Les plasmas transitoires générés par ablation laser à haute fluence sont des phénomènes complexes impliquant une multitude de processus, comme l’absorption de la radiation optique dans la matière, l’augmentation de température et les transitions de phase dues au transfert d’énergie, l’hydrodynamique du gaz en expansion, les interactions électriques entre les particules chargées, ou l’interaction du rayonnement laser avec le plasma créé. Une compréhension la plus complète possible de ce phénomène est nécessaire tant du point de vue fondamental, que par rapport à la caractérisation de matériaux à fort potentiel technologique soumis à des flux d’énergie intenses.Afin d’accéder à une telle compréhension, nous avons développé une approche multi-diagnostics, en mettant en œuvre des techniques optiques et électriques : imagerie par caméra intensifiée rapide, spectroscopie optique d’émission résolue spatialement et temporellement, spectroscopie d’absorption par diode laser, sonde de Langmuir. Ces techniques ont été appliquées à la caractérisation des plasmas générés par ablation laser en régime nanoseconde à différentes longueurs d’onde sur des matériaux allant des plus simples (Al, Cu) aux plus complexes (céramiques, verres chalcogénures, ferromagnétiques). Les principaux résultats obtenus ont été la mise en évidence d’un processus de fractionnement du plasma en deux structures, et la caractérisation cinétique et énergétique des constituants de ces structures. Ces résultats trouvent un intérêt fondamental (développement d’un modèle hydrodynamique fractal) et appliqué (investigation du phénomène d’érosion dans les propulseurs spatiaux à plasma, dépôt de couches minces). / The transient plasmas generated by high-fluence laser ablation are complex phenomena involving multiple processes, as optical radiation absorption by the matter, temperature increase and phase transitions generated by the energy transfer, expanding gas hydrodynamics, electrical interactions between the charged particles, or the interaction of the laser radiation with the generated plasma. A most complete understanding of this phenomenon is therefore necessary from the fundamental point of view, but also for characterizing the behavior of high technological potential materials under intense irradiation. We have developed a multi-diagnostic approach, based on optical and electrical techniques: fast ICCD camera imaging, space- and time-resolved optical emission spectroscopy, diode laser absorption spectroscopy, Langmuir probe. These techniques have been used to characterize plasmas generated by nanosecond laser ablation of various samples, from simple Al and Cu metals, to more complicated ceramics, chalcogenide glasses or ferromagnetics. The main results have been the observation of the plasma splitting in two structures and the kinetic and energetic characterization of their constituents. These results present fundamental (development of a fractal hydrodynamic model) and applied (erosion of dielectric walls in space plasma thrusters, pulsed laser deposition of thin films) interest.

It was found that there was a specific interaction between peptidolipid C18H35O (Stearoyl)-Phe-Trp-Ser-His-Glu and paraoxon. The aromatic residue groups were involved in the recognition between paraoxon and the peptidolipid, because the fluorescence of Trp in the peptidolipid at 351 nm was quenched by paraoxon in the subphase. When paraoxon was dissolved in the subphase, the surface potential-area (delta V-A) isotherm for the peptidolipid A displayed an unusual shape. This was interpreted on the basis of Infrared Reflection-Absorption Spectroscopy (IRRAS) results as being due to the reorientation of the benzene ring of paraoxon, which changed from parallel to the air-water interface in the absence of a monolayer to a tilted orientation upon interacting with the peptidolipid Langmuir monolayer. The secondary structure of oganophosphorus acid anhydrolase (OPAA) Langmuir monolayer in the absence and presence of diisopropylfluorophosphate (DFP) in the subphase was also studied by the IRRAS and Polarization Modulated-IRRAS (PM-IRRAS). The shape of OPAA molecules is supposed to be elliptic and the long axis of OPAA was parallel to the air-water interface in the absence of DFP in the subphase, whereas the long axis became perpendicular in the presence of DFP. This result explains the decrease of the limiting molecular area of OPAA Langmuir monolayer when DFP was dissolved in the subphase. Using the Langmuir monolayer technique, the surface properties of aequorin were studied. The results showed that aequorin formed a stable Langmuir monolayer and the surface pressure-area isotherms were dependent on both pH and ionic strength. At a pH higher or lower than 7.6, the limiting molecular area decreased. The addition of calcium chloride to the Tris/HCl buffer subphase (pH 7.6) caused an increase of the limiting molecular area of the aequorin Langmuir monolayer. The fluorescence spectra of a Langmuir-Blodgett (LB) monolayer of aequorin in the presence of calcium chloride indicated that the aequorin transformed to the apoaequorin. The Langmuir monolayer of aequorin and apoaequorin was studied by IRRAS and PM-IRRAS techniques. The different behavior of aequorin and apoaequorin at the air-water interface was explained by the fact that aequorin formed dimers at air-water interface but apoaequorin was monomer. It was more difficult for a dimer to be tilted by the compression of the Langmuir monolayer.

