3,566 research outputs found

    Phenyl radical + propene: a prototypical reaction surface for aromatic-catalyzed 1,2-hydrogen-migration and subsequent resonance-stabilized radical formation

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    The C[subscript 9]H[subscript 11] potential energy surface (PES) was experimentally and theoretically explored because it is a relatively simple, prototypical alkylaromatic radical system. Although the C[subscript 9]H[subscript 11] PES has already been extensively studied both experimentally (under single-collision and thermal conditions) and theoretically, new insights were made in this work by taking a new experimental approach: flash photolysis combined with time-resolved molecular beam mass spectrometry (MBMS) and visible laser absorbance. The C[subscript 9]H[subscript 11] PES was experimentally accessed by photolytic generation of the phenyl radical and subsequent reaction with excess propene (C[subscript 6]H[subscript 5] + C[subscript 3]H[subscript 6]). The overall kinetics of C[subscript 6]H[subscript 5] + C[subscript 3]H[subscript 6] was measured using laser absorbance with high time-resolution from 300 to 700 K and was found to be in agreement with earlier measurements over a lower temperature range. Five major product channels of C[subscript 6]H[subscript 5] + C[subscript 3]H[subscript 6] were observed with MBMS at 600 and 700 K, four of which were expected: hydrogen (H)-abstraction (measured by the stable benzene, C[subscript 6]H[subscript 6], product), methyl radical (CH[subscript 3])-loss (styrene detected), H-loss (phenylpropene isomers detected) and radical adduct stabilization. The fifth, unexpected product observed was the benzyl radical, which was rationalized by the inclusion of a previously unreported pathway on the C[subscript 9]H[subscript 11] PES: aromatic-catalysed 1,2-H-migration and subsequent resonance stabilized radical (RSR, benzyl radical in this case) formation. The current theoretical understanding of the C[subscript 9]H[subscript 11] PES was supported (including the aromatic-catalyzed pathway) by quantitative comparisons between modelled and experimental MBMS results. At 700 K, the branching to styrene + CH[subscript 3] was 2-4 times greater than that of any other product channel, while benzyl radical + C[subscript 2]H[subscript 4] from the aromatic-catalyzed pathway accounted for ∼10% of the branching. Single-collision conditions were also simulated on the updated PES to explain why previous crossed molecular beam experiments did not see evidence of the aromatic-catalyzed pathway. This experimentally validated knowledge of the C[subscript 9]H[subscript 11] PES was added to the database of the open-source Reaction Mechanism Generator (RMG), which was then used to generalize the findings on the C[subscript 9]H[subscript 11] PES to a slightly more complicated alkylaromatic system.Think Global Education Trus

    Relative seismic velocity variations correlate with deformation at KÄ«lauea volcano

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    Seismic noise interferometry allows the continuous and real-time measurement of relative seismic velocity through a volcanic edifice. Because seismic velocity is sensitive to the pressurization state of the system, this method is an exciting new monitoring tool at active volcanoes. Despite the potential of this tool, no studies have yet comprehensively compared velocity to other geophysical observables on a short-term time scale at a volcano over a significant length of time. We use volcanic tremor (~0.3 to 1.0 Hz) at Kīlauea as a passive source for interferometry to measure relative velocity changes with time. By cross-correlating the vertical component of day-long seismic records between ~230 station pairs, we extract coherent and temporally consistent coda wave signals with time lags of up to 120 s. Our resulting time series of relative velocity shows a remarkable correlation between relative velocity and the radial tilt record measured at Kīlauea summit, consistently correlating on a time scale of days to weeks for almost the entire study period (June 2011 to November 2015). As the summit continually deforms in deflation-inflation events, the velocity decreases and increases, respectively. Modeling of strain at Kīlauea suggests that, during inflation of the shallow magma reservoir (1 to 2 km below the surface), most of the edifice is dominated by compression—hence closing cracks and producing faster velocities—and vice versa. The excellent correlation between relative velocity and deformation in this study provides an opportunity to understand better the mechanisms causing seismic velocity changes at volcanoes, and therefore realize the potential of passive interferometry as a monitoring tool.The work was funded by graduate studentships from the Natural Environment Research Council (NE/L002507/1 and NE/K500884/1 for C.D. and R.G.G., respectively) and Department of Earth Sciences, University of Cambridge (contribution number ESC3863). C.C. acknowledges a Wiener-Anspach postdoctoral fellowship and an F.R.S.-FNRS Chargé de Recherches/Université Libre de Bruxelles fellowship. The U.S. alumnae of Newnham College, Cambridge awarded a travel grant

