Defect chemistry of Ti and Fe impurities and aggregates in Al2O3

We report a theoretical evaluation of the properties of iron and titanium impurities in sapphire (corundum structured α-Al2O3). Calculations using analytical force fields have been performed on the defect structure with the metals present in isolated, co-doped and tri-cluster configurations. Crystal field parameters have been calculated with good agreement to available experimental data. When titanium and iron are present in neighbouring face and edge-sharing orientations, the overlap of the d-orbitals facilitates an intervalence charge transfer (FeIII/TiIII → FeII/TiIV) with an associated optical excitation energy of 1.85 eV and 1.76 eV in the respective configurations. Electronic structure calculations based on density functional theory confirm that FeIII/TiIII is the ground-state configuration for the nearest-neighbour pairs, in contrast to the often considered FeII/TiIV pair. Homonuclear intervalence charge transfer energies between both FeIII/FeII and TiIV/TiIII species have also been calculated, with the energy lying in the infra-red region. Investigation of multiple tri-clusters of iron and titanium identified one stable configuration, TiIII–(TiIV/FeII), with the energy of electron transfer remaining unchanged

Microscopic origin of the optical processes in blue sapphire

Al2O3 changes from transparent to a range of intense colours depending on the chemical impurities present. In blue sapphire, Fe and Ti are incorporated; however, the chemical process that gives rise to the colour has long been debated. Atomistic modelling identifies charge transfer from Ti(III) to Fe(III) as being responsible for the characteristic blue appearance

Monitoring the condition of Marine Renewable Energy Devices through underwater acoustic emissions: Case study of a wave energy converter in Falmouth Bay, UK

Abstract Maintaining the engineering health of Marine Renewable Energy Devices (MREDs) is one of the main limits to their economic viability, because of the requirement for costly marine interventions in challenging conditions. Acoustic Emission (AE) condition monitoring is routinely and successfully used for land-based devices, and this paper shows how it can be used underwater. We review the acoustic signatures expected from operation and likely failure modes of MREDs, providing a basis for a generic classification system. This is illustrated with a Wave Energy Converter tested at Falmouth Bay (UK), monitored for 2 years. Underwater noise levels have been measured between 10 Hz and 32 kHz throughout this time, covering operational and inactive periods. Broadband MRED contributions to ambient noise are generally negligible. Time-frequency analyses are used to detect acoustic signatures (60 Hz–5 kHz) of specific operational activities, such as the active Power Take Off, and relate them to engineering and environmental conditions. These first results demonstrate the feasibility of using underwater Acoustic Emissions to monitor the health and performance of MREDs.JW is funded by the Natural Environment Research Council (NERC grant NE/L002434/1) as part of the GW4+ Doctoral Training Partnership (http://www.nercgw4plus.ac.uk/). IB is funded through the SuperGen UK Centre for Marine Energy Research (EPSRC grant EP/M014738/1). The authors would also like to thank M.J. Witt (U. Exeter) for his invaluable assistance with acoustic data collection [14] and [15], funded by ESF, PRIMaRE, MERiFIC, TSB and Fred Olsen Renewables

Vitamin D and subsequent all-age and premature mortality: a systematic review

<br>Background: All-cause mortality in the population < 65 years is 30% higher in Glasgow than in equally deprived Liverpool and Manchester. We investigated a hypothesis that low vitamin D in this population may be associated with premature mortality via a systematic review and meta-analysis.</br> <br>Methods: Medline, EMBASE, Web of Science, the Cochrane Library and grey literature sources were searched until February 2012 for relevant studies. Summary statistics were combined in an age-stratified meta-analysis.</br> <br>Results: Nine studies were included in the meta-analysis, representing 24,297 participants, 5,324 of whom died during follow-up. The pooled hazard ratio for low compared to high vitamin D demonstrated a significant inverse association (HR 1.19, 95% CI 1.12-1.27) between vitamin D levels and all-cause mortality after adjustment for available confounders. In an age-stratified meta-analysis, the hazard ratio for older participants was 1.25 (95% CI 1.14-1.36) and for younger participants 1.12 (95% CI 1.01-1.24).</br> <br>Conclusions: Low vitamin D status is inversely associated with all-cause mortality but the risk is higher amongst older individuals and the relationship is prone to residual confounding. Further studies investigating the association between vitamin D deficiency and all-cause mortality in younger adults with adjustment for all important confounders (or using randomised trials of supplementation) are required to clarify this relationship.</br&gt

