Adsorption on solid surfaces from solution is a fundamental property of a surfactant. It might even be the most important aspect of surfactant behavior, since it influences many applications, such as cleaning, detergency, dispersion, separation, flotation, and lubrication. Consequently, fundamental investigations of surfactant adsorption are relevant to many areas. The main aim of this thesis has been to elucidate the adsorption properties, primarily on the solid/water interface, of a particular class of polyhydroxyl based surfactants: the alkyl glucosides. By the use of ellipsometry, the equilibrium and kinetic aspects of adsorption on titanium dioxide with respect to structural effects has been studied. Furthermore, the effects of small amounts of cationic surfactant additives on the adsorption on silica have been investigated. The results have been compared with similar studies for other nonionic surfactants. We have found that the surfactant structure has a strong effect on the adsorption properties. An increase in the surfactant chain length increases the cooperativity of the system. An increase in the head group polymerization decreases the cooperativity and the plateau adsorbed amount at equilibrium. The effect of surfactant structure on the adsorption kinetics depends on the concentration relative to the cmc, while the there is a decrease in the rate of desorption with increasing hydrophobic chain length independent of the concentration. The adsorption/desorption process is concluded to be diffusion driven, as suggested by the model used. When comparing these results with studies on ethylene oxide based surfactants, we conclude that the two types of surfactants exhibit similar trends on surfaces onto which they adsorb. Adsorption from binary surfactant solutions is even more interesting than adsorption from single surfactant solutions, since it brings us one step closer to the systems used in applications. In addition, adsorption from a mixture can be very different from adsorption from any of the single surfactants in the mixture. Alkyl glucosides alone do not adsorb on silica, but addition of small amounts of a cationic surfactant to the alkyl glucoside solution allows for adsorption on silica. A comparison between the adsorption and bulk properties has shown that mixed micellization explains most, but not all, effects of the coadsorption properties. Changing the pH in the mixed systems reveals that a surfactant with a pH-dependent charge and the ability to adapt its charge to the environment, e.g. a surface, enhances the adsorbed amount over a wider range of pH values than a purely cationic surfactant. It is well known that alkyl glucosides and ethylene oxides adsorb differently on different types of hydrophilic surfaces. As a consequence, replacing ethylene oxides with alkyl glucosides might not be all straight-forward; however, we have shown that the effect of the surface can be eliminated by the use of a cosurfactant. / <p>QC 20101018</p>

The cellular response to a biomaterial, such as a dental implant, is mainly governed by the surface properties, and can thus be altered by the introduction of a surface coating. In this thesis the buildup of a biomacromolecule-based coating formed by layerby-layer (LbL) deposition of the charged polypeptides poly(L-lysine) (PLL) and poly(L-glutamic acid) (PGA) has been studied. In an attempt to make these coatings bioactive and useful for bone-anchored implants, an amelogenin protein mixture (EMD), has been immobilized in these thin polyelectrolyte multilayer (PEM) films. Multilayers were also built by LbL deposition of the natural biomacromolecules collagen (Col) and hyaluronic acid (HA). Multilayer films of these two extra-cellular biomacromolecules should be of interest for use as a scaffold for tissue engineering. The buildup of the multilayer films has been followed in situ, using ellipsometry, quartz crystal microbalance with dissipation (QCM-D), and dual polarization interferometry (DPI). The studied PLL/PGA multilayers were found to be highly hydrated, and to exhibit a two-regime buildup behavior, with an initial “slow-growing” regime, and a second “fast-growing” regime with a linear growth in film thickness and more than linear growth in mass. A net diffusion of polypeptides into the film during the buildup led to an increase in density of the films for each layer adsorbed. A change in density was also observed in the Col/HA film, where HA penetrated and diffused into the porous fibrous Col network. The formed PLL/PGA films were further found to be rather stable during drying, and post-buildup changes in temperature and pH, not losing any mass as long as the temperature was not raised too rapidly. The film thickness responded to changes in the ambient media and collapsed reversibly when dried. A swelling/de-swelling behavior of the film was also observed for changes in the temperature and pH. The EMD protein adsorbed to silica surfaces as nanospheres, and could by itself form multilayers. The adsorption of EMD onto PLL/PGA multilayer films increased at lower pH (5.0), and EMD could be immobilized in several layers by alternate deposition of EMD and PGA. / QC 20101019

