Les propriétés physiques, chimiques, mécaniques et rhéologiques des matériaux pulvérulents dépendent de manière notable de leur état granulaire. Ceci justifie la multiplicité des techniques granulométriques. Du fait de leur conception et de leur technologie, la plupart de ces techniques requièrent une préparation ou un prélèvement qui peuvent altérer l'état granulaire de l'échantillon. Une sonde granulométrique utilisable <i>in situ</i> présente donc un intérêt majeur, autant pour caractériser et contrôler en continu un procédé que pour obtenir des informations sur un mécanisme. C'est dans ce but que nous avons développé une sonde turbidimétrique spectrale. En effet, les mesures de turbidité sont réalisables par un capteur de petites dimensions utilisable <i>in situ</i> et relié à un ensemble spectrophotométrie. La distribution granulométrique d'une poudre en suspension est théoriquement accessible par le calcul à partir de son spectre de turbidité. Différents algorithmes et leurs logiciels correspondants ont été conçus ou mis au point Les possibilités et les limites de la turbidimétrie comme méthode granulométrique sont définies à partir de spectres mesurés ou simulés. Le domaine de sensibilité maximale ainsi déterminé est de [0.1-10 µm] pour les diamètres et inférieur à 10^-3pour la fraction volumique. Ces contraintes destinent la méthode aux applications en milieu peu chargé. La deuxième partie de ce travail est consacrée à l'étude particulière d'un phénomène de fragmentation de cristaux de suIfate de potassium dans un cristallisoir agité. L'objectif visé est double : prouver la faisabilité de la méthode pour suivre un processus réel dans un réacteur de type industriel et caractériser <i>in situ</i> un phénomène essentiel en cristallisation puisqu'il est responsable de la formation de la plupart des germes. Une telle étude en ligne n'a jamais été réalisée jusqu'à présent. Les paramètres du système sont la vitesse de rotation de l'agitateur, la nature du milieu liquide, le nombre et le diamètre des grains introduits initialement (grain "parents"). L'augmentation de la turbidité constatée expérimentalement est due à la production de petits fragments dont la taille est calculée grâce au logiciel évoqué plus haut. Dans l'éthanol, ces fragments microniques restent libres alors que dans une solution aqueuse saturée ils s'agglomèrent. Les influences de la plupart des paramètres sont expliquées. Le capteur turbidimétrique conçu et validé dans ce travail a été également appliqué avec succès à l'étude d'autres processus intervenant en cristallisation et en particulier la germination primaire, la germination secondaire et I'agglomération.

Cette étude a été consacrée à l'analyse du processus d'agglomération du sulfate de potassium et de l'alumine dans un milieu liquide turbulent. La turbidité constitue une technique tout à fait adaptée à la caractérisation de l'agglomération dont les effets sont ressentis essentiellement au niveau de la distribution granulométrique de la phase dispersée. Elle permet de quantifier et d'interpréter l'effet des différents paramètres qui interviennent au cours du développement du processus: - Paramètres hydrodynamiques : La cinétique d'agglomération est conditionnée par le mécanisme de rencontre des particules, lui-même dépendant des conditions hydrodynamiques; la morphologie des agglomérats peut témoigner de cette dépendance ; - Paramètres physico-chimiques : Lorsque les particules se rencontrent les interactions interviennent et assurent ou non la cohésion de l'amas formé. Il est nécessaire, enfin, de tenir compte de l'agglomération lorsque le comportement d'un système diphasique est influencé par l'évolution de la distribution granulométrique de la phase dispersé : C'est le cas dans la plupart des procédés de cristallisation.

