97 research outputs found

    Generation of defects and disorder from deeply quenching a liquid to form a solid

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    We show how deeply quenching a liquid to temperatures where it is linearly unstable and the crystal is the equilibrium phase often produces crystalline structures with defects and disorder. As the solid phase advances into the liquid phase, the modulations in the density distribution created behind the advancing solidification front do not necessarily have a wavelength that is the same as the equilibrium crystal lattice spacing. This is because in a deep enough quench the front propagation is governed by linear processes, but the crystal lattice spacing is determined by nonlinear terms. The wavelength mismatch can result in significant disorder behind the front that may or may not persist in the latter stage dynamics. We support these observations by presenting results from dynamical density functional theory calculations for simple one- and two-component two-dimensional systems of soft core particles.Comment: 25 pages, 11 figure

    Derivation of greenhouse gas emission factors for peatlands managed for extraction in the Republic of Ireland and the United Kingdom

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    Drained peatlands are significant hotspots of carbon dioxide (CO2) emissions and may also be more vulnerable to fire with its associated gaseous emissions. Under the United Nations Framework Convention on Climate Change (UNFCCC) and the Kyoto Protocol, greenhouse gas (GHG) emissions from peatlands managed for extraction are reported on an annual basis. However, the Tier 1 (default) emission factors (EFs) provided in the IPCC 2013 Wetlands Supplement for this land use category may not be representative in all cases and countries are encouraged to move to higher-tier reporting levels with reduced uncertainty levels based on country- or regional-specific data. In this study, we quantified (1) CO2-C emissions from nine peat extraction sites in the Republic of Ireland and the United Kingdom, which were initially disaggregated by land use type (industrial versus domestic peat extraction), and (2) a range of GHGs that are released to the atmosphere with the burning of peat. Drainage-related methane (CH4) and nitrous oxide (N2O) emissions as well as CO2-C emissions associated with the off-site decomposition of horticultural peat were not included here. Our results show that net CO2-C emissions were strongly controlled by soil temperature at the industrial sites (bare peat) and by soil temperature and leaf area index at the vegetated domestic sites. Our derived EFs of 1.70 (±0.47) and 1.64 (±0.44) t CO2-C ha−1 yr−1 for the industrial and domestic sites respectively are considerably lower than the Tier 1 EF (2.8 ± 1.7 t CO2-C ha−1 yr−1) provided in the Wetlands Supplement. We propose that the difference between our derived values and the Wetlands Supplement value is due to differences in peat quality and, consequently, decomposition rates. Emissions from burning of the peat (g kg−1 dry fuel burned) were estimated to be approximately 1346 CO2, 8.35 methane (CH4), 218 carbon monoxide (CO), 1.53 ethane (C2H6), 1.74 ethylene (C2H4), 0.60 methanol (CH3OH), 2.21 hydrogen cyanide (HCN) and 0.73 ammonia (NH3), and this emphasises the importance of understanding the full suite of trace gas emissions from biomass burning. Our results highlight the importance of generating reliable Tier 2 values for different regions and land use categories. Furthermore, given that the IPCC Tier 1 EF was only based on 20 sites (all from Canada and Fennoscandia), we suggest that data from another 9 sites significantly expand the global data set, as well as adding a new region

    A dinuclear ruthenium(II) complex excited by near-infrared light through two-photon absorption induces phototoxicity deep within hypoxic regions of melanoma cancer spheroids

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    The dinuclear photo-oxidizing RuII complex [{Ru(TAP2)}2(tpphz)]4+ (TAP = 1,4,5,8- tetraazaphenanthrene, tpphz = tetrapyrido[3,2-a:2',3'-c:3'',2''- h:2''',3'''-j]phenazine), 14+ is readily taken up by live cells localizing in mitochondria and nuclei. In this study, the two-photon absorption cross-section of 14+ is quantified and its use as a two-photon absorbing phototherapeutic is reported. It was con-firmed that the complex is readily photo-excited using near infrared, NIR, light through two-photon absorption, TPA. In 2-D cell cul-tures, irradiation with NIR light at low power results in precisely focused photo-toxicity effects in which human melanoma cells were killed after 5 minutes of light exposure. Similar experiments were then carried out in human cancer spheroidsthat provide a realistic tumor model for the development of therapeutics and phototherapeutics. Using the characteristic emission of the complex as a probe, its up-take into 280 µm spheroids was investigated and confirmed that the spheroid takes up the complex. Notably TPA excitation results in more intense luminescence being observed throughout the depth of the spheroids, although emission intensity still drops off toward the necrotic core. As 14+ can directly photo-oxidize DNA without the mediation of singlet oxygen or other reactive oxygen species, photo-toxicity within the deeper, hypoxic layers of the spheroids was also investigated. To quantify the penetration of these phototoxic effects, 14+ was photo-excited through TPA at a power of 60 mW, which was progressively focused in 10 µm steps throughout the entire z-axis of individual spheroids. These experiments revealed that, in irradiated spheroids treated with 14+, acute and rapid photo-induced cell death was observed throughout their depth, including the hypoxic region