<p>The cellular response to a biomaterial, such as a dental implant, is mainly governed by the surface properties, and can thus be altered by the introduction of a surface coating. In this thesis the buildup of a biomacromolecule-based coating formed by layerby-layer (LbL) deposition of the charged polypeptides poly(L-lysine) (PLL) and poly(L-glutamic acid) (PGA) has been studied. In an attempt to make these coatings bioactive and useful for bone-anchored implants, an amelogenin protein mixture (EMD), has been immobilized in these thin polyelectrolyte multilayer (PEM) films. Multilayers were also built by LbL deposition of the natural biomacromolecules collagen (Col) and hyaluronic acid (HA). Multilayer films of these two extra-cellular biomacromolecules should be of interest for use as a scaffold for tissue engineering.</p><p>The buildup of the multilayer films has been followed in situ, using ellipsometry, quartz crystal microbalance with dissipation (QCM-D), and dual polarization interferometry (DPI). The studied PLL/PGA multilayers were found to be highly hydrated, and to exhibit a two-regime buildup behavior, with an initial “slow-growing” regime, and a second “fast-growing” regime with a linear growth in film thickness and more than linear growth in mass. A net diffusion of polypeptides into the film during the buildup led to an increase in density of the films for each layer adsorbed. A change in density was also observed in the Col/HA film, where HA penetrated and diffused into the porous fibrous Col network.</p><p>The formed PLL/PGA films were further found to be rather stable during drying, and post-buildup changes in temperature and pH, not losing any mass as long as the temperature was not raised too rapidly. The film thickness responded to changes in the ambient media and collapsed reversibly when dried. A swelling/de-swelling behavior of the film was also observed for changes in the temperature and pH.</p><p>The EMD protein adsorbed to silica surfaces as nanospheres, and could by itself form multilayers. The adsorption of EMD onto PLL/PGA multilayer films increased at lower pH (5.0), and EMD could be immobilized in several layers by alternate deposition of EMD and PGA.</p>

Des assemblages linéaires de porphyrines reliées par des cations métalliques ont été obtenus en solution et visualisés à l’interface HOPG-solvant par STM. Afin de contrôler la taille des assemblages synthétisés en solution, une stratégie par différenciation de la réactivité des deux sites de coordination externes des porphyrines a été exploitée. De fortes interactions électroniques ont été mises en évidence entre les sous-unités des assemblages multi-porphyriniques. Atteignant la limite de solubilité et de caractérisation en solution avec les molécules comportant six porphyrines, une seconde stratégie a été développée, afin de synthétiser les oligomères à l’interface HOPG-phényloctane. L’auto-assemblage de monomères de porphyrines possédant deux sites de coordination externes a été étudié par STM. Après ajout de l’ion connecteur, des nanorubans comportant plusieurs dizaines de porphyrines reliées par des cations métalliques ont été observés par STM à l’interface HOPG-solvant. / Linear assemblies of porphyrins linked by metal ions were prepared both in solution and at an HOPG/phenyloctane interface. In the first part of the project, controlling the size of the linear assemblies generated in solution was the main goal. Porphyrins bearing two different external coordination sites were used to prepare finite oligomers. Strong interactions between the subunits were found in these compounds. In a second part of the project, the organization of monomeric or dimeric porphyrins at a solid/liquid interface was studied. Finally, linear porphyrin oligomers were prepared directly by self-assembly at an HOPG/phenyloctane interface. These porphyrin nano-ribbons were visualized by STM and presented sizes of several dozen nanometers.

