Existence d'isomeres e et z d'ylures de cycloimmonium

E and Z isomers of p-nitrobenzoyl, 4-p-tolyl[1-2-4]triazolum methylide 5b and p-nitrobenzoyl, 4-p-phenyl[1-2-4]triazolium methylide 5e, have been characterised.     

Interdisciplinary study on pottery experimentally impregnated with wine

Experimentally developed ceramic pots, with two different sizes of grain, were half-filled with wine and subjected to thermal alteration at constant elevated temperature ((60 ± 2)°C) in darkness for 12 weeks. This work sought to characterise the samples thereby obtained from chemical and mineralogical perspectives using scanning electron microscopy and an energy-dispersive X-ray microanalysis system (SEM-EDX), Fourier transform infrared spectroscopy (FTIR) and capillary electrophoresis (CE) with UV detection as an alternative to chromatographic methods, due to its good resolution, automation, simplicity, high speed, low consumption of chemicals and short time required for sample preparation. The capillary electrophoresis method was used for the detection of five wine biomarkers: succinic acid, malic acid, tartaric acid, citric acid and lactic acid. In general, it was noted that the fine-grained ceramic assortment retained the organic material better than the coarser-grained ceramics. An interesting observation derived from this study was that not only could tartaric acid be considered as a biomarker for wine residues in archaeological pottery, but malic acid could also act similarly for white wine and lactic acid for red wine.     

The effect of the hydration degree on the hydrothermal and thermo-oxidative stability of some collageneous matrices

The methods of the thermal analysis (TG, DTG and DTA) were used in order to investigate the effect of the hydration degree on the thermal behaviour of some collageneous matrices. It was pointed out that the degradation of hydrated collagen in the temperature range 20-400°C occurs through two successive processes accompanied by mass losses. The first process, consisting in the collagen dehydration, is endothermic and takes place in the temperature range ≈25 - ≈125°C. The second process is exothermic and consists in the decomposition and/or thermo-oxidation of dry collagen. The thermal parameters of both processes depend on the hydration degree of collagen. The observed dependencies show that the hydrothermal and thermo-oxidative stability of collagen are strongly correlated with its water content. This revised version was published online in July 2006 with corrections to the Cover Date.     

Development of an enzymatic microreactor based on microencapsulated laccase with off-line capillary electrophoresis for measurement of oxidation reactions

Microencapsulation is used here as a new technique to immobilize enzymes in a microreactor coupled off-line to capillary electrophoresis (CE), allowing the determination of enzymatic reaction products. The redox enzyme laccase was encapsulated using the method of interfacial cross-linking of poly(ethyleneimine) (PEI). The 50 μm diameter capsules were slurry packed from a suspension into a capillary-sized reactor made easily and quickly from a short length of 530 μm diameter fused-silica tubing. The volume of the bed of laccase microcapsules in the microreactor was in the order of 1.1 μL through which 50 μL of the substrate o-phenylenediamine (OPD) was flowed. The oxidation product 2,3-diaminophenazine (DAP) and the remaining OPD were quantified by CE in a pH 2.5 phosphate buffer. Peak migration time reproducibility was in the order of 0.4% RSD and peak area reproducibility was less than 1.7% RSD within the same day. Using the OPD peak area calibration curve, a conversion efficiency of 48% was achieved for a 2-min oxidation reaction in the microreactor.     

An empirical MM2 augmented force field for the cycloimmonium ylides

An original procedure approach taking into account the implementation of parameters determined, using calculations based on density functional theory, for the amidocyano-pyridinium methylide in the MM2 augmented harmonic potential function has been proposed. A good agreement between theoretical force field calculation and X-ray diffraction data has been observed. Thus an empirical force field for cycloimmonium ylides has been established. It provides good quality geometries for cycloimmonium ylide molecules by energy minimization. In this study we proposed a new MM2 augmented atom-type for the ylidic carbon atom. To our knowledge no attempt has been done in this way for such organic systems. Thus, we have shown that parameterization established by the DFT method is able to reproduce or to predict with good accuracy the structures of the cycloimmonium ylide compounds. This study also includes a full conformational analysis.     

Conformational Study of Glycal-Type Neuraminidase Inhibitors

The conformational flexibility of two glycal-type neuraminidase inhibitors has been studied, using several molecular modeling techniques. In agreement with the experimental data available, an intramolecular hydrogen bond, representing a key structural feature that controls the conformer distribution in solution, has been identified. The contribution of each substituent to the overall equilibrium was evaluated using simplified derivatives. Additionally, four methods for estimating NMR coupling constants from dihedral angles were evaluated and the Haasnoot method was found to be appropriate for this class of sugars. These results should allow a better understanding of the structural parameters governing physico-chemical properties of glycal-like compounds. Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Carbohydrate Chemistry to view the free supplemental file.     

Rare earth doped cobalt ferrite thin films deposited by PLD

CoFe₂O₄ thin films with preferential texture structure, small grain size, and perpendicular magnetic anisotropy can be obtained by the pulsed laser deposition (PLD) technique. In this work, we studied the influence of the Fe³⁺ ions substitution by three elements from lanthanide group (Dy, La, and Gd) on the structural properties of the thin films. The samples were deposited by Nd:YAG laser (λ=532 nm, 10 ns) ablation of CoFe_1.8RE_0.2O₄, (RE=Dy, La, Gd) targets at various substrate temperatures ranging from room temperature to 600 °C. The microstructure and chemical composition of the thin films were investigated by Raman spectroscopy, XRD, SEM-EDS, and ToF-SIMS. The XRD patterns and Raman spectra of the thin films indicated the formation of a single spinel structure. Thus, the desired substitution of the iron ions in the spinel lattice with the RE elements was achieved in the thin films, although in the bulk material, their presence determined the formation of a residual phase with a perovskite-type structure.     

Etude par desorption thermique programmee des proprietes des argiles modifiees

The present work tries to emphasize the effect of acid/basis properties of montmorillonite type clays by ion exchange with cations of different natures. The acidity and basicity measuring was made by thermo programated desorption (TPD)1,2, using ammonia like basis agent and carbon dioxide like acid agent. With TPD method we can determine acid/basis proprietes by measuring of the quantity of the ammonia and carbon dioxide termodesorbed. Clays are crystalline aluminosilicates, similar with the zeolyts, who presents the property of ion exchanging. That propriety can be applicated for pollutants cations from aquatic solutions. Ion exchanging propriety depends of a lot of factors: the cation nature, the valence and the ionic ray of the cation present in the impregnated solution. That's an advantage for depollution process of heavy metals by fixing of these metals by montmorillonite structure. By using TPD metod we can obtaine a caracteristic diagram. This revised version was published online in July 2006 with corrections to the Cover Date.