Microdétermination des constantes physiques des acides aminés

Résumé Les constantes physiques à la fusion sont préconisées comme moyen d'identification des acides aminés.Les méthodes microchimiques deKofler ont permis d'obtenir des résultats. L'étude des températures de fusion des acides aminés purs a révélé une amélioration des données de la littérature, sans toutefois permettre de préconiser cette constante comme moyen d'identification.Les températures de fusion des eutectiques ont donné des résultats plus encourageants. Des valeurs définies ont été obtenues qui pourraient être utilisées pour l'identification de chaque individu. La netteté des lectures et la précision des mesures sont très satisfaisantes.

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Summary Physical constants are recommended as means of identifying amino acids. With the microKofler methods the melting temperature of these compounds is more accessible than previously. Better, however, are the melting temperatures of eutectics to identify amino acids. The accuracy of the rendings is very satisfactory.

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Zusammenfassung Die physikalischen Konstanten von Aminosäure-Schmelzen wurden zur Identifizierung dieser Substanzen vorgeschlagen. Mit Hilfe derKoflerschen Mikromethoden durchgeführte Untersuchungen der Schmelztemperaturen reiner Aminosäuren führten zwar zu einer Verbesserung der in der Literatur angegebenen Werte, ohne daß jedoch diese Kennzahlen zur Identifizierung solcher Verbindungen empfohlen werden könnten. Die Schmelzpunkte eutektischer Gemische geben besser verwertbare Resultate. Es konnten gut definierte Werte beobachtet werden, die sich zur Identifizierung jeder einzelnen Verbindung dieser Reihe verwenden lassen. Die Eindeutigkeit und Genauigkeit der Messungen ist durchaus befriedigend.

     

Modélisation des temps de réponse des capteurs chimiques

Modelling consists of considering the response and recovery times of a sensor to the target chemical species, as the sum of an ‘intrinsic’ response/recovery time, independent of the experimental conditions, and of an ‘extrinsic’ one, linked to the volume of the measurement cell and to the fluid flow. The experimental response/recovery times being almost always dominated by the extrinsic part, a dissymmetry between the response and recovery signals is observed for sensors whose response is not linear with the concentration of the target chemical species.     

Étude des propriétés des mélanges pebd régénéré / pebd vierge

This study is a contribution to the valorization of recycled low-density polyéthyléne (LDPE). First the characterization of five recycled LDPE produced from wastes coming from different sources was performed. The physical properties (density, melt flow index), chemical structure (Fourier transform infra-red spectroscopy) and mechanical properties (tensile strength and hardness) were investigated. The effect of the ratio of virgin LDPE on these physical and mechanical properties was studied in the case of the blends of recycled LDPE / virgin LDPE.     

Échelles caractéristiques des domaines tourbillonnaires apparaissant près des irrégularités des frontières

The possibility of the formation of a vortex domain of finite size near complex boundaries is analysed. For the proposed model, when such a scenario is attainable, the curve configuration delimiting the non-zero vorticity domain is found. This curve represents an approximate solution of an integral-differential equation obtained using the proposed model. It is shown that the vorticity level is a function of the characteristic dimension of the vortex domain, which depends on the size of the obstacle and is a homogeneous function of the Reynolds number.     

Analyse des molecules organochlorées piegées dans la matrice minérale des REFIOM

Analysis of the chloroorganic trapped in the mineral matrix of fly ash. Incineration is often considered as the most efficient process for urban waste destruction. Although it is a rather clean technique, it is often suspected to be the source of severe pollutions such as metal pollution or dioxin and furan emissions. In order to reduce hazardous emissions, various operating furnace parameters can be controlled, like gas residence time, flame temperature and excess air flow rate, among others. According to European regulations, incineration fly ash corresponds to class I disposal landfills, which demonstrates that it is considered as a toxic waste. The aim of this work was to develop a non equilibrium plasma process in order to study the behaviour of chloroorganics trapped on fly ash by on-line mass spectrometric analysis. The identification of the desorption of chloroorganics trapped within the mineral matrix presents juridical and scientific aspects. This study shows the existence of chemical reactions between the excited species produced from the plasma and the molecules desorbed from the mineral matrix of fly ash during the plasma treatment through the chemical analysis of the gaseous effluent. Special emphasis was put on the physicochemical properties of fly ash (composition of mineral matrix, particles size…)     

Caractérisation des structures spatio-temporelles: régimes dynamiques des ondes d'ionisation

In order to characterise the dynamical regimes and bifurcation scenarios in non-linear spatially extended systems, specific signal processing methods are required. These methods depart from the classical spectral analysis based on Fourier techniques commonly used to analyse purely temporal behaviour, but not well suited to multivariate data characterisation. Among these new approaches the biorthogonal decomposition (BOD) is a very powerful technique for investigating the complexity, and identifying underlying structures in space-time data. Here, after a short presentation of the BOD, we report on the characterisation of space-time structures of ionisation waves in the plasma of the positive column of a glow discharge in neon gas.     