Synthetic nuclear diagnostics for inferring plasma properties of inertial confinement fusion implosions

A suite of synthetic nuclear diagnostics has been developed to post-process radiation hydrodynamics simulations performed with the code Chimera. These provide experimental observables based on simulated capsule properties and are used to assess alternative experimental and data analysis techniques. These diagnostics include neutron spectroscopy, primary and scattered neutron imaging, neutron activation, γ-ray time histories and carbon γ-ray imaging. Novel features of the neutron spectrum have been analysed to infer plasma parameters. The nT and nD backscatter edges have been shown to provide a shell velocity measurement. Areal density asymmetries created by low mode perturbations have been inferred from the slope of the downscatter spectrum down to 10 MeV. Neutron activation diagnostics showed significant aliasing of high mode areal density asymmetries when observing a capsule implosion with 3D multimode perturbations applied. Carbon γ-ray imaging could be used to image the ablator at a high convergence ratio. Time histories of both the fusion and carbon γ signals showed a greater time difference between peak intensities for the perturbed case when compared to a symmetric simulation

ERK1/2 signaling dominates over RhoA signaling in regulating early changes in RNA expression induced by endothelin-1 in neonatal rat cardiomyocytes

Cardiomyocyte hypertrophy is associated with changes in gene expression. Extracellular signal-regulated kinases 1/2 (ERK1/2) and RhoA [activated by hypertrophic agonists (e.g. endothelin-1)] regulate gene expression and are implicated in the response, but their relative significance in regulating the cardiomyocyte transcriptome is unknown. Our aim was to establish the significance of ERK1/2 and/or RhoA in the early cardiomyocyte transcriptomic response to endothelin-1.Cardiomyocytes were exposed to endothelin-1 (1 h) with/without PD184352 (to inhibit ERK1/2) or C3 transferase (C3T, to inhibit RhoA). RNA expression was analyzed using microarrays and qPCR. ERK1/2 signaling positively regulated approximately 65% of the early gene expression response to ET-1 with a small (approximately 2%) negative effect, whereas RhoA signaling positively regulated approximately 10% of the early gene expression response to ET-1 with a greater (approximately 14%) negative contribution. Of RNAs non-responsive to endothelin-1, 66 or 448 were regulated by PD184352 or C3T, respectively, indicating that RhoA had a more significant effect on baseline RNA expression. mRNAs upregulated by endothelin-1 encoded a number of receptor ligands (e.g. Ereg, Areg, Hbegf) and transcription factors (e.g. Abra/Srf) that potentially propagate the response.ERK1/2 dominates over RhoA in the early transcriptomic response to endothelin-1. RhoA plays a major role in maintaining baseline RNA expression but, with upregulation of Abra/Srf by endothelin-1, RhoA may regulate changes in RNA expression over longer times. Our data identify ERK1/2 as a more significant node than RhoA in regulating the early stages of cardiomyocyte hypertrophy

Microbiological, histological, immunological, and toxin response to antibiotic treatment in the mouse model of Mycobacterium ulcerans disease.

Mycobacterium ulcerans infection causes a neglected tropical disease known as Buruli ulcer that is now found in poor rural areas of West Africa in numbers that sometimes exceed those reported for another significant mycobacterial disease, leprosy, caused by M. leprae. Unique among mycobacterial diseases, M. ulcerans produces a plasmid-encoded toxin called mycolactone (ML), which is the principal virulence factor and destroys fat cells in subcutaneous tissue. Disease is typically first manifested by the appearance of a nodule that eventually ulcerates and the lesions may continue to spread over limbs or occasionally the trunk. The current standard treatment is 8 weeks of daily rifampin and injections of streptomycin (RS). The treatment kills bacilli and wounds gradually heal. Whether RS treatment actually stops mycolactone production before killing bacilli has been suggested by histopathological analyses of patient lesions. Using a mouse footpad model of M. ulcerans infection where the time of infection and development of lesions can be followed in a controlled manner before and after antibiotic treatment, we have evaluated the progress of infection by assessing bacterial numbers, mycolactone production, the immune response, and lesion histopathology at regular intervals after infection and after antibiotic therapy. We found that RS treatment rapidly reduced gross lesions, bacterial numbers, and ML production as assessed by cytotoxicity assays and mass spectrometric analysis. Histopathological analysis revealed that RS treatment maintained the association of the bacilli with (or within) host cells where they were destroyed whereas lack of treatment resulted in extracellular infection, destruction of host cells, and ultimately lesion ulceration. We propose that RS treatment promotes healing in the host by blocking mycolactone production, which favors the survival of host cells, and by killing M. ulcerans bacilli