>Magister Scientiae - MSc / Amperometric sensors for Tenofovir, a model nucleotide/ nucleoside reverse transcriptase inhibitor ARV drug, were studied based on the principle of ion-transfer electrochemistry at the membrane-stabilized oil/ water interface (O||W) in a four-electrode cell set-up. Solutions of the hydrophobic salts tetradodecylammonium tetrakis(4-chlorophenyl) borate (ETH500), ethyl violet tetraphenylborate (EthVTPB), tetrabutylammonium tetraphenylborate (TBATPB), tetraphenylphosphnium tetraphenylborate (TPphTPB) and three ionic liquids (Methyltrioctylammonium bis(trifluoromethyl sulfonyl)imide (IL1), 1-butyl-3- methylimdazolium bis(trifluoromethyl sulfonyl)imide (IL3) and 1-propyl-3- methylimdazolium bis(trifluoromethylsulfonyl)imide (IL4)) in nitrobenzene (NB), 1,2- dichloroethane (DCE), and 2-nitrophenyloctyl ether (NPOE) were each tested as O-phases. The cyclic voltammograms of the resulting O||W interfaces in aq. Li2SO4 or aq. MgSO4 were compared with respect to noise, potential window, and other parameters. The three ILs were also tested as self-sufficient salts without a solvent medium. In the end, the ETH500/ DCE salt/ solvent pair was found to yield the best behaved polarizable O||W interface in aq. MgSO4. The analytical characteristics of the resulting sensors to tenofovir without (Ag|ETH500/DCE||) and with the dibenzo-18-crown-6 (Ag|ETH5000/DB18C6/DCE|| in the O-phase were studied with respect to the two pairs of peaks in the CV, namely the WO ion transfer peak and the reverse OW peak. Both sensors exhibited operational stability of 90 min. After consideration of reasonable S/N ratio and sample throughput rates, the scan rate of 25 mV/ s was used in subsequent signal interrogation with CV. The final potential windows were 0.95 V wide for Ag|ETH500 (10 mM)/ DCE|| in aq. MgSO4 (50 mM) and 0.70 V wide for Ag|ETH500 (10 mM)/ DB18C6 (50 mM)/ DCE|| in aq. MgSO4 (50 mM). From plots of peak currents versus square of scan rate, tenofovir diffusion coefficients of about 2.48 × 10-11 cm2/ s were estimated, which indicated diffusion through the supporting membrane as the rate limiting process. Based on WO ion transfer peaks, the first one exhibited a detection limit of about 5 M, a linear range of 15 – 100 M, and sensitivity of 7.09 nA M-1 towards tenofovir, whereas for the second one these were respectively 3 M, 6.32 nA M-1, and 9 – 100 M. In this way, a four-electrode amperometric detection of ion transfer process at liquid | liquid interface, both under simple and ionophore-facilitated mode, has been demonstrated as promising for analysis of tenofovir as a representative of the nucleotide/ nucleoside reverse transcriptase inhibitor ARV drugs

L’objectif de ce travail de thèse s’inscrit dans le cadre de l’étude de la réponse immune innée contre le virus influenza porcin (SIV) et de son contrôle dans l’espèce porcine par les protéines suppressors of cytokine signaling (SOCS) et la cytokine-inducible SH2 domain containing protein (CISH). L’analyse de l’expression des ARNm de SOCS à l’homéostasie a montré une expression significative dans le thymus suggérant un rôle dans la différenciation des cellules T. La réponse immune innée contre une souche de SIV de sous-type H3N2 a été analysée in vitro et ex vivo. L’expression de transcrits impliqués dans la réponse antivirale et de SOCS a été évaluée. Une surexpression des ARNm des gènes antiviraux et de SOCS1 a été observée notamment à 24h post-infection. L’infection expérimentale des cellules NPTr par le virus H3N2 induit une activation des voies de signalisation impliquant MAPK et JAK/STAT. L’utilisation d’inhibiteurs spécifiques de la voie JAK/STAT a conduit à une diminution de l’expression des transcrits antiviraux et ceux de SOCS1 ainsi que l’expression des interférons de type I et III. Afin de développer un outil alternatif in vitro d’étude de la réponse immune innée, la culture en interface air-liquide (ALI) des cellules NPTr a été réalisée. Des cellules à mucus, des jonctions serrées et une résistance transépithéliale élevée ont été observées. Cependant, ces cellules n’ont pas développé de cils. La culture des cellules NPTr dans des conditions ALI, a permis une représentation partielle de l’épithélium respiratoire porcin et constitue ainsi une alternative d’étude in vitro. / The aim of this work was to investigate the innate immune response to swine influenza virus (SIV) and its regulation in swine by the suppressors of cytokine signaling SOCS and the cytokine-inducible SH2 domain containing protein (CISH). The assessment of SOCS constitutive mRNA expression showed significant mRNA expression of SOCS1 in thymus suggesting a key role of this protein in T cell differentiation. The innate immune response against an SIV H3N2 subtype was then assessed in vitro and ex vivo by measuring antiviral and SOCS transcripts expression. The induction of several antiviral genes along with SOCS1 gene was observed. Experimental infection of NPTr cells with H3N2 virus induced MAPK and JAK/STAT signaling pathways activation. The inhibition of JAK/STAT pathway clearly reduced antiviral transcript expression, SOCS1 and both interferon types I and III mRNA expression as well. In order to develop an alternative in vitro tool to study the innate immune response, NPTr epithelial cell line were cultured at the air-liquid interface. This system promotes the differentiation of mucus producing cells, tight junctions development and enables high trans-epithelial electronic resistance values. Nonetheless, the NPTr cells do not develop cilia. The culture of NPTr cells in ALI conditions allows a partial in vitro representation to investigate some aspects of host/respiratory pathogen interaction in pigs.

