Thermal behaviour of polyacrylamidoxime-copper chelates

The purpose of this work was to investigate the effect of several factors (anion type in the copper salt, pH and concentration of the salt solution) on the structure and thermo-oxidative degradation of the polyacrylamidoxime-copper chelates, by using elemental analysis, IR spectroscopy and dynamic thermogravimetry. The chelates containing copper ions as sulphate exhibit a better initial thermal stability than the polyacrylamidoxime fibre presumably due to the crosslinking generated by the intermolecular complexation of the ions; the removal of the sulphate anions takes place concomitantly with the second step of polymeric chain decomposition. The initial thermal decomposition of the chelates formed by copper ions as nitrate begins at lower temperatures as compared to the polyacrylamidoxime fibre, probably by the nitrate anion release, which partly overlaps the initial decomposition of the copper ion-crosslinked polymeric chains. Copper ions as either sulphate or nitrate catalyse the reactions involved in the main step of polyacrylamidoxime fibre decomposition; the higher the copper amount, the stronger the catalytic effect.     

Periodic unfolding and Robin problems in perforated domains

The periodic unfolding method was introduced in 2002 by D. Cioranescu et al. for the study of classical periodic homogenization. In this Note, we extend this method to perforated domains introducing also a boundary unfolding operator. As an application, we study the homogenization of some elliptic problems with Robin condition on the boundary of the holes. To cite this article: D. Cioranescu et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Laser flash photolysis of diphenylsulfonyldiazomethane: detection of the sulfene and a sulfene-pyridine ylide

The photochemistry of diphenylsulfonyldiazomethane (DSD) was studied by means of nanosecond laser flash photolysis. The photochemical behavior of this molecule upon UV irradiation is characterized by sulfene formation, presumed to arise via Wolff rearrangement of a carbene. We were able to detect the sulfene and the sulfene ylide formed upon sulfene trapping by pyridine. Sulfene quenching by nucleophiles was also examined.     

Comparison between radioimmunoanalysis and Mancini methods for a case of ascorbic acid radioprotection on rats contaminated with tritiated water

The recovery of humoral immune response has been comparatively studied by a radioimmunoanalysis (RIA) method and by Mancini single immunoradial diffusion method in an experiment consisting in chronic contamination with low doses of tritiated water (HTO) and oral administration of high doses of ascorbic acid on rats as radioprotector. The radioprotective effect of ascorbic acid was found to be dependent both on the radiation dose and the amount of ascorbic acid administered.     

Mesomorphic behaviour and TSDC measurements of ortho-metallated palladium(II) and platinum(II) complexes with S,O-donor co-ligands

A series of ortho-metallated Pd and Pt complexes containing an imine ligand carrying three alkoxy chains and N-benzoylthiourea derivatives as co-ligands were prepared and their liquid crystalline properties investigated. Their structures were assigned based on elemental analysis, IR and ¹H NMR spectroscopy, whereas thermal properties were investigated by differential scanning calotimetry and polarising optical microscopy. All the compounds exhibit monotropic transitions involving nematic and smectic A phases, with the mesomorphic behaviour strongly related to the type of N-benzoylthiourea as well as the metal centre used. The thermally stimulated depolarisation current technique was employed to determine the conduction mechanism, phase transition temperature and the activation energies for one of the ortho-metallated Pd complexes.     

Capillary Atmospheric Pressure Electron Capture Ionization (cAPECI): A Highly Efficient Ionization Method for Nitroaromatic Compounds

We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O₂ ^– or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O₂ ^– leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.

Synthesis of core‐shell structured carboxylated microparticles with a straightforward procedure and their evaluation as a polymer support

Poly(trimethylolpropane trimethacrylate) microspheres with a narrow size distribution were obtained by precipitation polymerization. They were subsequently modified by surface grafting with acrylic acid in a polar ethanol–water reaction medium, without stabilizer, yielding core‐shell particles with diameters in the micrometer range. The resulting polymeric material was characterized by SEM and potentiometric titration, FTIR spectroscopy, and thermal analysis. It was shown that the particle characteristics (size, size distribution, and functionality) obtained by this straightforward procedure can be controlled by modifying the synthesis parameters (monomer concentration, agitation rate, and temperature). The high functionality, the chemical and physico‐mechanical stability, as well as the possibility to control the performances of the resulting polymeric materials by synthesis allow its applications in various areas. Envisaging separation and catalysis domains, Cu(II), Cd(II), and Cr(III) uptake capacity from aqueous solutions was investigated under noncompetitive conditions as a function of synthesized particle functionality, time, and pH range. It was also found that the addition of the carboxylated microparticles to polyethylene stabilized with α‐tocopherol improved the thermo‐oxidative behaviour of the polymeric material. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5889–5898, 2005     

The effect of hydrogen bubbles on the thymol blue velocity measurement technique

This note describes an experimental study of the damaging effect of hydrogen bubbles on the effectiveness of the thymol blue velocity measurement method. Specifically, we document the effect of flow velocity, cathode voltage, and cathode diameter on bubble formation and the quality of the thymol blue pattern. The time of bubble damage, i.e., the interval preceding the destruction of the blue pattern, was measured and reported as a function of flow velocity, cathode voltage, and cathode diameter.     

Second order parallel tensors and Ricci solitons in 3-dimensional normal paracontact geometry

The aim of this paper is to study two problems in the framework of paracontact geometry of dimension \(3\) , namely, the class of parallel symmetric tensor fields of \((0, 2)\) -type and possible Lorentz Ricci solitons. We search for two types of Ricci solitons: the first when its potential vector field is exactly the characteristic vector field \(\xi \) of the paracontact structure and the second when the potential vector field is a paracontact-holomorphic one. For the former case we find all variants of Ricci solitons, expanding, steady and shrinking, and the fact that \(\xi \) is a conformal Killing vector field. A class of examples is completely discussed.     

The Prandtl number effect near the onset of Bénard convection in a porous medium

This note focuses on Kladias and Prasad's claim that the critical Rayleigh number for the onset of Bénard convection in an infinite horizontal porous layer increases as the Prandtl number decreases, and argues that the critical Rayleigh number (Ra_c) depends only on the Darcy number (Da), as linear stability analysis indicates. The two-dimensional steady-convection problem is then solved numerically to document the convection heat transfer effect of the Rayleigh number, Darcy number, Prandtl number, and porosity. The note concludes with an empirical correlation for the overall Nusselt number, which shows the effect of Prandtl number at above-critical Rayleigh numbers. The correlation is consistent with the corresponding correlation known for Bénard convection in a pure fluid.