The TW Hya Rosetta Stone Project IV: A Hydrocarbon-rich Disk Atmosphere

Connecting the composition of planet-forming disks with that of gas giant exoplanet atmospheres, in particular through C/O ratios, is one of the key goals of disk chemistry. Small hydrocarbons like C2H and C3H2 have been identified as tracers of C/O, as they form abundantly under high C/O conditions. We present resolved c–C3H2 observations from the TW Hya Rosetta Stone Project, a program designed to map the chemistry of common molecules at 15–20 au resolution in the TW Hya disk. Augmented by archival data, these observations comprise the most extensive multi-line set for disks of both ortho and para spin isomers spanning a wide range of energies, Eu = 29–97 K. We find the ortho-to-para ratio of c–C3H2 is consistent with 3 throughout extent of the emission, and the total abundance of both c–C3H2 isomers is (7.5–10) × 10−11 per H atom, or 1%–10% of the previously published C2H abundance in the same source. We find c–C3H2 comes from a layer near the surface that extends no deeper than z/r = 0.25. Our observations are consistent with substantial radial variation in gas-phase C/O in TW Hya, with a sharp increase outside ~30 au. Even if we are not directly tracing the midplane, if planets accrete from the surface via, e.g., meridional flows, then such a change should be imprinted on forming planets. Perhaps interestingly, the HR 8799 planetary system also shows an increasing gradient in its giant planets' atmospheric C/O ratios. While these stars are quite different, hydrocarbon rings in disks are common, and therefore our results are consistent with the young planets of HR 8799 still bearing the imprint of their parent disk's volatile chemistry

The TW Hya Rosetta Stone Project. II. Spatially Resolved Emission of Formaldehyde Hints at Low-temperature Gas-phase Formation

Formaldehyde (H2CO) is an important precursor to organics like methanol (CH3OH). It is important to understand the conditions that produce H2CO and prebiotic molecules during star and planet formation. H2CO possesses both gas-phase and solid-state formation pathways, involving either UV-produced radical precursors or CO ice and cold (lesssim20 K) dust grains. To understand which pathway dominates, gaseous H2CO's ortho-to-para ratio (OPR) has been used as a probe, with a value of 3 indicating "warm" conditions and <3 linked to cold formation in the solid state. We present spatially resolved Atacama Large Millimeter/submillimeter Array observations of multiple ortho- and para-H2CO transitions in the TW Hya protoplanetary disk to test H2CO formation theories during planet formation. We find disk-averaged rotational temperatures and column densities of 33 ± 2 K, (1.1 ± 0.1) × 1012 cm−2 and 25 ± 2 K, (4.4 ± 0.3) × 1011 cm−2 for ortho- and para-H2CO, respectively, and an OPR of 2.49 ± 0.23. A radially resolved analysis shows that the observed H2CO emits mostly at rotational temperatures of 30–40 K, corresponding to a layer with z/R ≥ 0.25. The OPR is consistent with 3 within 60 au, the extent of the pebble disk, and decreases beyond 60 au to 2.0 ± 0.5. The latter corresponds to a spin temperature of 12 K, well below the rotational temperature. The combination of relatively uniform emitting conditions, a radial gradient in the OPR, and recent laboratory experiments and theory on OPR ratios after sublimation, led us to speculate that gas-phase formation is responsible for the observed H2CO across the TW Hya disk