Interprétation des mesures potentiométriques au moyen des courbes de polarisation

The observed experimental results of the potentiometric determinations can be explained by means of the polarisation curves. Thus explanations are given of the following phenomena: Electro-activity and non-electro-activity of ions. Nature of the potential taken by an electrode. Time required to establish a stable potential. Significance of the limiting potentials and the limiting concentrations. Influence of oxygen on the value of the measured potentials and on the limit of electro-activity of the oxidants. Significance of the “irreversible” potentials. Formulas giving the potentials in the presence of oxygen. Utility of removing the oxygen from the solution in view of potentiometric determinations. It appears that for all the “slow” redox systems, which are very numerous in inorganic and organic chemistry, the knowledge of the polarisation curves is fundamental.     

Réactions colorées de stéroĭdes

A number of colour reactions for the identification and determination of steroids are described.     

Prévision des courbes de dosages potentiométriques

The knowledge of polarisation curves can be used to explain the facts observed in the neighbourhood of the equivalent point in the course of potentiometric determinations as well as the anomalies presented by certain determination curves.It is also possible to interpret the role of a “potential mediator” during the determinations of oxido-reduction potentials.     

Influence des réactions chimiques préalables sur la forme des courbes de polarisation

Equations have been established for polarographic waves observed while a chemical reaction slowly takes place before the exchange of electrons.The method of calculation is analogous to that already used by one of the authors in the case of polarisation curves relative to the reversible or irreversible systems.The variation of the two half-wave potentials and the limiting densities of current have been deduced. The results have been verified by means of the experimental results of R. brdicka concerning pyruvic and phenylglyoxylic acids.     

Prévision des courbes de dosage par potentiométrie bimétallique au moyen des courbes de polarisation

The knowledge of polarisation curves permits the interpretation and prediction of the form of the curves obtained by bimetallic potentiometric determination.     

Remarques sur les définitions des acides et des bases

In the present state of knowledge it is not possible to account for the reactions used in analytical chemistry by setting up a single table of the “acids” and “bases” defined according to LEWIS.The most general definition which can be usefully adopted involves taking into account the exchange of “particles” (electrons, protons, ions, molecules) in the reactions. It follows from this that there arc as many types of reactions as there are “particles”.In accordance with the brönsted theory, in the case where the “particle” exchanged is the proton, an acid-base reaction is involved.     

Microanalyse fonctionnelle organique basée sur la détermination des constantes physiques. Identification des acides aminés

Résumé Le présent travail, tout en s'inscrivant comme contribution aux microdéterminations des constantes physiques des corps organiques, est en même temps une contribution à la microanalyse fonctionnelle organique, en ce sens qu'il préconise l'emploi de deux constantes physiques: la température de fusion eutectique et l'indice de réfraction pour identifier les acides aminés.Toutes les déterminations se font en une minute et sur un cristal. Cette méthode est extensible à d'autres classes de composés et susceptible de rendre de grands services dans le contrôle industriel et biochimique.La méthode préconisée ici pour l'identification des corps organiques concurrence avantageusement celle de préparation des dérivés des substances organiques et permettrait en outre d'accélérer les déductions de l'analyse qualitative organique classique, basées sur les différences, de solubilité (méthode deStaudinger, Kamm, Shriner, etc.). Ces nouvelles techniques se prêtent aussi à une extension quantitative.

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Summary This study, though entitled as a contribution to the microdetermination of the physical constants of organic compounds, is at the same time a contribution to functional organic microanalysis, in the sense that it involves the use of two physical constants: the eutectic fusion temperature and the index of refraction for identifying amino acids.All the determinations can be made in one minute and on only one crystal. This method may be extended to other classes of compounds and is capable of rendering great service in industrial and biochemical control.The method given here for the identification of organic compounds competes advantageously with that of preparing derivatives of organic materials and furthermore it permits speeding up the deductions of classical qualitative organic analysis based on the differences in solubility (method ofStaudinger, Kamm, Shriner, etc.). Quantitative developments are being studied.

