1,235 research outputs found

    Synthesis of oxetane and azetidine ethers as ester isosteres by BrĂžnsted acid catalysed alkylation of alcohols with 3-aryl-oxetanols and 3-aryl-azetidinols

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    Oxetanes and azetidines continue to draw significant interest in medicinal chemistry, as small, polar and non-planar motifs. Oxetanes also represent interesting surrogates for carbonyl-containing functional groups. Here we report a synthesis of 3,3- disubstituted oxetane- and azetidine-ethers, with comparisons made to the ester functional group. The tertiary benzylic alcohols of the 4-membered rings are selectively activated using BrĂžnsted acid catalysis and reacted with simple alcohols to form the ethers and maintain the oxetane ring intact. This approach avoids the use of strong bases and halide alkylating agents and allows alcohol libraries to be leveraged. Oxetane ethers demonstrate excellent chemical stability across a range of conditions and an improved stability vis-Ă -vis analogous esters under basic and reducing conditions

    Means and covariance functions for geostatistical compositional data: an axiomatic approach

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    This work focuses on the characterization of the central tendency of a sample of compositional data. It provides new results about theoretical properties of means and covariance functions for compositional data, with an axiomatic perspective. Original results that shed new light on the geostatistical modeling of compositional data are presented. As a first result, it is shown that the weighted arithmetic mean is the only central tendency characteristic satisfying a small set of axioms, namely continuity, reflexivity and marginal stability. Moreover, this set of axioms also implies that the weights must be identical for all parts of the composition. This result has deep consequences on the spatial multivariate covariance modeling of compositional data. In a geostatistical setting, it is shown as a second result that the proportional model of covariance functions (i.e., the product of a covariance matrix and a single correlation function) is the only model that provides identical kriging weights for all components of the compositional data. As a consequence of these two results, the proportional model of covariance function is the only covariance model compatible with reflexivity and marginal stability

    Controlling Cherenkov angles with resonance transition radiation

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    Cherenkov radiation provides a valuable way to identify high energy particles in a wide momentum range, through the relation between the particle velocity and the Cherenkov angle. However, since the Cherenkov angle depends only on material's permittivity, the material unavoidably sets a fundamental limit to the momentum coverage and sensitivity of Cherenkov detectors. For example, Ring Imaging Cherenkov detectors must employ materials transparent to the frequency of interest as well as possessing permittivities close to unity to identify particles in the multi GeV range, and thus are often limited to large gas chambers. It would be extremely important albeit challenging to lift this fundamental limit and control Cherenkov angles as preferred. Here we propose a new mechanism that uses constructive interference of resonance transition radiation from photonic crystals to generate both forward and backward Cherenkov radiation. This mechanism can control Cherenkov angles in a flexible way with high sensitivity to any desired range of velocities. Photonic crystals thus overcome the severe material limit for Cherenkov detectors, enabling the use of transparent materials with arbitrary values of permittivity, and provide a promising option suited for identification of particles at high energy with enhanced sensitivity.Comment: There are 16 pages and 4 figures for the manuscript. Supplementary information with 18 pages and 5 figures, appended at the end of the file with the manuscript. Source files in Word format converted to PDF. Submitted to Nature Physic

    From Oxford to Hawaii Ecophysiological Barriers Limit Human Progression in Ten Sport Monuments

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    In order to understand the determinants and trends of human performance evolution, we analyzed ten outdoor events among the oldest and most popular in sports history. Best performances of the Oxford-Cambridge boat race (since 1836), the channel crossing in swimming (1875), the hour cycling record (1893), the Elfstedentocht speed skating race (1909), the cross country ski Vasaloppet (1922), the speed ski record (1930), the Streif down-hill in KitzbĂŒhel (1947), the eastward and westward sailing transatlantic records (1960) and the triathlon Hawaii ironman (1978) all follow a similar evolutive pattern, best described through a piecewise exponential decaying model (r2 = 0.95±0.07). The oldest events present highest progression curvature during their early phase. Performance asymptotic limits predicted from the model may be achieved in fourty years (2049±32 y). Prolonged progression may be anticipated in disciplines which further rely on technology such as sailing and cycling. Human progression in outdoor sports tends to asymptotic limits depending on physiological and environmental parameters and may temporarily benefit from further technological progresses

    Explicit de Sitter Flux Vacua for Global String Models with Chiral Matter

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    We address the open question of performing an explicit stabilisation of all closed string moduli (including dilaton, complex structure and Kaehler moduli) in fluxed type IIB Calabi-Yau compactifications with chiral matter. Using toric geometry we construct Calabi-Yau manifolds with del Pezzo singularities. D-branes located at such singularities can support the Standard Model gauge group and matter content. In order to control complex structure moduli stabilisation we consider Calabi-Yau manifolds which exhibit a discrete symmetry that reduces the effective number of complex structure moduli. We calculate the corresponding periods in the symplectic basis of invariant three-cycles and find explicit flux vacua for concrete examples. We compute the values of the flux superpotential and the string coupling at these vacua. Starting from these explicit complex structure solutions, we obtain AdS and dS minima where the Kaehler moduli are stabilised by a mixture of D-terms, non-perturbative and perturbative alpha'-corrections as in the LARGE Volume Scenario. In the considered example the visible sector lives at a dP_6 singularity which can be higgsed to the phenomenologically interesting class of models at the dP_3 singularity.Comment: 49 pages, 5 figures; v2: references adde

    Combined Anterior-Posterior Surgery Versus Posterior Surgery for Thoracolumbar Burst Fractures: A Systematic Review of the Literature

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    Abstract: Study Design: A systematic quantitative review of the literature. Objective: To compare combined anterior-posterior surgery versus posterior surgery for thoracolumbar fractures in order to identify better treatments. Summary of Background Data: Axial load of the anterior and middle column of the spine can lead to a burst fracture in the vertebral body. The management of thoracolumbar burst fractures remains controversial. The goals of operative treatment are fracture reduction, fixation and decompressing the neural canal. For this, different operative methods are developed, for instance, the posterior and the combined anterior-posterior approach. Recent systematic qualitative reviews comparing these methods are lacking. Methods: We conducted an electronic search of MEDLINE, EMBASE, LILACS and the Cochrane Central Register for Controlled Trials. Results: Five observational comparative studies and no randomized clinical trials comparing the combined anteriorposterior approach with the posterior approach were retrieved. The total enrollment of patients in these studies was 755 patients. The results were expressed as relative risk (RR) for dichotomous outcomes and weighted mean difference (WMD) for continuous outcomes with 95% confidence intervals (CI). Conclusions: A small significantly higher kyphotic correction and improvement of vertebral height (sagittal index) observed for the combined anterior-posterior group is cancelled out by more blood loss, longer operation time, longer hospital stay, higher costs and a possible higher intra- and postoperative complication rate requiring re-operation and the possibility of a worsened Hannover spine score. The surgeons’ choices regarding the operative approach are biased: worse cases tended to undergo the combined anterior-posterior approach
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