Le syndrome du QT long (SQTL) est une anomalie du coeur caractérisée par une prolongation de l'intervalle de repolarisation entre les ondes Q et T sur l'électrocardiogramme. Ce syndrome pouvant provoquer de l'arythmie et même la mort peut être causé par des mutations génétiques, ou par la prise de certains médicaments. Plusieurs médicaments vendus sous ordonnance qui induisaient le syndrome du QT long ont été retirés du marché au cours de la dernière décennie et plusieurs autres ont échoué les tests de contrôle avant même leur sortie en pharmacie. La plupart de ces médicaments provoquent le SQTL à des doses thérapeutiques et dans pratiquement tous les cas, le syndrome est causé par une interaction du médicament avec le canal potassique transmembranaire du human ether-à-go-go-related-gene (hERG). Selon plusieurs études, la majorité des molécules qui bloquent le canal hERG se lieraient à des sites localisés dans la partie intracellulaire de la région du pore (hélice transmembranaire S5 et/ou S6) ou dans la région extracellulaire qui connecte S5 et S6. Dans la présente recherche, le rôle du segment extracellulaire (lIe583 -Tyr597 ) dans le fonctionnement du canal hERG et dans le mécanisme du SQTL fut étudié. Pour ce faire, l'interaction de ce segment avec quatre médicaments cardiotoxiques (bépridil, cétirizine, diphenhydramine, pentamidine) fut analysée en plus de vérifier l'interaction de ce segment et des médicaments avec des membranes modèles. Une approche combinant la RMN de l'état liquide et de l'état solide jumelée avec des analyses de dichroïsme circulaire a permis d'obtenir les conclusions suivantes. Tout d'abord, les résultats des interactions peptide-médicaments étudiées par RMN de l'état liquide du ¹H par des mesures de diffusion à l'aide de gradients de champ pulsés suggèrent une faible interaction du peptide avec chacun des médicaments dans un environnement aqueux. Cependant, une très forte interaction des médicaments et du peptide avec la membrane a été observée, suggérant un rôle potentiel de cette dernière dans la cardiotoxicité des médicaments provoquant le SQTL. Ensuite, les résultats des interactions médicaments-membranes et peptide-membrane étudiées par RMN de l'état solide du ²H et du ³¹P suggèrent une importante perturbation de la membrane (tant au niveau des têtes polaires que des chaînes acyle) par le segment extracellulaire lIe583 -Tyr597 . Finalement, les analyses de dichroïsme circulaire ont permis de démontrer que ce segment n'adopte pas une structure secondaire bien définie malgré sa forte interaction avec la membrane. Cependant, la conformation de ce segment varie en fonction de la nature et de la charge de la membrane modèle, ce qui prouve sa grande flexibilité structurale. Ces résultats suggèrent que la membrane joue un rôle important dans le fonctionnement du canal hERG, probablement en stabilisant des conformations transitoires durant les processus d'ouverture et de fermeture contrôlés par voltage. En terminant, les expériences biochimiques réalisées ont permis d'exprimer avec succès le segment S5. Des expériences sont toujours en cours pour purifier ce segment. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Syndrome du QT long, hERG, Médicaments cardiotoxiques, Membrane modèle, RMN de l'état liquide, RMN de l'état solide, Interaction médicaments-membranes, Interaction peptide-membranes.

Photoionization cross section calculations are performed for the ground ([Ne]3s23p63d 2D ) and the first two excited ([Ne]3s23p63d 2D and [Ne]3s23p64s 2S ) states of potassium-like transition metal ions (Sc+2, Ti+3, V+4, Cr+5, Mn+6, Fe+7), along with photoionization calculations for K-like Ca+ ions in the ground ([Ne]3s23p64s 2S ) state and the first two excited ([Ne]3s23p63d 2D and [Ne]3s23p63d 2D ) states. The discrete N-electron final state ion system orbitals are generated using the computer program AUTOSTRUCTURE; 24 configurations are included in the configuration-interaction (CI) calculation for transition metal ions, and 30 configurations for the case of Ca+ ions. The initial and final (N+1)-electron wavefunctions are generated using R-matrix along with photoionization cross sections. In addition to the non-relativistic (LS-coupling) R-matrix, we have used the relativistic (Breit-Pauli) R -matrix method to carry out these calculations to focus on relativistic effects. Relativistic and non-relativistic results are compared to demonstrate the influence of relativistic effects. The prominent 3p → 3d giant resonances are analyzed and identified, and our calculated positions and widths are compared with experimental results for K-like ions such as Ca+, Sc+2 and Ti+3. In the case of lower Z (22  Z  20) ions (Ca+, Sc+2 and Ti+3), the photoionization cross section spectra are dominated by the giant (3p  3d excitation) resonances, while in cases of higher Z (26  Z  23) ions (V+4, Cr+5, Mn+6 and Fe+7), the 3p  3d resonances lie below the ionization threshold, and the cross sections are dominated by 3p53d nd and 3p53d n’s Rydberg series of resonances. Comparison of the Ca+, Sc+2 and Ti3+ results with available theoretical and experimental data shows good agreement.

