Monitoring of the pre-equilibrium step in the alkyne hydration reaction catalyzed by au(Iii) complexes: A computational study based on experimental evidences

The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl 12, BF4 12, OTf 12, H2 O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF4 12 and OTf 12 have very similar coordination ability towards [(ppy)Au(IPr)]2+ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]2+ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]2+ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf 12 and BF4 12, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H2 O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts

The Role of Spleen and Liver Elastography and Color-Doppler Ultrasound in the Assessment of Transjugular Intrahepatic Portosystemic Shunt Function

The reference standard for assessing transjugular intrahepatic portosystemic shunt (TIPS) function is venography with portosystemic pressure gradient (PPG) measurement. This procedure is invasive and expensive; thus, we assessed the feasibility, reproducibility and diagnostic accuracy of color-Doppler ultrasound (CDUS) and spleen and liver stiffness (LS) measurements for identifying TIPS dysfunction. Twenty-four patients (15 undergoing TIPS placement and nine undergoing TIPS revision) consecutively underwent CDUS examination and LS and spleen stiffness (SS) determination by transient elastography (TE) and point shear-wave elastography (pSWE). All parameters were taken before TIPS placement/revision (1\u201315 d before) and 24 h after, just before revision by venography. pSWE inter-observer agreement was assessed by intra-class correlation coefficient (ICC). CDUS and elastographic data were correlated (Pearson coefficient) with pressure gradients (hepatic venous pressure gradient [HVPG], PPG). Main determinants of TIPS dysfunction were investigated by linear regression. Forty-nine paired examinations were performed in total: 49 (100%) SS reliable measurements by pSWE and 38 (88%) by TE. The ICC for pSWE values was 0.90 (95% confidence interval [CI] 0.81\u20120.94). SS values significantly correlated with HVPG and PPG (R = 0.51, p = 0.01). The area under the Receiver-Operating Characteristic (AUROC) curve of SS for diagnosing TIPS dysfunction was 0.86 (95% CI 0.70\u20120.96) using a 25 kPa cutoff. At multivariate analysis, the flow direction of the intrahepatic portal vein branches and SS values were independently associated to TIPS dysfunction. The intrahepatic portal vein branches flow direction and SS value are two simple, highly sensitive parameters accurately excluding TIPS dysfunction. SS measurement by pSWE is feasible, reproducible and both positively and significantly correlates with HVPG and PPG values

Five thousand years of fire history in the high North Atlantic region: Natural variability and ancient human forcing

Biomass burning influences global atmospheric chemistry by releasing greenhouse gases and climate-forcing aerosols. There is controversy about the magnitude and timing of Holocene changes in biomass burning emissions from millennial to centennial timescales and, in particular, about the possible impact of ancient civilizations. Here we present a 5gkyr record of fire activity proxies levoglucosan, black carbon, and ammonium measured in the RECAP (Renland ice cap) ice core, drilled in coastal eastern Greenland, and therefore affected by processes occurring in the high North Atlantic region. Levoglucosan and ammonium fluxes are high from 5 to 4.5gkyrgBP (thousand years before 2000gCE) followed by an abrupt decline, possibly due to monotonic decline in Northern Hemisphere summer insolation. Levoglucosan and black carbon show an abrupt decline at 1.1gkyrgBP, suggesting a decline in the wildfire regime in Iceland due to the extensive land clearing caused by Viking colonizers. All fire proxies reach a minimum during the second half of the last century, after which levoglucosan and ammonium fluxes increase again, in particular over the last 200 years. We find that the fire regime reconstructed from RECAP fluxes seems mainly related to climatic changes; however over the last millennium human activities might have influenced wildfire frequency/occurrence substantially

Performance of ALICE pixel prototypes in high energy beams

The two innermost layers of the ALICE inner tracking system are instrumented with silicon pixel detectors. Single chip assembly prototypes of the ALICE pixels have been tested in high energy particle beams at the CERN SPS. Detection efficiency and spatial precision have been studied as a function of the threshold and the track incidence angle. The experimental method, data analysis and main results are presented.Comment: 10 pages, 9 figures, contribution to PIX2005 Workshop, Bonn (Germany), 5-8 September 200

Beam Test Performance and Simulation of Prototypes for the ALICE Silicon Pixel Detector

The silicon pixel detector (SPD) of the ALICE experiment in preparation at the Large Hadron Collider (LHC) at CERN is designed to provide the precise vertex reconstruction needed for measuring heavy flavor production in heavy ion collisions at very high energies and high multiplicity. The SPD forms the innermost part of the Inner Tracking System (ITS) which also includes silicon drift and silicon strip detectors. Single assembly prototypes of the ALICE SPD have been tested at the CERN SPS using high energy proton/pion beams in 2002 and 2003. We report on the experimental determination of the spatial precision. We also report on the first combined beam test with prototypes of the other ITS silicon detector technologies at the CERN SPS in November 2004. The issue of SPD simulation is briefly discussed.Comment: 4 pages, 5 figures, prepared for proceedings of 7th International Position Sensitive Detectors Conference, Liverpool, Sept. 200

200-year ice core bromine reconstruction at Dome C (Antarctica): observational and modelling results

Bromine enrichment (Brenr) has been proposed as an ice core proxy for past sea-ice reconstruction. Understanding the processes that influence bromine preservation in the ice is crucial to achieve a reliable interpretation of ice core signals and to potentially relate them to past sea-ice variability. Here, we present a 210 years bromine record that sheds light on the main processes controlling bromine preservation in the snow and ice at Dome C, East Antarctic plateau. Using observations alongside a modelling approach, we demonstrate that the bromine signal is preserved at Dome C and it is not affected by the strong variations in ultraviolet radiation reaching the Antarctic plateau due to the stratospheric ozone hole. Based on this, we investigate whether the Dome C Brenr record can be used as an effective tracer of past Antarctic sea ice. Due to the limited time window covered by satellite measurements and the low sea-ice variability observed during the last 30 years in East Antarctica, we cannot fully validate Brenr as an effective proxy for past sea-ice reconstructions at Dome C.</p

New results from the NA57 experiment

We report results from the experiment NA57 at CERN SPS on hyperon production at midrapidity in Pb-Pb collisions at 158 $A$ GeV/$c$ and 40 $A$ GeV/$c$. $\Lambda$, $\Xi$ and $\Omega$ yields are compared with those from the STAR experiment at the higher energy of the BNL RHIC. $\Lambda$, $\Xi$, $\Omega$\ and preliminary $K_S^0$ transverse mass spectra are presented and interpreted within the framework of a hydro-dynamical blast wave model.Comment: 8 pages, 3 figures, contribution to the proceedings of The XXXVIIIth Rencontres de Moriond "QCD and High Energy Hadronic Interactions

Centrality dependence of the expansion dynamics in Pb-Pb collisions at 158 A GeV/c

Two-particle correlation functions of negatively charged hadrons from Pb-Pb collisions at 158 GeV/c per nucleon have been measured by the WA97 experiment at the CERN SPS. A Coulomb correction procedure that assumes an expanding source has been implemented. Within the framework of an expanding thermalized source model the size and dynamical state of the collision fireball at freeze-out have been reconstructed as a function of the centrality of the collision. Less central collisions exhibit a different dynamics than central ones: both transverse and longitudinal expansion velocities are slower, the expansion duration is shorter and the system freezes out showing smaller dimensions and higher temperature.Comment: 22 pages, 11 figures, Te