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-23T12:35:07Z No. of bitstreams: 1 Leila Friedrich.pdf: 945666 bytes, checksum: 6bd01ba22dfd6b6e880b4f9a131adaee (MD5) / Made available in DSpace on 2013-04-23T12:35:07Z (GMT). No. of bitstreams: 1 Leila Friedrich.pdf: 945666 bytes, checksum: 6bd01ba22dfd6b6e880b4f9a131adaee (MD5) Previous issue date: 2006 / As tubulações de aço carbono, para a produção e transporte de produtos químicos, apresentam limitações como resistência à ação da corrosão, sob ação do calor, causando desgaste. Por esse motivo se faz o uso de revestimentos que reduzem o contato da superfície com o meio corrosivo. No entanto, os revestimentos usados para o escoamento de fluídos têm ainda que apresentar uma menor interação com a superfície, uma menor tensão interfacial. Uma grande aplicação destes revestimentos é em dutos de petróleo, devido às obstruções ocasionadas à medida que o óleo escoa através do duto, pois este perde calor para o meio e conseqüentemente se dá à deposição de compostos parafínicos. Análises destes revestimentos com a técnica PLF-FI são de suma importância para avaliar a tensão interfacial dinâmica, pois esta técnica difere das tradicionais para a caracterização da superfície, por ser um método não destrutível e dinâmico. Para a confecção das amostras alguns tempos e temperaturas de cura foram aplicados. Neste presente trabalho, avaliamos quais as superfícies apresentam menor molhabilidade sob condições de fluxo com a superfície, visando um menor número de ocorrências de obstruções das tubulações e paradas para manutenções. Os valores de polarização máxima são verificados para as amostras curadas numa faixa de temperatura entre 120°C a 140°C e tempos de 6 a 10 horas, e sendo estes as variáveis de processo mais indicadas para a produção em alta escala. O presente trabalho foi organizado em 5 capítulos, apresentando-se no Capítulo 1 uma introdução do estudo realizado para a otimização do processo de cura em resinas epóxi modificada com agentes de cura a base de amina. No capítulo 2, apresenta-se uma revisão das tubulações, resina epóxi, a composição, e a cura dos revestimentos. No 12 capítulo 3, revisam-se as técnicas de análises e descrevem-se todas as técnicas experimentais realizadas. No capítulo 4, discutem-se os resultados adquiridos pelas técnicas utilizadas. No capítulo 5, relatam-se as conclusões deste trabalho. / Salvador

L’extraction réductrice liquide-liquide est une des voies pyrochimiques les plusprometteuses pour assurer le retraitement des déchets nucléaires. Cette techniqueconsiste à extraire à haute température des éléments initialement en solution dansun sel fondu sur une nappe métallique. Afin d’améliorer les transferts de masse,l’utilisation de forces électromagnétiques permettant de brasser sans contact matérielle coeur des bains et l’interface elle-même a été envisagée.Les cinétiques d’extraction de trois lanthanides (cérium, néodyme et samarium)ont été étudiées expérimentalement. Une étude préalable nous a conduit à travaillersur le couple fluorure de lithium/antimoine et à utiliser le lithium comme agentréducteur. Les investigations réalisées ont démontré que le mécanisme contrôlant lacinétique rapide des transferts est la diffusion des espèces réactives à l’interface.La simulation numérique du réacteur expérimental faisant intervenir de multiplescouplages a également été réalisée. Elle a permis de déterminer les écoulementsturbulents dans chacune des phases. Les transferts de masse simulés ont ensuiteété comparés aux mesures expérimentales. / Reductive extraction is one of the most promising pyroprocess for processing spentnuclear fuel. The extraction of elements from a molten salt to a liquid metal occurs athigh temperature. At the interface between the two immiscible flows mass transfersare ensured via a redox reaction. To increase these transfers, electromagnetic forcescan be used to stir the bulk of both phases and of the interface itself without materialcontact.The kinetic of extraction of three lanthanides (cerium, neodymium and samarium)has been experimentally studied. We worked on lithium fluoride/antimony system,the reducing agent being lithium. Theses experiments show that mass transfers arefast for all studied lanthanides and are controlled by diffusion of reactive species atthe interface.The numerical simulation of experimental reactor which involves many stronglycoupled phenomenon has been performed. Turbulent flows have been computed inboth phases. Mass transfers have then been deduced and compared to experimentalresults.