No description available.

Groundwater at many existing and former industrial sites and disposal areas is contaminated by halogenated organic compounds that were released into the environment. The chlorinated solvent trichloroethylene (TCE) is one of the most ubiquitous of these compounds. In situ chemical oxidation (ISCO) has been successfully used for the removal of TCE. The objective of this study was to apply the ISCO technology to remediate TCE-contaminated groundwater. In this study, potassium permanganate (KMnO4) was used as the oxidant during the ISCO process. The study consisted bench-scale and pilot-scale experiments. In the laboratory experiments, the major controlling factors included oxidant concentrations, effects of soil oxidant demand (SOD) on oxidation efficiency, and addition of dibasic sodium phosphate on the inhibition of production of manganese dioxide (MnO2). Results show that higher molar ratios of KMnO4 to TCE corresponded with higher TCE oxidation rate under the same initial TCE concentration condition. Moreover, higher TCE concentration corresponded with higher TCE oxidation rate under the same molar ratios of KMnO4 to TCE condition. Results reveal that KMnO4 is a more stable and dispersive oxidant, which is able to disperse into the soil materials and react with organic contaminants effectively. Significant amount of MnO2 production can be effectively inhibited with the addition of Na2HPO4. Results show that the increase in the first-order decay rate was observed when the oxidant concentration was increased, and the half-life was approximately 24.3 to 251 min. However, the opposite situation was observed when the second-order decay rate was used to describe the reaction. Results from the column experiment show that the breakthrough volumes were approximately 50.4 to 5.06 pore volume (PV). Injection of KMnO4 would cause the decrease in TCE concentration through oxidation. Results also indicate that the addition of Na2HPO4 would not inhibit the TCE removal rate. In the second part of this study, a TCE-contaminated site was selected for the conduction of pilot-scale study. A total of eight remediation wells were installed for this pilot-scale study. The initial TCE concentrations of the eight wells were as follows: C1 = 0.59 mg/L, C1-E = 0.64 mg/L, C1-W = 0.61 mg/L, EW-1 = 0.65 mg/L, EW-1E = 0.62 mg/L, EW-1W = 0.57 mg/L, C2 = 0.62 mg/L, C3 = 0.35 mg/L. C1, EW-1, C2, and C3 were located along the groundwater flow direction from the upgradient (C1) to the downgradient location (C3), and the distance between each well was 3 m. C1-E and C1-W were located in lateral to C1 with a distance of 3 m to C1. EW-1E and EW-1W were in lateral to EW-1 with a distance of 3 m to EW-1. In the first test, 2,700 L of KMnO4 solution was injected into each of the three injection wells (C1, C1-E, and C1-W) with concentration of 5,000 mg/L. Three injections were performed with an interval of 6 hr between each injection. After injection, the TCE concentrations in those three wells dropped down to below detection limit (<0.0025 mg/L). However, no significant variations in TCE concentrations were observed in other wells. In the second test, 2,700 L of KMnO4 solution was injected into injection well (EW-1) with concentration of 5,000 mg/L. Six injections were performed with an interval of 6 hr between each injection. After injection, the TCE concentrations in the injection well dropped down to below detection limit (<0.0025 mg/L). TCE concentrations in (C1, C1-E, C1-W, EW-1E, EW-1W, C2, and C3) dropped to 0.35-0.49 mg/L. After injection, no significant temperature and pH variation was observed. However, increase in conductivity and oxidation-reduction potential (ORP) was observed. This indicates that the KMnO4 oxidation process is a potential method for TCE-contaminate site remediation. The groundwater conductivity increased from 500 £gS/cm to 1,000 £gS/cm, and ORP increased from 200 to 600 mv. Increase in KMnO4, MnO2, and total Mn was also observed in wells. Results from the slug tests show that the hydraulic conductivity remained in the range from 10-4 to 10-5 m/sec before and after the KMnO4 injection.

