One-pot amide synthesis from allyl or benzyl halides and amines by Pd-catalysed carbonylation

Amides can be prepared from allyl or benzyl halides and primary or secondary amines, using Pd(0) catalyst under CO pressure, in a one-pot synthesis. The reaction proceeds through the acyl palladium halide formation which undergoes an acylic nucleophilic substitution from the amine.     

Population kinetics in turbulent plasmas: The role of non-Markovian fluctuations

A novel approach to the modeling of atomic populations in turbulent plasmas is applied to ionization-recombination balance calculations. Fluctuations of the fluid parameters are retained using a time-dependent statistical approach, suitable for cases where the turbulence characteristic times are of the same order as or smaller than the typical atomic relaxation times. We show that the populations are sensitive to the shape of the autocorrelation function of the fluctuations. An illustration is proposed through an ideal two-level system forced by non-Markovian temperature fluctuations.     

Densely Functionalized 2-Methylideneazetidines: Evaluation as Antibacterials

Twenty-two novel, variously substituted nitroazetidines were designed as both sulfonamide and urethane vinylogs possibly endowed with antimicrobial activity. The compounds under study were obtained following a general procedure recently developed, starting from 4-nitropentadienoates deriving from a common β-nitrothiophenic precursor. While being devoid of any activity against fungi and Gram-negative bacteria, most of the title compounds performed as potent antibacterial agents on Gram-positive bacteria (E. faecalis and three strains of S. aureus), with the most potent congener being the 1-(4-chlorobenzyl)-3-nitro-4-(p-tolyl)azetidine 22, which displayed potency close to that of norfloxacin, the reference antibiotic (minimum inhibitory concentration values 4 and 1–2 μg/mL, respectively). Since 22 combines a relatively efficient activity against Gram-positive bacteria and a cytotoxicity on eucharyotic cells only at 4-times higher concentrations (inhibiting concentration on 50% of the cultured eukaryotic cells: 36 ± 10 μM, MIC: 8.6 μM), it may be considered as a promising hit compound for the development of a new series of antibacterials selectively active on Gram-positive pathogens. The relatively concise synthetic route described herein, based on widely available starting materials, could feed further structure–activity relationship studies, thus allowing for the fine investigation and optimization of the toxico-pharmacological profile.     

Directed and elliptic flow in 197Au+197Au at intermediate energies

Directed and elliptic flow for the ¹⁹⁷Au+¹⁹⁷Au system at incident energies between 40 and 150 MeV per nucleon has been measured using the INDRA 4π multi-detector. For semi-central collisions, the excitation function of elliptic flow shows a transition from in-plane to out-of-plane emission at around 100 MeV per nucleon. The directed flow changes sign at a bombarding energy between 50 and 60 MeV per nucleon and remains negative at lower energies. Molecular dynamics calculations (CHIMERA) indicate sensitivity of the global squeeze-out transition on the σ _NN and demonstrate the importance of angular momentum conservation in transport codes at low energies.     

Spectral line shapes modeling in turbulent plasmas

In this work we investigate the influence of low frequency turbulence on Doppler spectral line shapes in magnetized plasmas. Low frequency refers here to fluctuations whose typical time scale is much larger than those characterizing the atomic processes, such as radiative decay, collisions and charge exchange. This ordering is in particular relevant for drift wave turbulence, ubiquitous in edge plasmas of fusion devices. Turbulent fluctuations are found to affect line shapes through both the spatial and time averages introduced by the measurement process. The profile is expressed in terms of the fluid fields describing the plasma. Assuming the spectrometer acquisition time to be much larger than the turbulent time scale, an ordering generally fulfilled in experiments, allows to develop a statistical formalism. We proceed by successively investigating the effects of density, fluid velocity and temperature fluctuations on the Doppler profile of a spectral line emitted by a charge exchange population of neutrals. Line shapes, and especially line wings are found to be affected by ion temperature or fluid velocity fluctuations, and can in some cases exhibit a power-law behavior. These effects are shown to be measurable with existing techniques, and their interpretation in each particular case would rely on already existing tools. From a fundamental point of view, this study gives some insights in the appearance of non-Boltzmann statistics, such as Lévy statistics, when dealing with averaged experimental data.     

A Hybrid Micro­Macro­Model for the Description of Evolving Anisotropy in Finite Polycrystal Plasticity

The paper outlines recent developments of an efficient computational micro-macro modeling of evolving anisotropies in metallic polycrystals. Main focus is put onto large strain deformation processes where the anisotropy is caused by developments of crystallographic texture. We construct a hybrid micro-macro framework that mixes ingredients of a purely macroscopic modeling with scale bridging operations of selected micromechanisms. On the micromechanical side, we develop a new algorithmic procedure to capture the crystal reorientation for evolving fcc and bcc textures based on a parametrization of rotations in the Rodigues space. The computational model provides a fast and robust method for the estimation of evolving textures. This computational tool for texture estimation is incorporated in a modular format into a micro-macro-model, where it governs the evolution of macrostructural tensors due to texture development. The general framework for the hybrid embedding is a purely phenomenological setting of anisotropic finite plasticity in the logarithmic strain space. The model provides an efficient and computationally handable two-scale approach for the prediction of effects caused by complex microstructural changes in polycrystals. The capability of the proposed method is demonstrated by means of representative numerical examples. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Neutralizing the Impact of the Virulence Factor LecA from Pseudomonas aeruginosa on Human Cells with New Glycomimetic Inhibitors

Bacterial adhesion, biofilm formation and host cell invasion of the ESKAPE pathogen Pseudomonas aeruginosa require the tetravalent lectins LecA and LecB, which are therefore drug targets to fight these infections. Recently, we have reported highly potent divalent galactosides as specific LecA inhibitors. However, they suffered from very low solubility and an intrinsic chemical instability due to two acylhydrazone motifs, which precluded further biological evaluation. Here, we isosterically substituted the acylhydrazones and systematically varied linker identity and length between the two galactosides necessary for LecA binding. The optimized divalent LecA ligands showed improved stability and were up to 1000-fold more soluble. Importantly, these properties now enabled their biological characterization. The lead compound L2 potently inhibited LecA binding to lung epithelial cells, restored wound closure in a scratch assay and reduced the invasiveness of P. aeruginosa into host cells.     

Prompt light particle emission in the 36Ar + 58Ni reaction at 95 MeV/nucleon

The prompt component at intermediate velocity of light charged particles is investigated. An improved coalescence model coupled to the intra-nuclear cascade code ISABEL is used to obtain light complex particle energy spectra and multiplicities as a function of impact parameter. The results are compared with experimental data from the ³⁶Ar + ⁵⁸Ni experiment at 95 MeV/nucleon, performed with the INDRA 4π detection system. The calculated prompt component is found to rather well reproduce proton spectra. For complex light charged particles the calculated components well populate the high energy part of spectra. Prompt emission can therefore explain the large transverse energies experimentally observed at mid-rapidity. Received: 27 July 2000 / Accepted: 20 November 2000     

Conservative methods for the Toda lattice equations

We are concerned with the numerical integration of the Todalattice equations by using different conservative methods. Numericalexperiments suggest that the global error for isospectral schemesdecreases exponentially with time but it is almost constantfor either symplectic or more general integrators. We providea theoretical explanation for these experimental findings.     

Finite Element Analysis of General Magnetomechanical Coupling Phenomena

In this paper we consider the derivation of a finite element model for fully–coupled magneto–mechanical boundary value problems based on a vector–valued magnetic potential. The formulation allows for the incorporation of nonlinear, anisotropic and hysteretic constitutive response. A piezomagnetic inclusion problem is computed to test the implementation. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)