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Zusammenfassung Die vorliegende Arbeit ist sowohl ein Beitrag zur Mikrobestimmung physikalischer Konstanten organischer Stoffe, wie gleichzeitig auch ein Beitrag zur funktionellen organischen Mikroanalyse. Es wird vorgeschlagen, die Bestimmung zweier physikalischer Konstanten, nämlich der eutektischen Temperatur und des Brechungsindex zur Identifizierung von Aminosäuren zu verwenden.Diese Bestimmungen sind in einer Minute an nur einem Kristall ausführbar. Die Methode ist auch auf andere Arten von Verbindungen übertragbar und geeignet, bei der Untersuchung technischer und biochemischer Produkte gute Dienste zu leisten.Die vorgeschlagene Methode ist vorteilhafter als die Identifizierung organischer Stoffe über den Weg der Herstellung von Derivaten. Außerdem läßt sich mit ihrer Hilfe die Ausführung des klassischen organischen Analysenganges nach dem Prinzip der Löslichkeitsunterschiede (Staudinger, Kamm, Shriner u. a.) beschleunigen. Die quantitative Auswertung der angegebenen Verfahren ist in Aussicht genommen.

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Ce travail a été subsidié par leFonds national de la recherche scientifique de Belgique.     

Interférences de deux modes propagatifs aux basses fréquences dans des conduits couplés par des perforations périodiques

A discrete model for low frequency acoustic propagation in a lattice made of two waveguides periodically coupled by perforations is presented. Firstly, it is shown that when at least one lattice mode is strongly evanescent, at any frequency, the lattice is equivalent to a simple waveguide with a locally reacting treatment on its walls (equivalent to an impedance); secondly, the resonant maxima of the insertion loss coefficient of a perforated tube muffler is due to the interference of the two modes of the lattice, which can both propagate even at low frequencies if the perforation ratio is not too large.     

Interprétation de l'isoréflectance des dépôts périodiques

From the two envelopes of reflectance obtained in the passband of a periodic optical filter, the concept of monochromatic isoreflectance already defined for a single wavelength is generalised to an exended spectral range. A method is proposed to obtain coatings with this property. These coatings are interesting for the design and the manufacture.     

Électroactivité des halogénures

The intensity-potential curves pertaining to the oxidation of iodides, bromides and chlorides at a polished platinum electrode, undergo deformations when the following factors are varied: initial concentration of halogen, pH, addition of ions that complex or reduce the halogen formed. Analysis of these deformations has led us to assume that the electrochemical behaviour of the three halides can be represented by a reaction of the type: 2 x₃^--2e ? 3 x₂ and not of the type: 2 x^-- 2e ? x₂ As far as bromides and chlorides are concerned the coulometric study agrees with this hypothesis     

Microlensing photométrique et détermination des masses stellaires

Microlensing was suggested for stellar mass determination of nearby stars by several authors (e.g. Paczyński). There are two aspects in gravitational microlensing: photometry and astrometry. Here only the photometric aspect, i.e. magnification of a background source by a stellar lens, will be considered. The first study in this domain was done by Paczyński. An attempt to investigate some observational constraints (Alard et al.) takes its origin in this study. It will be shown here that blending of the source by the lens not only induces a degeneracy which has been pointed out by Woźniak and Paczyński and can be removed by measuring the flux of the source outside the microlensing event, but also strongly reduces the photometric cross section as well as the duration of microlensing events. The expected number of events decreases strongly with blending. Blending effects can be reduced by selecting faint lens candidates. Unfortunately however, it is difficult to monitor a sufficient number of lens candidates per night, and restricting oneself to nearby and high proper motion objects would lead to a very small number of lens candidates. In the case of short duration events, the light curve must be sampled at short time intervals. When sampling daily, the condition is very strong and the expected rate of events very small. Observing from space would increase significantly the rate, but this gain is still insufficient. We conclude that the event rate will be very small and that the project does not seem to be feasible, at least under current observing conditions and even in the near future.     

Méthode indépendante des propriétés locales pour le calcul des indices de rétention en Chromatographie en phase gazeuse à température programmée

Retention indices of some phthalates, separated by temperature-programmed gas chromatography, computed using B-spline interpolations are more consistent with the scheme of this retention parameter. In applying this technique to a mixture of reference n-alkanes, which two successive members do not defer of more than four carbon atoms, it is possible to recover classical retention indices.