grain boundaries on the dissolution kinetics of UO2 fuel analogues and reduce uncertainty in the long-term performance of spent fuel in geological disposal

Solvent contribution to the stability of a physical gel characterized by quasi-elastic neutron scattering

The dynamics of a physical gel, namely the Low Molecular Mass Organic Gelator {\textit Methyl-4,6-O-benzylidene-$\alpha$ -D-mannopyranoside ($\alpha$-manno)} in water and toluene are probed by neutron scattering. Using high gelator concentrations, we were able to determine, on a timescale from a few ps to 1 ns, the number of solvent molecules that are immobilised by the rigid network formed by the gelators. We found that only few toluene molecules per gelator participate to the network which is formed by hydrogen bonding between the gelators' sugar moieties. In water, however, the interactions leading to the gel formations are weaker, involving dipolar, hydrophobic or $\pi-\pi$ interactions and hydrogen bonds are formed between the gelators and the surrounding water. Therefore, around 10 to 14 water molecules per gelator are immobilised by the presence of the network. This study shows that neutron scattering can give valuable information about the behaviour of solvent confined in a molecular gel.Comment: Langmuir (2015

Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses

Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO42–) exhibit very low solubility (∼1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO3 with incorporation of rare-earth oxides (for example, Nd2O3) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO3 in rare-earth containing aluminoborosilicate glasses has been proposed

Chemical state mapping of simulant Chernobyl lava-like fuel containing material using micro-focused synchrotron X-ray spectroscopy

Uranium speciation and redox behaviour is of critical importance in the nuclear fuel cycle. X-ray absorption near-edge spectroscopy (XANES) is commonly used to probe the oxidation state and speciation of uranium, and other elements, at the macroscopic and microscopic scale, within nuclear materials. Two-dimensional (2D) speciation maps, derived from microfocus X-ray fluorescence and XANES data, provide essential information on the spatial variation and gradients of the oxidation state of redox active elements such as uranium. In the present work, we elaborate and evaluate approaches to the construction of 2D speciation maps, in an effort to maximize sensitivity to the U oxidation state at the U L3-edge, applied to a suite of synthetic Chernobyl lava specimens. Our analysis shows that calibration of speciation maps can be improved by determination of the normalized X-ray absorption at excitation energies selected to maximize oxidation state contrast. The maps are calibrated to the normalized absorption of U L3 XANES spectra of relevant reference compounds, modelled using a combination of arctangent and pseudo-Voigt functions (to represent the photoelectric absorption and multiple-scattering contributions). We validate this approach by microfocus X-ray diffraction and XANES analysis of points of interest, which afford average U oxidation states in excellent agreement with those estimated from the chemical state maps. This simple and easy-to-implement approach is general and transferrable, and will assist in the future analysis of real lava-like fuel-containing materials to understand their environmental degradation, which is a source of radioactive dust production within the Chernobyl shelter

Characterization of and structural insight into struvite-K, MgKPO4·6H2O, an analogue of struvite

Struvite-K (MgKPO4·6H2O) is a magnesium potassium phosphate mineral with naturally cementitious properties, which is finding increasing usage as an inorganic cement for niche applications including nuclear waste management and rapid road repair. Struvite-K is also of interest in sustainable phosphate recovery from wastewater and, as such, a detailed knowledge of the crystal chemistry and high-temperature behavior is required to support further laboratory investigations and industrial applications. In this study, the local chemical environments of synthetic struvite-K were investigated using high-field solid-state 25Mg and 39K MAS NMR techniques, alongside 31P MAS NMR and thermal analysis. A single resonance was present in each of the 25Mg and 39K MAS NMR spectra, reported here for the first time alongside the experimental and calculated isotropic chemical shifts, which were comparable to the available data for isostructural struvite (MgNH4PO4·6H2O). An in situ high-temperature XRD analysis of struvite-K revealed the presence of a crystalline–amorphous–crystalline transition that occurred between 30 and 350 °C, following the single dehydration step of struvite-K. Between 50 and 300 °C, struvite-K dehydration yielded a transient disordered (amorphous) phase identified here for the first time, denoted δ-MgKPO4. At 350 °C, recrystallization was observed, yielding β-MgKPO4, commensurate with an endothermic DTA event. A subsequent phase transition to γ-MgKPO4 was observed on further heating, which reversed on cooling, resulting in the α-MgKPO4 structure stabilized at room temperature. This behavior was dissimilar from that of struvite exposed to high temperature, where NH4 liberation occurs at temperatures >50 °C, indicating that struvite-K could potentially withstand high temperatures via a transition to MgKPO4

Spectroscopic evaluation of UVI–cement mineral interactions: ettringite and hydrotalcite

Portland cement based grouts used for radioactive waste immobilization contain high replacement levels of supplementary cementitious materials, including blast-furnace slag and fly ash. The minerals formed upon hydration of these cements may have capacity for binding actinide elements present in radioactive waste. In this work, the minerals ettringite (Ca6Al2(SO4)3(OH)12·26H2O) and hydro­talcite (Mg6Al2(OH)16CO3·4H2O) were selected to investigate the importance of minor cement hydrate phases in sequestering and immobilizing UVI from radioactive waste streams. U LIII-edge X-ray absorption spectroscopy (XAS) was used to probe the UVI coordination environment in contact with these minerals. For the first time, solid-state 27Al magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy was applied to probe the Al coordination environment in these UVI-contacted minerals and make inferences on the UVI coordination, in conjunction with the X-ray spectroscopy analyses. The U LIII-edge XAS analysis of the UVI-contacted ettringite phases found them to be similar (>∼70%) to the uranyl oxyhydroxides present in a mixed becquerelite/metaschoepite mineral. Fitting of the EXAFS region, in combination with 27Al NMR analysis, indicated that a disordered Ca- or Al-bearing UVI secondary phase also formed. For the UVI-contacted hydro­talcite phases, the XAS and 27Al NMR data were interpreted as being similar to uranyl carbonate, that was likely Mg-containing