    Electroproduction of the d* dibaryon

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    The unpolarized cross section for the electroproduction of the isoscalar Jπ=3+J^\pi = 3^+ di-delta dibaryon d∗d^* is calculated for deuteron target using a simple picture of elastic electron-baryon scattering from the ΔΔ(7D1)\Delta \Delta (^7D_1) and the NN(3S1)NN (^3S_1) components of the deuteron. The calculated differential cross section at the electron lab energy of 1 GeV has the value of about 0.24 (0.05) nb/sr at the lab angle of 10∘^\circ (30∘^\circ) for the Bonn B potential when the dibaryon mass is taken to be 2.1 GeV. The cross section decreases rapidly with increasing dibaryon mass. A large calculated width of 40 MeV for d∗(ΔΔ7S3)d^*(\Delta\Delta ^7S_3) combined with a small experimental upper bound of 0.08 MeV for the d∗d^* decay width appears to have excluded any low-mass d∗d^* model containing a significant admixture of the ΔΔ(7S3)\Delta\Delta (^7S_3) configuration.Comment: 11 journal-style pages, 8 figure

    Asteroseismology

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    Asteroseismology is the determination of the interior structures of stars by using their oscillations as seismic waves. Simple explanations of the astrophysical background and some basic theoretical considerations needed in this rapidly evolving field are followed by introductions to the most important concepts and methods on the basis of example. Previous and potential applications of asteroseismology are reviewed and future trends are attempted to be foreseen.Comment: 38 pages, 13 figures, to appear in: "Planets, Stars and Stellar Systems", eds. T. D. Oswalt et al., Springer Verla

    Description and evaluation of an EBM curriculum using a block rotation

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    BACKGROUND: While previous authors have emphasized the importance of integrating and reinforcing evidence-based medicine (EBM) skills in residency, there are few published examples of such curricula. We designed an EBM curriculum to train family practice interns in essential EBM skills for information mastery using clinical questions generated by the family practice inpatient service. We sought to evaluate the impact of this curriculum on interns, residents, and faculty. METHODS: Interns (n = 13) were asked to self-assess their level of confidence in basic EBM skills before and after their 2-week EBM rotation. Residents (n = 21) and faculty (n = 12) were asked to assess how often the answers provided by the EBM intern to the inpatient service changed medical care. In addition, residents were asked to report how often they used their EBM skills and how often EBM concepts and tools were used in teaching by senior residents and faculty. Faculty were asked if the EBM curriculum had increased their use of EBM in practice and in teaching. RESULTS: Interns significantly increased their confidence over the course of the rotation. Residents and faculty felt that the answers provided by the EBM intern provided useful information and led to changes in patient care. Faculty reported incorporating EBM into their teaching (92%) and practice (75%). Residents reported applying the EBM skills they learned to patient care (86%) and that these skills were reinforced in the teaching they received outside of the rotation (81%). All residents and 11 of 12 faculty felt that the EBM curriculum had improved patient care. CONCLUSIONS: To our knowledge, this is the first published EBM curriculum using an individual block rotation format. As such, it may provide an alternative model for teaching and incorporating EBM into a residency program

    The APOSTEL recommendations for reporting quantitative optical coherence tomography studies

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    OBJECTIVE: To develop consensus recommendations for reporting of quantitative optical coherence tomography (OCT) study results. METHODS: A panel of experienced OCT researchers (including 11 neurologists, 2 ophthalmologists, and 2 neuroscientists) discussed requirements for performing and reporting quantitative analyses of retinal morphology and developed a list of initial recommendations based on experience and previous studies. The list of recommendations was subsequently revised during several meetings of the coordinating group. RESULTS: We provide a 9-point checklist encompassing aspects deemed relevant when reporting quantitative OCT studies. The areas covered are study protocol, acquisition device, acquisition settings, scanning protocol, funduscopic imaging, postacquisition data selection, postacquisition data analysis, recommended nomenclature, and statistical analysis. CONCLUSIONS: The Advised Protocol for OCT Study Terminology and Elements recommendations include core items to standardize and improve quality of reporting in quantitative OCT studies. The recommendations will make reporting of quantitative OCT studies more consistent and in line with existing standards for reporting research in other biomedical areas. The recommendations originated from expert consensus and thus represent Class IV evidence. They will need to be regularly adjusted according to new insights and practices

    Ontology-based employer demand management

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    Skills shortages globally pose a real and urgent need for proper investigation and workforce development planning into the future. Analysing workforce development and employer demand needs through electronic job market allows much deeper and wider research into skill shortages. Current methods do not provide the level of depth required to address such important economic implications. In this paper, we present a system aiming to gather and analyse current employer demand information from online job advertisements. It identifies current employer demand needs analysed from electronic job market

    Theoretical and Phenomenological Constraints on Form Factors for Radiative and Semi-Leptonic B-Meson Decays

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    We study transition form factors for radiative and rare semi-leptonic B-meson decays into light pseudoscalar or vector mesons, combining theoretical constraints and phenomenological information from Lattice QCD, light-cone sum rules, and dispersive bounds. We pay particular attention to form factor parameterisations which are based on the so-called series expansion, and study the related systematic uncertainties on a quantitative level. In this context, we also provide the NLO corrections to the correlation function between two flavour-changing tensor currents, which enters the unitarity constraints for the coefficients in the series expansion.Comment: 52 pages; v2: normalization error in (29ff.) corrected, conclusion about relevance of unitarity bounds modified; form factor fits unaffected; references added; v3: discussion on truncation of series expansion added, matches version to be published in JHEP; v4: corrected typos in Tables 5 and
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