Recent progress in numerical methods for the determination of thermokinetics

The results of a multinational concerted programme on the determination of thermokinetics are presented. The purpose of the programme was to compare different numerical methods which have been independently proposed for the determination of thermokinetics from experimental calorimetric data. To achieve this end, the same experimental data, obtained from two heat-flow calorimeters, were distributed and successively analyzed by the different methods. Numerical methods based on the state function theory, on Fourier transform analysis, on dynamic optimization and on a simple differentiation of the data were thus critically tested.

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Zusammenfassung Es wurden die Ergebnisse der gemeinsamen Arbeiten über die Bestimmung der Thermokinetik mit 4 numerischen Methoden (dynamische Optimalisierung, Methode der Zustandfunktionen, harmonische Analyse und umgekehrte Korrektion) vorgestellt. Die experimentellen Daten wurden mit Hilfe von 2 Kalorimetern mit einer konstanten Temperatur des Isoliermantels ermittelt. Die Durchführung der Versuche ermöglichte ein Vergleich der angewandten Methoden.

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Résumé Les résultats d'un programme de recherches concerté multinational sur la détermination des données thermocinétiques sont présentés. Le but du programme était de comparer différentes méthodes numériques proposées indépendamment pour la détermination des données thermocinétiques à partir des mesures calorimétriques expérimentales. Pour celà, les mêmes données expérimentales fournies par deux calorimètres à flux de chaleur ont été distribué es et analysées successivement par 4 méthodes: utilisation des variables d'état, analyse de la transformée de Fourier, optimalisation dynamique et simple différentiation des données.

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Exchange interactions and theoretical analysis of (31)P NMR spectra in VO(HPO(4)).0.5H(2)O

Based on combined DFT/broken symmetry approach, a theoretical analysis of the exchange interactions in the VO(HPO(4)).0.5H(2)O solid is performed. Depending on the crystallographic structures reported in the literature, two very different spin models are formulated. In addition, a complete fit of the temperature-dependent (31)P NMR chemical shift is performed to determine exchange and hyperfine constants. The magnetic models used in the fit are those obtained by our theoretical calculations. The comparison between the calculated and fitted exchange constants confirms the adequacy of an isolated dimer model and rules out the alternating antiferromagnetic chain model for VO(HPO(4)).0.5H(2)O.     

Preparation and characterization of a new enzyme electrode based on solid paraffin and activated graphite particles

A new electrochemical biosensor was developed by incorporating an enzyme into a solid-paraffin-graphite-particle matrix. Tyrosinase served as model enzyme and the biosensor response was characterized with respect to its response to dopamine. The influence of different experimental parameters (tyrosinase loading, flow rate, oxygen dependence, pH, etc.) was investigated in order to optimize the biosensor performance. The electrode response was fast, reversible and linear in a large concentration domain (0.1 muM-1 mM). The enzyme-solid paraffin carbon paste electrode (CPE) showed markedly improved stability in flow injection analysis compared to the classical liquid paraffin-graphite-based biosensors. The biosensor allowed a sampling rate of 79 samples per hour, the repeatability of the injections was improved with respect to the classical CPE with a relative standard deviation of 2.2% (N = 63), and the detection limit for dopamine was 50 nM. The biosensor response to some phenol and catechol derivatives was also investigated.     

Accelerated weathering of polyaramid and polybenzimidazole firefighter protective clothing fabrics

Exposure to simulated ultraviolet sunlight at 50 °C and 50% relative humidity caused a significant deterioration in the mechanical performance of polyaramid and polyaramid/polybenzimidazole based outer shell fabrics used in firefighter jacket and pants. After 13 days of exposure to these conditions the tear resistance and tensile strength of both fabrics decreased by more than 40%. The polybenzimidazole containing fabric was less impacted by these conditions as it maintained approximately 20% more of its mechanical properties. These conditions also significantly degraded a water repellant coating on the fabric, which is critical to the water absorption performance of the outer shell fabrics. However, these conditions had little impact on the ultraviolet light protection of the outer shell as both fabrics still blocked 94% of ultraviolet light after 13 days of exposure. Confocal microscopy showed these conditions caused significant surface decomposition of and the switch from ductile to brittle failure of the polyaramid fibers. Cleavage of the amide linkages and the formation of oxidation species (as observed by Infrared spectroscopy) suggested these conditions caused photo-oxidation of the polyaramid fibers. There was little evidence of polybenzimidazole fiber degradation.     

