The Enantiomers of Trinorbornane and Derivatives Thereof

Herein, we report the synthesis of the enantiomers of trinorbornane, a tetracyclic saturated hydrocarbon with the chemical formula C11H16. The preparation of these rigid carbon scaffolds was enabled by the successful chiral separation of its tricyclic precursor, thus allowing the enantiomers to be synthesized through a reductive radical cyclization reaction. Assignment of the absolute conformation of the enantiomers was achieved through VCD experiments. Further, we report an alternative cyclization procedure providing access to hydroxyl and phenyl sulfone functionalized trinorbornanes

Evaluating postoperative rotator cuff healing: Prospective comparison of MRI and ultrasound

AbstractBackgroundThe objective of this prospective comparative single centre study was to compare postoperative rotator cuff healing rates as assessed by magnetic resonance imaging (MRI) versus ultrasonography (US).Material and methodsBetween October 2012 and February 2013, 61 patients underwent arthroscopic repair of postero-superior rotator cuff tears. Each patient underwent MRI and US 6 months later. The findings were assessed independently by two observers. We compared intra-observer and inter-observer levels of agreement regarding healing rates assessed by MRI and US.ResultsIntra-observer agreement regarding the MRI interpretation was 95% (κ coefficient, 0.83) for one observer and 98% (κ coefficient, 0.94) for the other. Values of κ for inter-observer agreement ranged across readings from 0.76 to 0.90. When MRI was taken as the reference, US had 80% sensitivity and 98% specificity.DiscussionMRI and US provide similar assessments of postoperative rotator cuff healing, although US is less sensitive. Intra-observer and inter-observer agreements are very good.Level of evidenceIII

Characterization of Metal Aggregates by Scanning Microscopy: Particle Sizes and Space Distribution in Intermetallic Particles

Various metal aggregates prepared using ionizing radiation were studied by microscopy techniques. A metal deposit onto a carbon felt obtained from solutions containing Pt and Ru was shown to consist of nanometric particles containing both metals. Another study deals with a subnanometric silver aggregate. The nuclearity of the aggregate was studied by scanning tunneling microscopy (STM). Additional information from pulse radiolysis experiments allowed the determination of the Ag73+ stoichiometry. The third material consisted of Ag/Pd submicron powders (70/30 or 75/25% w/w) used in electronics, and made of spherical bimetallic grains; X-ray diffraction showed segregation. The spatial distribution of each metal was obtained by combining space-resolved X-ray microanalysis in the transmission electron microscope, X-ray photoelectron spectroscopy and secondary ion mass spectrometry. Each grain was shown to be core/rind structured (core: pure Ag; rind: 10-15 nm thick 11% Ag/89% Pd w/w alloy)

Xenon isotopes in Archean and Proterozoic insoluble organic matter: a robust indicator of syngenecity?

Insoluble organic materials (kerogens) isolated from ancient sedimentary rocks provide unique insights into the evolution of early life. However, establishing whether these kerogens are indeed syngenetic with the deposition of associated sedimentary host rocks, or contain contribution from episodes of secondary deposition, is not straightforward. Novel geochemical criterions are therefore required to test the syngenetic origin of Archean organic materials. On one hand, the occurrence of mass-independent fractionation of sulphur isotopes (MIF-S) provides a tool to test the Archean origin of ancient sedimentary rocks. Determining the isotope composition of sulphur within kerogens whilst limiting the contribution from associated minerals (e.g., nano-pyrites) is however challenging. On the other end, the Xe isotope composition of the Archean atmosphere has been shown to present enrichments in the light isotopes relative to its modern composition, together with a mono-isotopic deficit in ¹²⁹Xe. Given that the isotopic composition of atmospheric Xe evolved through time by mass dependent fractionation (MDF) until ∼2.5-2.0 Ga, the degree of MDF of Xe isotopes trapped in kerogens could provide a time stamp for the last chemical equilibration between organic matter and the atmosphere. However, the extent to which geological processes could affect the signature of Xe trapped in ancient kerogen remains unclear. In this contribution, we present new Ar, Kr and Xe isotopic data for four kerogens isolated from 3.4 to 1.8 Gy-old cherts and confirm that Xe isotopes from the Archean atmosphere can be retained within kerogens. However, new Xe-derived model ages are lower than expected from the ages of host rocks, indicating that initially trapped Xe components were at least partially lost and/or mixed together with some Xe carried out by younger generations of organic materials, therefore complicating the Xe-based dating method. Whilst non-null Δ³³S values and ¹²⁹Xe deficits relative to modern atmosphere constitute reliable imprints from the Archean atmosphere, using Xe isotopes to provide information on the syngenetic origin of ancient organic matter appears to be a promising - but not unequivocal - tool that calls for further analytical development

Large Deviations Analysis for Distributed Algorithms in an Ergodic Markovian Environment

We provide a large deviations analysis of deadlock phenomena occurring in distributed systems sharing common resources. In our model transition probabilities of resource allocation and deallocation are time and space dependent. The process is driven by an ergodic Markov chain and is reflected on the boundary of the d-dimensional cube. In the large resource limit, we prove Freidlin-Wentzell estimates, we study the asymptotic of the deadlock time and we show that the quasi-potential is a viscosity solution of a Hamilton-Jacobi equation with a Neumann boundary condition. We give a complete analysis of the colliding 2-stacks problem and show an example where the system has a stable attractor which is a limit cycle

Is good clinical practice becoming poor clinical care?

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