Synthesis, X-ray, and electronic structures of a new nickel dibromide complex. Activity in the regioselective catalyzed dimerization of ethylene into 1-butene

Reaction of the bis-(3,4)-dimethylphosphole-Xanthene 1b with [NiBr2(DME)] afforded a new nickel(II) dibromide complex, 2. Both its color and its NMR behavior change with temperature and solvent due to changes in the spin state of the complex. This led us to study the complex spin states using DFT calculations. Furthermore, the activity of 2 in catalyzed ethylene dimerization was studied, revealing both high activity and selectivity toward the production of 1-butene.     

Metric Sample Spaces of Continuous Geometric Curves and Estimation of Their Centroids

The metric sample space of Fréechet curves (Fréechet , 1934,1951,1961) is based on a generalization of regular curves that covers continuous curves in full generality. This makes it possible to deal with both smooth and non-smooth, even non-rectifiable geometric curves in statistical analysis. In the present paper this sample space is further extended in two directions that are relevant in practice: to incorporate information on landmark points in the curves and to impose invariance with respect to an arbitrary group of isometric spatial transformations. Properties of the introduced sample spaces of curves are studied, specially those concerning to the generation and representation of random curves by random functions.In order to provide measures of central tendency and dispersion of random curves, centroids and restricted centroids ofrandom curves are defined in a general metric framework, and methods for their consistent estimation are derived.     

Hepatic butyltin concentrations in beluga whales (Delphinapterus leucas) from the St Lawrence Estuary and northern Quebec,Canada

Butyltin (tributyltin TBT; dibutyltin DBT and monobutyltin MBT) speciation was measured in the liver of beluga whales from the St Lawrence Estuary and Hudson Strait (northern Quebec). Using GC–MS, liver samples were analysed from 21 beluga whales found dead, stranded along the shores of the St Lawrence during the period 1995–1998. In all cases, including a neonate specimen, the liver was contaminated with butyltin compounds with concentrations in the range 0.04–2.1 mg Sn kg⁻¹ on a dry weight basis. Liver samples of five beluga whales from Hudson Strait obtained in the summer of 1998 were also analysed. For these animals, hepatic butyltin concentrations were consistently below the detection limit (<0.5 ng Sn g⁻¹ for MBT and <0.2 ng Sn g⁻¹ for DBT and TBT). Compared with published data on the contamination by TBT of the marine mammals of the St Lawrence in 1988, these contemporary results clearly indicate that the level of contamination of the beluga whales in this coastal marine ecosystem has not decreased ten years after regulating the use of TBT‐based antifoulants on small craft. Copyright © 2000 John Wiley & Sons, Ltd.     

Biological Effects of Quinolones: A Family of Broad-Spectrum Antimicrobial Agents

Broad antibacterial spectrum, high oral bioavailability and excellent tissue penetration combined with safety and few, yet rare, unwanted effects, have made the quinolones class of antimicrobials one of the most used in inpatients and outpatients. Initially discovered during the search for improved chloroquine-derivative molecules with increased anti-malarial activity, today the quinolones, intended as antimicrobials, comprehend four generations that progressively have been extending antimicrobial spectrum and clinical use. The quinolone class of antimicrobials exerts its antimicrobial actions through inhibiting DNA gyrase and Topoisomerase IV that in turn inhibits synthesis of DNA and RNA. Good distribution through different tissues and organs to treat Gram-positive and Gram-negative bacteria have made quinolones a good choice to treat disease in both humans and animals. The extensive use of quinolones, in both human health and in the veterinary field, has induced a rise of resistance and menace with leaving the quinolones family ineffective to treat infections. This review revises the evolution of quinolones structures, biological activity, and the clinical importance of this evolving family. Next, updated information regarding the mechanism of antimicrobial activity is revised. The veterinary use of quinolones in animal productions is also considered for its environmental role in spreading resistance. Finally, considerations for the use of quinolones in human and veterinary medicine are discussed.     

