Reactivity studies of 2,3,5,6-Tetra(2-pyridyl) pyrazine (tppz) with first-row transition metal ions

Reactions of 2,3,5,6-tetra(2-pyridyl) pyrazine (tppz) with [ML₆][X]₂ (L = CH₃CN, H₂O;X = [BF₄]⁻, [ClO₄]⁻, [NO₃]⁻ [BArF]⁻(BArF - B[3,5-C₆H₃(CF₃)₂]₄) lead to the high-yield formation of mononuclear [M(tppz)₂]²⁺, (M = Mn^II, Fe^II, Co^II, and Ni^II) and dinuclear [Ni₂(tppz)(CH₃CN)₆]⁴⁺ species. The new compounds were fully characterized by X-ray crystallographic, spectroscopic, and magnetic susceptibility measurements. Surprisingly, the 2:1 M:tppz reactions did not lead to isolation of the dinuclear species except in the case of Ni(II). It was further noted that even in the case of the Ni reactions, the nuclearity of the product depends on the choice of anions and the reaction conditions. Magnetic measurements of the mononuclear species [Co(tppz)₂]²⁺ revealed thermally induced spin-crossover behavior from a high-spin S = 3/2 at higher temperatures to a low-spin S = 1/2 complex at lower temperatures. The dinuclear compound [Ni₂(tppz)(CH₃CN)₆]⁴⁺ exhibits a weak anti-ferromagnetic interaction through the bridging tppz ligand.     

Structure,homogeneity ranges,magnetic, and electrical properties of the ordered Laves phases RENi4Mg with MgCu4Sn type structure

New ordered Laves phases RENi₄Mg (RE = Sc, Sm, Tb–Lu) were synthesized from the elements in sealed tantalum ampoules in an induction furnace. Six of the structures were refined on the basis of X-ray single crystal data. The diffraction experiments gave hint for small homogeneity ranges RE_1+xNi₄Mg_1?x. Magnetic susceptibility measurements show Curie–Weiss behavior for RE = Gd, Dy, Ho, Tm, Yb and the resulting effective magnetic moments suggest both stable trivalent states for all RE and a non-magnetic state for Ni. Gd_1+xNi₄Mg_1?x (x ≈ 0.12) orders antiferromagnetically at a Néel temperature of T_N = 4.6(5) K. Resistivity measurements reflect the metallic nature of these compounds.     

Adsorption kinetics and mechanical properties of thiol-modified DNA-oligos on gold investigated by microcantilever sensors

Immobilised DNA-oligo layers are scientifically and technologically appealing for a wide range of sensor applications such as DNA chips. Using microcantilever-based sensors with integrated readout, we demonstrate in situ quantitative studies of surface-stress formation during self-assembly of a 25-mer thiol-modified DNA-oligo layer. The self-assembly induces a surface-stress change, which closely follows Langmuir adsorption model. The adsorption results in compressive surface-stress formation, which might be due to intermolecular repulsive forces in the oligo layer. The rate constant of the adsorption depends on the concentration of the oligo solution. Based on the calculated rate constants a surface free energy of the thiol-modified DNA-oligo adsorption on gold is found to be -32.4 kJ mol(-1). The adsorption experiments also indicate that first a single layer of DNA-oligos is assembled on the gold surface after which a significant unspecific adsorption takes place on top of the first DNA-oligo layer. The cantilever-based sensor principle has a wide range of applications in real-time local monitoring of chemical and biological interactions as well as in the detection of specific DNA sequences, proteins and particles.     

Two Dimensional Aggregation Procedure: An Alternative to the Matrix Algebraic Algorithm

The aggregation procedure is an important theoretical and empirical topic of economics. It appears in the Microeconomics and Macroeconomics, in Panel and Cross-Sectional Data Analysis, in Data Mining Analysis, in Input–Output and Agent-based Computational Economics Modelling. The question of the choice of algorithm is became important since the size of the sample data has became more important, and despite of the speed of the computers. In this paper we present the “classical” algorithm (the “matrix algebraic” one) of aggregation of the two-dimensional sample data, and compare it to the alternative algorithms (the “vectorial” one) we developed. Then we present some extensions to the multidimensional aggregation.      

Ignition and Charring of PVC-Based Electric Cables

Fire Technology - The ignition of four different PVC-based electric cables was studied using cone calorimeter and the influence of the charring phenomenon on ignition was investigated. The...     

A Novel Constellation Shaping Technique for Bit-Interleaved Coded Modulation

We present a new and simple method which consists to apply constellation shaping to bit-interleaved turbo-coded modulation (BICTM) over additive white Gaussian noise channels. By assuming the example of a 3-bit/dim 16-PAM BITCM, it is shown that this technique can provide shaping gain of 0.79 dB.     

Predicting the Thermal Conductivity of AlSi/Polyester Abradable Coatings: Effects of the Numerical Method

The final target of this study is to achieve a better understanding of the behavior of thermally sprayed abradable seals such as AlSi/polyester composites. These coatings are used as seals between the static and the rotating parts in aero-engines. The machinability of the composite coatings during the friction of the blades depends on their mechanical and thermal effective properties. In order to predict these properties from micrographs, numerical studies were performed with different software packages such as OOF developed by NIST and TS2C developed at the UTBM. In 2008, differences were reported concerning predictions of effective thermal conductivities obtained with the two codes. In this article, a particular attention was paid to the mathematical formulation of the problem. In particular, results obtained with a finite difference method using a cell-centered approach or a nodal formulation allow explaining the discrepancies previously noticed. A comparison of the predictions of the computed effective thermal conductivities is thus proposed. This study is part of the NEWAC project, funded by the European Commission within the 6th RTD Framework programm (FP6).     

Biology-based modeling to analyze uranium toxicity data on Daphnia magna in a multigeneration study

Recent studies have investigated chronic toxicity of waterborne depleted uranium on the life cycle and physiology of Daphnia magna. In particular, a reduction in food assimilation was observed. Our aims here were to examine whether this reduction could fully account for observed effects on both growth and reproduction, for three successive generations, and to investigate through microscope analyses whether this reduction resulted from direct damage to the intestinal epithelium. We analyzed data obtained by exposing Daphnia magna to uranium over three successive generations. We used energy-based models, which are both able to fit simultaneously growth and reproduction and are biologically relevant. Two possible modes of action were compared - decrease in food assimilation rate and increase in maintenance costs. In our models, effects were related either to internal concentration or to exposure concentration. The model that fitted the data best represented a decrease in food assimilation related to exposure concentration. Furthermore, observations of consequent histological damage to the intestinal epithelium, together with uranium precipitates in the epithelial cells, supported the assumption that uranium has direct effects on the digestive tract. We were able to model the data in all generations and showed that sensitivity increased from one generation to the next, in particular through a significant increase of the intensity of effect, once the threshold for appearance of effects was exceeded.     

A sensitivity study for an indoor channel

The context of this paper is the 3D wave propagation simulation with a software based on a ray tracing technique in typical indoor environments. The presented works are complementary to these of the literature which propose the validation of a propagation model in comparison with measurements. Indeed, the presented study consists of a sensitivity analysis of an already validated propagation model. The considered parameters are electromagnetic, geometric and electric; they directly intervene in the two parts of a simulation: the modelling of the wave propagation and of the environment. The aim of this study is to contribute to the setting up of parameterisation rules of a simulation software according to two criteria: the accuracy and the compromise between accuracy and computation time.