L’évaporation d’une solution solvant/soluté est un processus transitoire qui prend fin lorsque le solvant a totalement disparu. Le refroidissement créé par le changement de phase provoque des gradients à la fois thermiques et de concentration en solvant. Ces homogénéités diffusent ensuite dans l’épaisseur de la solution et sont susceptibles d’engendrer un écoulement fluide. L’origine de cette convection peut être liée à des variations de tension de surface ou de densité. Des travaux expérimentaux ont montré que l’épaisseur des dépôts issus de séchages de solutions solvant/soluté semblait pouvoir être corrélée avec les cellules de convection de la zone fluide. Une compréhension approfondie des phénomènes à l’origine de la convection devrait donc participer à un meilleur contrôle de la qualité des dépôts.Sur la base de travaux numériques et expérimentaux publiés, nous avons étudié l’apparition de la convection pour trois types de modèles représentant le processus d’évaporation d’une solution de Polyisobutylène-Toluène : un modèle purement thermique qui s’applique pour les temps courts, un modèle solutal qui est valable sur les temps longs et enfin un modèle couplé thermique/solutal qui représente les transferts sur l’ensemble de la gamme des temps étudiés. Le caractère transitoire de l’évaporation induit une difficulté pour caractériser la naissance de la convection à partir d’un régime de conduction. En effet, cette convection apparaît à partir d’un germe qui est une petite perturbation de la solution diffusive. Si l’amplitude de cette perturbation est trop faible, son amplification à des intensités suffisantes ne pourra pas avoir lieu avant la fin du régime transitoire et l’écoulement ne deviendra donc jamais convectif. Le rôle de la perturbation est donc primordial. Dans des travaux numériques antérieurs, cette perturbation a été imposée à l’état initial, généralement avec une distribution aléatoire du champ thermique ou de vitesse. Lors de cette thèse, nous avons opté pour un modèle plus physique, basé sur l’introduction d’un transfert thermique sur les parois latérales qui joue le rôle de perturbateur de l’écoulement diffusif transitoire.Dans cette thèse, nous avons établi par voie numérique les seuils de transition entre une solution diffusive et un écoulement convectif pour les modèles thermique, solutal et couplé, dans le cas d’une approximation bidimensionnelle du film liquide et des simulations pleinement tridimensionnelles. Des diagrammes spatio-temporels et l’étude des cellules à la surface libre par des reconstructions de Voronoï nous ont permis de mieux comprendre la naissance et la propagation des instabilités dans la solution fluide / The evaporation of a solvent/solute solution is a transient phenomenon which ends when the whole solvent has disappeared. Phase change generates a cooling of the liquid-gas interface, and consequently, it creates thermal and solutal gradients. These homogeneities spread in the core solution and produce, eventually, a fluid flow. This convection can be due to the surface tension and/or buoyancy variations. Experimental works have shown that some coating thicknesses stemming from drying processes are correlated to the size of the convection cells in the fluid region. A thorough understanding of the physical phenomena responsible to fluid convection should contribute to improve the control of deposit quality.Based on numerical and experimental works, we have studied the onset of convection for three kinds of models for the drying process of a Polyisobutylene-Toluène solution: A pure thermal model which is valid for short times, a solutal model devoted to the simulation of long times, only, and a thermal/solutal coupled model which takes into account the heat and mass transfer over a long time period of the evaporation process. The transient nature of the evaporation problem raises the issue of how to define the onset of the convective flow from a diffusive solution. Indeed, this flow motion occurs from a seed which is a small perturbation of the transient diffusive solution. If the perturbation is too weak, the necessary time interval for a significant growing of its magnitude will be greater than the time scale of the transient regime: thus the solution will never be considered