Thèse (Ph. D.)--Université Laval, 2008. / Bibliogr. Publié aussi en version électronique dans la Collection Mémoires et thèses électroniques.

No description available.

The purpose of this work was to examine the behaviour of the soluble elastin derivative, alpha-elastin, under a variety of conditions.

Le résidu de bauxite communément appelé boue rouge est un déchet industriel généré lors de la production d'alumine. Le stockage de ces déchets est considéré comme un important problème environnemental, notamment du fait de la nature caustique du matériau (pH >10) et des quantités générées (d’environ 1,5 t par tonne d’alumine produit). La production de l’alumine vénézuélienne (par CVG Bauxilum) a ainsi généré plus de 15 millions de m3 de résidus de bauxite. Paradoxalement, aucune recherche n’a encore été menée sur les propriétés de ces résidus en tant que matériau pouvant être utilisé dans le domaine environnemental. Les objectifs principaux de ce travail de thèse sont une caractérisation physico-chimique du résidu de bauxite vénézuélienne (fraction solide) ainsi qu’une évaluation des options de valorisation, notamment comme agent de remédiation des systèmes pollués. Une approche intégrée couplant la chimie, la minéralogie, le pH, la granulométrie, la surface spécifique et le contenu en radionucléides, avec des études de spéciation chimique et de biodisponibilité, a permis de mettre en évidence certaines des caractéristiques très importantes notamment 1) une teneur élevée en Th et U et leur isotopes respectifs Th232 et U238, ainsi qu’en lanthanides 2) le risque potentiel chimiotoxique du résidu vis-à-vis de fractions très labiles pour des éléments tels que l’aluminium et l’uranium 3) des propriétés de sorption intéressantes vis à vis d’éléments toxiques, Pb, Zn et As, du fait de la grande surface spécifique du résidu, notamment en milieu acide (cas d’un drainage minier acide). L’ensemble des résultats de ce travail, a montré que l’utilisation potentielle des résidus de bauxite vénézuélienne dans des domaines clés tels que l'assainissement des systèmes pollués (comme amendement ou un agent sorbant) et dans la récupération de métaux d’intérêt économique pourrait être une voie possible pour la valorisation de ce déchet. / The bauxite residue commonly called ‘red mud’ is an industrial waste generated during the production of alumina. The storage of this waste is considered as a major environmental problem, especially because of its caustic nature (pH> 10) and the huge produced quantities (about 1.5 t per tonne of alumina produced). The production of Venezuelan alumina (CVG Bauxilum) has generated more than 15 million m3 of bauxite residue. Moreover, no research has yet been conducted on the properties of these residues and their utilization in the environmental field. The main goals of this study focus on the physical and chemical characterization of Venezuelan bauxite residue (solid fraction) and in an evaluation of its applications as an agent for remediation of polluted systems. An integrated approach coupling chemical composition and adsorption properties, mineralogical phases, particle size, surface area and radionuclide content with studies of chemical speciation and bioavailability, yielded significant constraints including: 1) a high content of U and Th, and their respective isotopes Th232 and U238, as well as lanthanides 2) the potential risk of residue chemotoxicity towards a very labile fraction of elements such as aluminum and uranium 3) high sorption properties with respect to toxic elements, Pb, Zn and As, due to the large surface area of the residue, especially under acidic conditions (case of acid mine drainage). These results have shown the potential use of Venezuelan bauxite residue in key areas such as remediation of polluted systems (as amendment or sorbent agent) and in the recovery of metals of economic interest.