    Making the right link to theranostics : the photophysical and biological properties of dinuclear Ru^II-Re^I dppz complexes depend on their tether

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    The synthesis of new dinuclear complexes containing linked RuII(dppz) and ReI(dppz) moieties is reported. The photophysical and biological properties of the new complex, which incorporates a N,N′-bis(4-pyridylmethyl)-1,6-hexanediamine tether ligand, are compared to a previously reported RuII/ReI complex linked by a simple dipyridyl alkane ligand. Although both complexes bind to DNA with similar affinities, steady-state and time-resolved photophysical studies reveal that the nature of the linker affects the excited state dynamics of the complexes and their DNA photocleavage properties. Quantum-based DFT calculations on these systems offer insights into these effects. While both complexes are live cells permeant, their intracellular localizations are significantly affected by the nature of the linker. Notably, one of the complexes displayed concentration-dependent localization and possesses photophysical properties that are compatible with SIM and STED nanoscopy. This allowed the dynamics of its intracellular localization to be tracked at super resolutions

    Negotiating Value: Comparing Human and Animal Fracture Care in Industrial Societies

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    At the beginning of the twentieth-century, human and veterinary surgeons faced the challenge of a medical marketplace transformed by technology. The socio-economic value ascribed to their patients – people and domestic animals – was changing, reflecting the increasing mechanisation of industry and the decreasing dependence of society upon non-human animals for labour. In human medicine, concern for the economic consequences of fractures “pathologised” any significant level of post-therapeutic disability, a productivist perspective contrary to the traditional corpus of medical values. In contrast, veterinarians adapted to the mechanisation of horse-power by shifting their primary professional interest to companion animals; a type of veterinary patient generally valued for the unique emotional attachment of the owner, and not the productive capacity of the animal. The economic rationalisation of human fracture care and the “sentimental” transformation of veterinary orthopaedic expertise indicates how these specialists utilised increasingly convergent rhetorical arguments to justify the application of innovative fracture care technologies to their humans and animal patients. Keywords: Fracture care, Industrialisation, Veterinary History, Human/animal relation

    More than smell - COVID-19 is associated with severe impairment of smell, taste, and chemesthesis

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    Recent anecdotal and scientific reports have provided evidence of a link between COVID-19 and chemosensory impairments, such as anosmia. However, these reports have downplayed or failed to distinguish potential effects on taste, ignored chemesthesis, and generally lacked quantitative measurements. Here, we report the development, implementation, and initial results of a multilingual, international questionnaire to assess self-reported quantity and quality of perception in 3 distinct chemosensory modalities (smell, taste, and chemesthesis) before and during COVID-19. In the first 11 days after questionnaire launch, 4039 participants (2913 women, 1118 men, and 8 others, aged 19-79) reported a COVID-19 diagnosis either via laboratory tests or clinical assessment. Importantly, smell, taste, and chemesthetic function were each significantly reduced compared to their status before the disease. Difference scores (maximum possible change ±100) revealed a mean reduction of smell (-79.7 ± 28.7, mean ± standard deviation), taste (-69.0 ± 32.6), and chemesthetic (-37.3 ± 36.2) function during COVID-19. Qualitative changes in olfactory ability (parosmia and phantosmia) were relatively rare and correlated with smell loss. Importantly, perceived nasal obstruction did not account for smell loss. Furthermore, chemosensory impairments were similar between participants in the laboratory test and clinical assessment groups. These results show that COVID-19-associated chemosensory impairment is not limited to smell but also affects taste and chemesthesis. The multimodal impact of COVID-19 and the lack of perceived nasal obstruction suggest that severe acute respiratory syndrome coronavirus strain 2 (SARS-CoV-2) infection may disrupt sensory-neural mechanisms. © 2020 The Author(s) 2020. Published by Oxford University Press. All rights reserved

    Mouse Chromosome 11

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    Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/46996/1/335_2004_Article_BF00648429.pd
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