Mechanistic investigation of Rh(i)-catalysed asymmetric Suzuki–Miyaura coupling with racemic allyl halides

Understanding how catalytic asymmetric reactions with racemic starting materials can operate would enable new enantioselective cross-coupling reactions that give chiral products. Here we propose a catalytic cycle for the highly enantioselective Rh(I)-catalysed Suzuki–Miyaura coupling of boronic acids and racemic allyl halides. Natural abundance 13C kinetic isotope effects provide quantitative information about the transition-state structures of two key elementary steps in the catalytic cycle, transmetallation and oxidative addition. Experiments with configurationally stable, deuterium-labelled substrates revealed that oxidative addition can happen via syn- or anti-pathways, which control diastereoselectivity. Density functional theory calculations attribute the extremely high enantioselectivity to reductive elimination from a common Rh complex formed from both allyl halide enantiomers. Our conclusions are supported by analysis of the reaction kinetics. These insights into the sequence of bond-forming steps and their transition-state structures will contribute to our understanding of asymmetric Rh–allyl chemistry and enable the discovery and application of asymmetric reactions with racemic substrates

Model- and calibration-independent test of cosmic acceleration

We present a calibration-independent test of the accelerated expansion of the universe using supernova type Ia data. The test is also model-independent in the sense that no assumptions about the content of the universe or about the parameterization of the deceleration parameter are made and that it does not assume any dynamical equations of motion. Yet, the test assumes the universe and the distribution of supernovae to be statistically homogeneous and isotropic. A significant reduction of systematic effects, as compared to our previous, calibration-dependent test, is achieved. Accelerated expansion is detected at significant level (4.3 sigma in the 2007 Gold sample, 7.2 sigma in the 2008 Union sample) if the universe is spatially flat. This result depends, however, crucially on supernovae with a redshift smaller than 0.1, for which the assumption of statistical isotropy and homogeneity is less well established.Comment: 13 pages, 2 figures, major change

The Impact of Gaia and LSST on Binaries and Exoplanets

Two upcoming large scale surveys, the ESA Gaia and LSST projects, will bring a new era in astronomy. The number of binary systems that will be observed and detected by these projects is enormous, estimations range from millions for Gaia to several tens of millions for LSST. We review some tools that should be developed and also what can be gained from these missions on the subject of binaries and exoplanets from the astrometry, photometry, radial velocity and their alert system

The impact of Gaia and LSST on binary stars and exo-planets

Two upcoming large scale surveys, the ESA Gaia and LSST projects, will bring a new era in astronomy. The number of binary systems that will be observed and detected by these projects is enormous, estimations range from millions for Gaia to several tens of millions for LSST. We review some tools that should be developed and also what can be gained from these missions on the subject of binaries and exoplanets from the astrometry, photometry, radial velocity and their alert systems.Comment: 8 pages, 2 figures, Proceedings of the IAU Symposium No. 282: From Interacting Binaries to Exoplanets: Essential Modeling Tools. Tatranska Lomnica, Slovaki

Prevalence of pulmonary hypertension in the general population

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Search for charginos in e+e- interactions at sqrt(s) = 189 GeV

An update of the searches for charginos and gravitinos is presented, based on a data sample corresponding to the 158 pb^{-1} recorded by the DELPHI detector in 1998, at a centre-of-mass energy of 189 GeV. No evidence for a signal was found. The lower mass limits are 4-5 GeV/c^2 higher than those obtained at a centre-of-mass energy of 183 GeV. The (\mu,M_2) MSSM domain excluded by combining the chargino searches with neutralino searches at the Z resonance implies a limit on the mass of the lightest neutralino which, for a heavy sneutrino, is constrained to be above 31.0 GeV/c^2 for tan(beta) \geq 1.Comment: 22 pages, 8 figure

Search for composite and exotic fermions at LEP 2

A search for unstable heavy fermions with the DELPHI detector at LEP is reported. Sequential and non-canonical leptons, as well as excited leptons and quarks, are considered. The data analysed correspond to an integrated luminosity of about 48 pb^{-1} at an e^+e^- centre-of-mass energy of 183 GeV and about 20 pb^{-1} equally shared between the centre-of-mass energies of 172 GeV and 161 GeV. The search for pair-produced new leptons establishes 95% confidence level mass limits in the region between 70 GeV/c^2 and 90 GeV/c^2, depending on the channel. The search for singly produced excited leptons and quarks establishes upper limits on the ratio of the coupling of the excited fermio

Search for lightest neutralino and stau pair production in light gravitino scenarios with stau NLSP

Promptly decaying lightest neutralinos and long-lived staus are searched for in the context of light gravitino scenarios. It is assumed that the stau is the next to lightest supersymmetric particle (NLSP) and that the lightest neutralino is the next to NLSP (NNLSP). Data collected with the Delphi detector at centre-of-mass energies from 161 to 183 \GeV are analysed. No evidence of the production of these particles is found. Hence, lower mass limits for both kinds of particles are set at 95% C.L.. The mass of gaugino-like neutralinos is found to be greater than 71.5 GeV/c^2. In the search for long-lived stau, masses less than 70.0 to 77.5 \GeVcc are excluded for gravitino masses from 10 to 150 \eVcc . Combining this search with the searches for stable heavy leptons and Minimal Supersymmetric Standard Model staus a lower limit of 68.5 \GeVcc may be set for the stau mas

Hadronization properties of b quarks compared to light quarks in e+e- -> q qbar from 183 to 200 GeV

The DELPHI detector at LEP has collected 54 pb^{-1} of data at a centre-of-mass energy around 183 GeV during 1997, 158 pb^{-1} around 189 GeV during 1998, and 187 pb^{-1} between 192 and 200 GeV during 1999. These data were used to measure the average charged particle multiplicity in e+e- -> b bbar events, _{bb}, and the difference delta_{bl} between _{bb} and the multiplicity, _{ll}, in generic light quark (u,d,s) events: delta_{bl}(183 GeV) = 4.55 +/- 1.31 (stat) +/- 0.73 (syst) delta_{bl}(189 GeV) = 4.43 +/- 0.85 (stat) +/- 0.61 (syst) delta_{bl}(200 GeV) = 3.39 +/- 0.89 (stat) +/- 1.01 (syst). This result is consistent with QCD predictions, while it is inconsistent with calculations assuming that the multiplicity accompanying the decay of a heavy quark is independent of the mass of the quark itself.Comment: 13 pages, 2 figure

Uncoupling mobility and learning: When one does not guarantee the other

Mobile learning was an embedded component of the pedagogical design of an undergraduate course, Digital media and society. In the final semester of 2010 and the first semester of 2011, 135 students participated in an empirical study inquiring into their perceptual experience of mobile learning. To control for access to technology, an optional iPad student loan scheme was used. The iPads were loaded with an electronic textbook and a mobile application of the learning moderation system. Eighty students participated in ten-person focus groups. Feedback on mobility and the electronic text was positive and optimistic. However, the majority of students were not convinced that the trial made a difference to their learning. This result was interpreted to indicate that the presence or absence of mobile devices does not guarantee or preclude student learning. © 2011 Springer-Verlag