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La compréhension des mécanismes de transport et du comportement des radionucléides dans la biogéosphère sont nécessaires à l’évaluation des risques sanitaires et environnementaux de l’industrie nucléaire. Ces mécanismes sont contrôlés par la spéciation des radioéléments, c’est-à-dire leur répartition entre leurs différentes formes physico-chimiques dans l’environnement. Dans cette optique, cette thèse traite de la spéciation de l’uranium en milieu naturel. La biogéochimie de l’uranium a fait l’objet d’une synthèse bibliographique détaillée, qui a permis de restreindre le sujet à la complexation de l’uranium par l’acide oxalique, un acide organique hydrophile fréquemment rencontré dans les sols et doté de bonnes propriétés de complexation. L’établissement de diagrammes de spéciation à partir des constantes de complexation de la littérature a permis de définir les conditions analytiques de formation des complexes. Le choix de la technique analytique s’est porté sur le couplage d’une technique séparative (chromatographie liquide LC ou électrophorèse capillaire EC) à la spectrométrie de masse (ICPMS). La présence des complexes étudiés dans les échantillons synthétiques a été vérifiée par spectrophotométrie UV/visible. Les analyses menées par LC-ICPMS ont prouvé la labilité des complexes uranyle-acides organiques, c’est-à-dire leur propension à se dissocier pendant l’analyse, ce qui empêche une détermination fiable de la spéciation de l’uranium. En revanche, l’étude des complexes labiles d’un système métal-ligand par ECICPMS a été rendue possible par l’emploi de la méthode d’affinité, permettant de déterminer les constantes de complexations et les mobilités électrophorétiques. Cette thèse a permis de comparer les différentes méthodes de traitement mathématique de l’isotherme de complexation et de prendre en compte la force ionique et la concentration réelle du ligand. La méthode d’affinité a été employée avec succès sur les systèmes lanthane-oxalate, pris comme modèle, et uranyle-oxalate. Les résultats obtenus ont été validés sur un système naturel (site du Bouchet). Ceci montre l’apport de la méthode mise au point dans la modélisation de la spéciation de l’uranium. / To understand the transport mechanisms and the radionuclides behaviour in the biogeosphere is necessary to evaluate healthy and environmental risks of nuclear industry. These mechanisms are monitored by radioelements speciation, namely the distribution between their different physico-chemical forms in the environment. From this perspective, this PhD thesis deals with uranium speciation in a natural background. A detailed summary of uranium biogeochemistry has been written, which enables to restrict the PhD issue to uranium complexation with oxalic acid, a hydrophilic organic acid with good binding properties, ubiquitous in soil waters. Analytical conditions have been established by means of speciation diagrams. The speciation diagrams building by means of literature stability constants has allowed to define the analytical conditions of complex formation. The chosen analytical technique is the hyphenation of a separative technique (liquid chromatography LC or capillary electrophoresis CE) with mass spectrometry (ICPMS). The studied complexes presence in the synthetic samples has been confirmed with UV/visible spectrophotometry. LC-ICPMS analyses have proved the lability of the uranyl-organic acid complexes, namely their tendency to dissociate during analysis, which prevents from studying uranium speciation. CE-ICPMS study of labile complexes from a metal-ligand system has been made possible by employing affinity capillary electrophoresis, which enables to determine stability constants and electrophoretic mobilities. This PhD thesis has allowed to compare the different mathematical treatments of binding isotherm and to take into account ionic strength and real ligand concentration. Affinity CE has been applied successfully to lanthanum-oxalate (model system) and uranium-oxalate systems. The obtained results have been applied to a real system (situated in Le Bouchet). This shows the contribution of the developed method to the modelling of uranium speciation.

Heparin is a mixture of sulfonated polysaccharides which is negatively charged. Heparin is a substance which is important in organism and fundamentally affects its physiology. Main attribute of heparin is anticoagulation - it prevents the complete blood coagulation. This anticoagulant effect balances the hemocoagulation by influencing the coagulation pathway. In some cases a pharmacological application of heparin is needed so the heparin is administrated as a injection of physiological solution of sodium or calcium heparine salt. Monitoring of level of the heparin in blood is problematic - methods used today are based on the measurement of a time required for blood clot formation. The result evaluation is done by comparing a sample with reference solution. These methods are relatively imprecise, can not be used in "on-line" setting and are highly influenced by general health condition of patient. In this work some principles of affinity capillary electrophoresis were adapted from another work - heparin was determined indirectly by monitoring of decrease of the peak area of protamine. Protamine is medically used antidote of heparin because they create a stable complex together. In this work protamine was replaced by well defined tetraarginine because the most frequent amino acid in protamine is...

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In 1745 a Scotch Benedictine monk Andrew Gordon discovered Contact Charge Electrophoresis (CCEP) which remained in dormant state for centuries until gaining renewed prominence in the field of particle manipulation and actuation. Contact Charge Electrophoresis (CCEP) refers to the continuous to and fro motion of a conductive object between two electrodes subject to an applied voltage. The continuous motion of the conductive particle and the low power requirement provide an attractive alternative to traditional methods for particle manipulation techniques such as dielectrophoresis. Recent efforts to understand and apply CCEP have focused on the motion of single particles and we present dynamics of multiple conductive particles dispersed in non-conducting media that utilize CCEP to perform tasks like pumping and cargo transport operations as well as multiparticle clusters capable of tailored trajectories. Chapters 1 provides motivation for this work and background on CCEP. Providing brief details on development of microfluidic devices and modeling that are covered in more details in subsequent chapters. It also focuses on the historical aspect of CCEP, relevant background, mechanism, physics, application strategies in literature, strategies developed for single particle systems and possible extension to multiparticle systems. Chapters 2 and 3 talk about the dynamics and modeling of multiple conductive particles both in dispersion and aggregates/clusters powered by CCEP. In Chapter 2, we propose a new hybrid approach based on image-based method proposed earlier by Bonnecaze[18] for modeling CCEP. It covers challenges to modeling a multiple particle system in confinement, dynamics of chain formation and dynamics of cluster comprising conductive and non-conductive particles between two electrodes. While Chapter 3 focuses on details of methods and techniques used in development of the simulation for dispersion of conductive particles in confinement. Here we also illustrate variation of conductivity for complete range of electrode separation with varying volume fraction. Chapter 4 expands on multiple particle CCEP and shows that when we physically constrain particle trajectories to parallel tracks between the electrodes, the traveling waves of mechanical actuation can be realized in linear arrays of electromechanical oscillators that move and interact via electrostatic forces. Conductive spheres oscillate between biased electrodes through cycles of contact charging and electrostatic actuation. The combination of repulsive interactions among the particles and spatial gradients in their natural frequencies lead to phase locked states characterized by gradients in the oscillation phase. The frequency and wavelength of these traveling waves can be specified independently by varying the applied voltage and the electrode separation. We demonstrate how traveling wave synchronization can enable the directed transport of material cargo. Our results suggests that simple energy inputs can power complex patterns of mechanical actuation with potential opportunities for soft robotics and colloidal machines. Chapter 5 systematically investigate the dynamics of cluster comprising multiple spherical conductive particles driven via contact charge electrophoresis (CCEP). We are specifically interested in understanding dynamics of closed packed cluster of particles with both conductive and non-conductive particles in three dimensions(3D). Finally, Chapter 6 summarizes new ideas and proposes possible applications for multiple particle Contact charge electrophoresis motivated by this dissertation.

Thesis (Ph. D. in Chemical Engineering)--Vanderbilt University, Dec. 2007. / Title from title screen. Includes bibliographical references.