Laser-driven proton acceleration and applications: Recent results

The acceleration of high-energy ion beams following the interaction of short (t < 1 ps) and intense (Iλ² > 10¹⁸ W cm^-2 μm²) laser pulses with solid targets is a field of research currently attracting high interest in the scientific community, due to some of the unique properties of these ion sources, promising routes toward the optimization of their energy content, and a number of possible, innovative applications in the scientific, technological and medical areas. Work on the characterization and development of these sources has progressed enormously over the past few years, thanks to the contribution of many groups worldwide. This paper will report some recent results, obtained in experiments carried out at the RAL and LULI laboratories, in which we investigated the ion acceleration mechanism, developed a technique to control the ion beam divergence and energy spectrum, and applied a proton radiography technique to investigate electric and magnetic field production following laser-matter interaction.     

Experimental and theoretical study of the mechanism for the kinetic of elimination of methyl carbazate in the gas phase

The elimination kinetic of methyl carbazate in the gas phase was determined in a static system over the temperature range of 340–390 °C and pressure range of 47–118 Torr. The reaction is homogeneous, unimolecular, and obeys a first order rate law. The decomposition products are methyl amine, nitrous acid, and CO gas. The variation of the rate coefficients with temperatures is given by the Arrhenius expression: log k₁ (s^?1) = (11.56 ± 0.34) ? (180.7 ± 4.1) kJ mol^?1(2.303 RT)^?1. The estimated kinetics and thermodynamics parameters are in good agreement to the experimental values using B3LYP/6‐31G (d,p), and MP2/6‐31G (d,p) levels of theory. These calculations imply a molecular mechanism involving a concerted non‐synchronous quasi three‐membered ring cyclic transition state to give an unstable intermediate, 1,2‐oxaziridin‐3‐one. Bond order analysis and natural charges implies that polarization of O (alkyl)? C (alkyl) bond of the ester is rate determining in this reaction. Copyright © 2008 John Wiley & Sons, Ltd.     

Calibration of discrete element modeling:Scaling laws and dimensionless analysis

In this paper,dynamic similarity conditions are derived for discrete element simulations by non-dimensionalising the governing equations.These conditions must b...     

A nonlinear theory for shells with slowly varying thickness

We study the Γ-limit of 3d nonlinear elasticity for shells of small, variable thickness, around an arbitrary smooth 2d surface. To cite this article: M. Lewicka et al., C. R. Acad. Sci. Paris, Ser. I 347 (2009).     

HS-SPME determination of volatile carbonyl and carboxylic compounds in different matrices

Specific chromatographic methodologies are developed for the analysis of carboxylic acids (C(2)-C(6), benzoic) and aldehydes (C(2)-C(10)) of low molecular weight in diverse matrices, such as air, automotive exhaust gases, human breath, and aqueous matrices. For carboxylic acids, the method is based on their reaction with pentafluorobenzyl bromide in aqueous solution, followed by the separation and identification of the resultant pentafluorobenzyl esters by means of headspace (HS)-solid-phase microextraction (SPME) combined with gas chromatography (GC) and electron capture detection (ECD). Detection limits in the microg/m(3) range are reached, with relative standard deviation (RSD) less than 10% and linear response (R(2) > 0.99) over two orders of magnitude. The analytical methodology for aldehydes is based on SPME with simultaneous derivatization of the analytes on the fiber, by reaction with pentafluorophenylhydrazine. The derivatization reagent is previously deposited on the SPME fiber, which is then exposed to the gaseous matrix or the HS of the sample solution. The pentafluorophenyl hydrazones formed on the fiber are analyzed selectively by means of GC-ECD, with detection limits in the ng/m(3) range, RSD less than 10%, and linear response (R(2) > 0.99) over two orders of magnitude.     

Chemical activation of carbon mesophase pitches

This paper studies the chemical activation of mesophase pitches of different origins in order to obtain activated carbons suitable for use as electrodes in supercapacitors. The effect that the activating agent (NaOH, LiOH, and KOH), the alkaline hydroxide/pitch ratio, and the activation temperature had on the characteristics of the resultant activated carbons was studied. LiOH was found to be a noneffective activating agent, while activation with NaOH and KOH yielded activated carbons with high apparent surface areas and pore volumes. The increase of the KOH/pitch ratio caused an increase of the chemical attack on the carbon, producing higher burnoffs and development of porosity. Extremely high apparent surface areas were obtained when the petroleum pitch was activated with 5:1 KOH/carbon ratio. The increase of the activation temperature caused an increase of the burnoff, although the differences were not as significant as those derived from the use of different proportions of activating agent.