A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation, in which palladium(II)-catalyzed cross-coupling of 9-(pyridin-2-yl)-9H-carbazoles with potassium aryltrifluoroborates is presented. Silver nitrate and tert-butanol were proved to be the best oxidant and solvent for the process, respectively. The product yields fluctuated from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, 9-(pyridin-2-yl)-9H-carbazole palladacycle was isolated and confirmed by X-ray crystallography. The kinetic isotope effect (kH/kD) for the C-H bond activation step was measured as 0.87. In addition, Hammett experiment gave a negative rho value, -2.14 with a reasonable correlation (R2 = 0.90). The directing group, pyridyl was demonstrated as a removable functional group. Finally, a rational catalytic mechanism is presented based on all experimental evidence.

Cyanide is a known toxic chemical, the production of plastics, electroplating, tanning, chemical syntheses, etc. At short-term exposure, cyanide causes rapid breathing, tremors, and long-term exposure to cyanide cause weight loss, thyroid effects, nerve damage and death. Although chemical and physical processes can be employed to degrade cyanide and its related compounds, they are often expensive and complex to operate. A proven alternative to these processes is biological treatment, which typically relies upon the acclimation and enhancement of indigenous microorganisms. Biological degradation of cyanide has often been offered as a potentially inexpensive and environmentally friendly alternative to conventional processes. The aims of first part of study were to evaluate the biodegradability of tetracyanonickelate (TCN) by Klebsiella oxytoca under anaerobic conditions. Results reveal that TCN can be biotransformed to methane by resting cells of K. oxytoca. Results also show that TCN biodegradation was inhibited by the addition of nitrate, nitrite, or ammonia at higher concentrations (5 and 10 mM). Moreover, it was found that the optimum pH for TCN conversion by K. oxytoca was about 7.1. Results from the fermenter experiment show that TCN can be completely degraded within 14 days. K. oxytoca is capable of using TCN as the nitrogen source under anaerobic conditions. TCN could be biotransformed to non-toxic end product (methane) by resting cells of K. oxytoca. Those studies provide us insight into the characteristics of TCN conversion by K. oxytoca under anaerobic conditions. In second part of this study, the technology of immobilized cells can be applied in biological treatment to enhance the efficiency and effectiveness of biodegradation. In this study, potassium cyanide (KCN) was used as the target compound and both alginate (AL) and cellulose triacetate (CT) gels were applied for the preparation of immobilized cells. The free suspension systems reveal that the cell viability was highly affected by initial KCN concentration and pH. Results show that immobilized cell systems could tolerate a higher level of KCN concentration and wider ranges of pH. In the batch experiments, the maximum KCN removal rates using alginate and cellulose triacetate immobilized beads were 0.108 and 0.101 mM h-1 at pH 7, respectively. Results also indicate that immobilized system can support a higher biomass concentration. Complete KCN degradation was observed after the operation of four consecutive degradation experiments with the same batch of immobilized cells. This suggests that the activity of immobilized cells can be maintained and KCN can be used as the nitrogen source throughout KCN degradation experiments. The maximum KCN removal rates using AL and CT immobilized beads in continuous-column system were 0.224 and 0.192 mM h-1 with initial KCN concentration of 3 mM, respectively. In third part of this study, a microbial process for the degradation of propionitrile by K. oxytoca was studied. The free and immobilized cells of K. oxytoca were then examined for their capabilities on degrading propionitrile under various conditions. The efficiency and produced metabolic intermediates and end-products of propionitrile degradation were monitored in bath and continuous bioreactor experiments. Results reveal that up to 100 mM and 150 mM of propionitrile could be removed completely by the free and immobilized cell systems, respectively. Furthermore, AL and CT immobilized cell systems show higher removal efficiencies in wider ranges of temperature (20-40¢XC) and pH (6-8) compared with the free cell system. Results also indicate that immobilized cell system could support a higher cell density to enhance the removal efficiency of propionitrile. Immobilized cells were reused in five consecutive degradation experiments, and up to 99% of propionitrile degradation was observed in each batch test. This suggests that the activity of immobilized cells can be maintained and reused throughout different propionitrile degradation processes. A two-step pathway was observed for the biodegradation of propionitrile. Propionamide was first produced followed by propionic acid and ammonia. Results suggest that nitrile hydratase and amidase were involved in the degradation pathways of K. oxytoca. In the continuous bioreactor, both immobilized cells were capable of removing 150 mM of propionitriles completely within 16 h, and the maximum propionitriles removal rates using AL and CT immobilized beads were 5.04 and 4.98 mM h-1, respectively. Comparing the removal rates obtained from batch experiments with immobilized cells (AL and CT were 1.57 and 2.18 mM h-1 at 150 mM of propionitrile, respectively), the continuous-flow bioreactor show higher potential for practical application. These findings would be helpful in designing a practical system inoculated with K. oxytoca for the treatment of cyanide-containing wastewater.