as convective. Consequently, the influence of the perturbation is fundamental. In previous numerical works, this perturbation was imposed at the initial state, often through a random spatial distribution applied to the velocity or temperature field. In the present contribution, we have adopted a physical model where the adiabatic lateral walls have been replaced by diathermal walls: The local thermal inhomogeneities create a very weak flow acting as a small disturbance for the transient diffusive solution.In this thesis, we have developed a numerical model to evaluate the thresholds between the diffusive solutions and the convective flows, for the thermal, solutal and thermal/solutal coupled models, for two- and three-dimensional approximations of the Polyisobutylene-Toluène liquid film. Space-time diagrams and convective cell reconstructions at the liquid-gas interface by a Voronoï algorithm allowed us to get a better understanding of the way the disturbances propagate from the lateral walls for finally giving rise to a convective flow in the core fluid

Nous nous sommes intéressés aux émulsions multiples stimulables formées en une étape d’émulsification mécanique. Ces émulsions sont stabilisées par des copolymères amphiphiles synthétisés par polymérisation radicalaire contrôlée par transfert d’atome. L’ajustement du pH et de la force ionique permet la préparation de différents types d’émulsion, dont des émulsions multiples à phase eau (E/H/E) ou huile (H/E/H) continue qui sont stables sur plusieurs mois. Nous avons étudié deux systèmes entièrement biocompatibles permettant la formation d’émulsions E/H/E stabilisées par un unique copolymère, de type poly(diméthylsiloxane)-b-poly(méthacrylate de diméthylamino éthyle). Les émulsions eau/ Miglyol® 812/eau ainsi formulées permettent l’encapsulation et la libération contrôlée de composés hydrophiles par les trois stimuli : pH, force ionique et température. Par ailleurs, nous nous sommes intéressés aux conditions de formation d’émulsions multiples à partir d’un système modèle eau – toluène – polystyrène-b-poly(styrène-st-méthacrylate de diméthylamino éthyle). Nous avons sondé la conformation du copolymère à l’interface eau – huile par réflectivité de neutrons. Les résultats obtenus montrent une corrélation entre cette conformation et le type d’émulsion. De plus, l’obtention d’émulsions multiples est favorisée par la réduction de la courbure des microémulsions formées dans l’eau, telles qu’étudiées par cryo-microscopie électronique à transmission et diffusion de neutrons aux petits angles. Enfin, des critères prédictifs de la formation d’émulsions multiples ont été obtenus grâce à des mesures de tension interfaciale et du partitionnement du copolymère entre les deux phases. / We studied stimuli-responsive multiple emulsions formed in a one-step mechanical emulsification process. These emulsions are stabilized by amphiphilic copolymers synthesized by atom transfer radical polymerization. Depending on pH, ionic strength and temperature, different emulsion types can be obtained, including water-continuous (W/O/W) and oil-continuous (O/W/O) multiple emulsions. These emulsions are stable during several months. We formed W/O/W emulsions with two entirely biocompatible systems using a poly(dimethylsiloxane)-b-poly(dimethylaminoethyl methacrylate) copolymer. Water/Miglyol® 812/water emulsions formulated with this copolymer enable the encapsulation and controlled release of hydrophilic species with the three stimuli: pH, ionic strength and temperature. Furthermore, we studied the formation conditions of multiple water – toluene – polystyrene-b-poly(styrene-st-dimethylaminoethyl methacrylate) emulsions. We probed the conformation of the polymer adsorbed at the water – oil interface using neutron reflectivity. Our results show an existing correlation between emulsion type and polymer conformation. Moreover, the formation of multiple emulsions is promoted by a decrease in the curvature of the microemulsions formed in water, which was assessed by cryo transmission electron microscopy and small angle neutron scattering. Finally, we settled predictive criteria for the formation of multiple emulsions. These criteria are based on interfacial tension and polymer partitioning measurements.