Use of coated capillaries for the electrophoretic separation of stereoisomers of a growth hormone secretagogue

The diastereoisomeric separation of peptidomimetics of hexarelin, a strong growth hormone secretagogue, in CE has been studied. Highly sulfated‐γ‐CD was found to be an appropriate selector for the separation of the stereoisomers. However, non‐repeatable analyses were obtained on bare fused silica capillary due to the progressive adsorption of the analytes on the capillary wall. Two types of polyelectrolyte coating agents were tested to prevent this phenomenon. Coating with neutral polyethylene oxide was found to be efficient but resulted in a very long analysis time (about 40 min). Coating with cationic poly(diallyldimethylammonium) chloride was found both to prevent analyte adsorption, reduce analysis time and alter separation selectivity. EOF measurement revealed that the highly sulfated‐γ‐CDs were strongly adsorbed on the poly(diallyldimethylammonium) chloride coating surface yielding a stable strong cathodic EOF, which considerably reduced analysis time (about 12 min). Very good repeatability of analysis was obtained (RSD_{migration time}<1%).     

2-(2-Pyridyl)Indole Derivatives Preparation Via Fischer Reaction on Montmorillnite K10/Zinc Chloride Under Microwave Irradiation

Fischer condensation was performed in 50-60% yield in lower temperatures and shorter times if conducted in solvent-free acid medium under microwave irradiation.     

Brownian dynamics of water confined in AOT reverse micelles: A field-cycling deuteron NMR relaxometry study

Reversed micelles and water in oil micro-emulsions can be used to solubilize biopolymers and genetic materials allowing analyzing their properties in a confined geometry. Nuclear Magnetic Resonance Dispersion (NMRD) provides a powerful and a noninvasive experimental technique to probe the long-term dynamics of these confined systems. However, the first step is to analyze and understand the slow dynamics of water inside these micro-reactors without any guest molecule. This is the aim of this presentation. Experimental results have been obtained for deuteron ²H NMRD of water confined in reverse micelles of bis (2-ethylhexyl) sodium sulfosuccinate (AOT) dispersed in isooctane C₈H₁₈. The water content is expressed as the molar ratio W₀ = [Water]/[AOT]. The radius of the spherical reversed micelles, R_m, increases almost linearly with W₀. In our case, W₀ is chosen in the range 20 ≤ W₀ ≤ 50 (35 ≤ R_m ≤ 80 Å). The frequency dependence for the spin-lattice relaxation rate R₁(ω) exhibits two regimes, for all W₀ values: a plateau at low frequency, proportional to 1/R_m, followed by the beginning of an algebraic decay. These experimental observations are discussed and compared to a numerical simulation of the intermittent Brownian diffusion of a water molecule inside a rotating reverse micelle. The possibility to probe some properties of the confinement, such as the localisation time on the sulfonated palisade and/or the water self-diffusion inside the water pool is emphasised.     

Réduction de modèle en convection naturelle par une méthode d'identificationModel Reduction in natural convection using an identification method.

In this numerical study, a natural convection Reduced Model (RM) is built by using results of a Detailed Model (DM, obtained by a pseudo-spectral method), associated with an optimisation problem. RM's structure is defined from a matrix formulation obtained after spatial discretisation of the problem local equations. RM's matrices are identified through the minimisation of a functional build on the discrepancy between DM's and RM's responses, for several values of Rayleigh number. The method is applied to a laminar steady flow in a 2D differentially heated cavity (Window problem). The RM allows one to strongly reduce computing time. To cite this article: M. Girault et al., C. R. Mecanique 332 (2004).     

Macrospin limit and configurational anisotropy in nanoscale permalloy triangles

In permalloy submicron triangles, configurational anisotropy—a higher-order form of shape anisotropy—yields three equivalent easy axes, imposed by the structures’ symmetry order. Supported by micromagnetic simulations, an experimental method was devised to evaluate the nanostructure dimensions for which a Stoner-Wohlfarth type of reversal could be used to describe this particular magnetic anisotropy. In this regime, a straightforward procedure using an in-plane rotating field allowed us to quantify experimentally the six-fold anisotropy fields for triangles of different thicknesses and sizes.