<p>Microwave materials have been widely used in a variety of applications ranging from communication devices to military satellite services, and the study of materials properties at microwave frequencies and the development of functional microwave materials have always been among the most active areas in solid-state physics, materials science, and electrical and electronic engineering. In recent years, the increasing requirements for the development of high speed, high frequency circuits and systems require complete understanding of the properties of materials function at microwave frequencies.</p><p>Ferroelectric materials usually have high dielectric constants, and their dielectric properties are temperature and electric field dependent. The change in permittivity as a function of electric field is the key to a wide range of applications. Ferroelectric materials can be used in fabrication capacitors for electronic industry because of their high dielectric constants, and this is important in the trend toward miniaturization and high functionality of electronic products. The simple tunable passive component based on ferroelectric films is a varactor which can be made as a planar structure, and electrically tunable microwave integrated circuits using ferroelectric thin films can be developed. Therefore, it is very important to characterize the dielectric constant and tunability of ferroelectric thin films.</p><p>This thesis shows experimental results for growth, crystalline properties and microwave characterization of Na0.5K0.5NbO3 (NKN), AgTa0.5Nb0.5O3 (ATN), Ba0.5Sr0.5TiO3 (BST) as well as AgTaO3 (ATO), AgNbO3 (ANO) thin films. The films were grown by Pulsed Laser Deposition (PLD) and rf-magnetron sputtering of a stoichiometric, high density, ceramic NKN, ATN, BST target onto single crystal LaAlO3(LAO), Al2O3 (sapphire), and Nd:YAlO3, and amorphous glass substrates. By x-ray diffractometry, NKN, ATN, BST films on LAO substrates were found to grow epitaxially, whereas films on r-cut sapphire substrates were found to be preferentially (00l) oriented.</p><p>Coplanar waveguide interdigital capacitor (CPWIDC) structures were fabricated by standard photolithography processing and metal lift-off technique. Microwave properties of the NKN/Sapphire and ATN/Sapphire with CPW structures were characterized using on-wafer microwave measurement technique. Measurement setup is composed of network analyzer, probe station, and microwave G-S-G probes. External electric field through the connection between network analyzer and power supply was applied to measure voltage tunability. Measured S-parameter were used for the calculation of capacitance, loss tanδ, tunability and K-factor.</p><p>The NKN films interdigital capacitors with 2 μm finger gap on Nd:YAlO3 showed superior performance compared to ATN in the microwave range from 1 to 40 GHz. Within this range, the voltage tunability (40V, 200 kV/cm) was about 29%, loss tangent ∼ 0.13, K-factor = tunability/tanδ from 152% @ 10GHz to 46% @ 40GHz.</p><p>The microwave performance of ATN film CPWIDC with 2 μm finger gap on sapphire substrate in the microwave range from 1 to 40 GHz showed that frequency dispersion is about 4.3%, voltage tunability was 4.7% @ 20GHz and 200 kV/cm, loss tangent ∼ 0.068 @ 20GHz, K-factor = tunability/tanδ is ranged from 124% @ 10GHz to 35% @ 40GHz.</p><p>The BST films CPWIDC with 2μmfinger gap on Al2O3 substrate showed frequency dispersion of capacitance in the microwave range from 1 to 40 GHz about 17%, voltage tunability = 1 - C(40V)/C(0) ∼ 22.2%, loss tangent ∼ 0.137 @ 20GHz, and K-factor = tunability/tanδ from 281% @ 10GHz to 95% @ 40GHz.</p>

La variété monoclinique de la zircone se transforme en variété quadratique à une température qui, selon le mode de préparation et le degré de pureté de l'échantillon, varie entre 1000° et 1100°C. Cette transformation est réversible bien qu'elle s'effectue avec retard au refroidissement. Elle s'accompagne d'une importante anomalie dilatométrie : au chauffage la contraction en volume est de l'ordre de 5%, elle interdit l'emploi de la zircone pure comme réfréctaire...