Filmes de Langmuir e Langmuir-Blodgett (LB) de ligninas extraídas do bagaço de cana-de-açúcar, via processo organossolve, foram fabricados. As isotermas de pressão revelaram uma área para a seção média da lignina em torno de 100 &#197 para a monocamada condensada, enquanto a modelagem a partir dos espectros elipsométricos indicou uma espessura por camada de cerca 60 &#197 para os filmes LB. Porém a deposição não se mostrou homogênea sobre toda a superfície do substrato como observado pelas medidas de microscopia de força atômica (AFM), de forma que filmes mais homogêneos foram obtidos a partir de uma solução mista de Iignina com estearato de cádmio. A área por molécula, calculada com base no número de moléculas de ácido esteárico sobre a subfase, aumenta com a quantidade de lignina na solução mista, indicando a presença de ambos os componentes também na monocamada. Os espectros de infravermelho com transformada de Fourier (FTIR) mostraram que tanto a lignina quanto o estearato de cádmio são transferidos e os espectros de ultravioleta visível (UV-vis) indicaram que esta deposição é homogênea até a 20&#170 camada. Os difratogramas de raios-X e as medidas de AFM mostram que a deposição de lignina e estearato de cádmio ocorre em domínios separados. As medidas de AFM revelaram ainda um aumento da rugosidade do filme com o aumento do número de camadas depositadas e com a maior irregularidade do substrato utilizado. Vale destacar que os filmes de lignina pura mostraram-se mais homogêneos que os filmes mistos, apesar da maior estabilidade destes sobre a subfase. A uniformidade macroscópica dos filmes LB foram confirmadas por medidas de potencial de superfície. Um estudo comparativo de filmes de Langmuir de ligninas extraídas por diferentes processos e de diferentes fontes (madeira mole, madeira dura e cana-de- açúcar) foi realizado. Destacou-se a importância dos grupos funcionais nas medidas de pressão e potencial de superfície, sendo que a área molecular média mostrou-se aumentar com a massa molar das ligninas em questão. A observação de uma inversão nos valores do potencial de superfície para filmes LB de lignina de cana e de pinus abriu caminho para uma investigação mais detalhada dos fatores que contribuem para o potencial de superfície dos filmes LB. Além da Iignina, filmes LB de polianilina e estearato de cádmio também foram estudados. Os resultados revelaram que os valores do potencial de superfície para estes filmes podem ser melhor compreendidos levando-se em consideração modelos teóricos que tratam tanto da contribuição dipolar das moléculas que constituem o filme como da contribuição da interface filme/substrato, a qual geralmente é negativa e se dá pela injeção de cargas. No caso dos filmes LB de estearato de cádmio o potencial é positivo para um número ímpar de camadas e negativo para um número par / Langmuir monolayers and Langmuir-Blodgett (LB) films were produced from lignins extracted from sugar cane bagasse, via the organosolv process The surface pressure isotherms revealed an area per molecule of 100 &#197 for a condensed monolayer, and the modelling of ellipsometric data led to a thickness of 60 &#197 per layer for the LB films. The latter were not homogeneous, as demonstrated by atomic force microscopy (AFM) studies, and therefore mixed monolayers of Iignin and cadmium stearate were transferred with the aim of achieving more homogeneous films. The area per molecule, based on the number of stearic acid molecules on the airlwater interface, increased with the lignin contents in the mixed monolayers, thus confirming the presence of both components in the Langmuir monolayer. Fourier transform infra-red (FTIR) spectroscopy of LB films indicated that cadmium stearate as well as lignin were transferred onto the substrate. An equal amount of material was transferred in each deposition step, as demonstrated by the linear increase in UV-vis absorbance with the number of deposited layers up to the 20&#170 layer. Lignin and cadmium stearate are transferred in separate domains, which was indicated in X-ray diffraction measurements and AFM images. The latter also reveal that the roughness increases with the number of layers and may depend upon the substrate. Interestingly, films of pure lignin were more homogeneous than mixed films with cadmium searate, in spite of the higher stability and transterability of the mixed monolayers. Surface potential measurements showed a unitorm profile when the probe was scanned across an LB film, which may be taken as demonstration of uniformity at least at the macroscopic levei, though the film comprises domains and is usually rough for a molecular film. A comparative study was made ot monolayer characteristics for lignins obtained trom different sources and using different extracting procedures. The importance of functional groups was highlighted in these measurements, in which the area per molecule increased with the molecular weight ot the material. The observation that LB films from pinus and sugar cane bagasse exhibit surface potentials ot inverted sign has prompted us to investigate the possible contributions to such surface potentials. In addition to Iignins, in this study cadmium stearate and polyaniline LB films were also used. The overall conclusion was that the surface potential depends on the dipole moment of the monolayer-torming molecules, but is also affected substantially by the contribution from the substrate/film interface. The latter arises from charge injection from the electrode and is generally negative. For simple cadmium stearate LB films, the surface potential is positive for an odd number of layers, but negative for even numbers, since the dipole contribution is cancelled out

Resultados antigos de potencial de superfície de filmes de Langmuir não eram reprodutíveis, devido B presença de impurezas na subfase aquosa sobre a qual os filmes se formavam. Dados recentes para o ácido esteárico, no entanto, mostram um comportamento reprodutível Neste trabalho, foi promovida com sucesso uma recaracterização através de medidas de pressão de superfície (II) e potencial de superfície (&#916V) de compostos alifáticos simples (álcoois, ésteres, ácido e amina), obtidos sobre subfases devidamente purificadas. Os resultados obtidos são inéditos e mostram que o potencial de superfície desses filmes é nulo para grandes valores de área molecular média (A), aumentando a partir de um valor de área crítico, Acr, até atingir um valor máximo, &#916Vmax. Modelos para o potencial de superfície de filmes de Langmuir mostram boa concordância com os resultados obtidos. As curvas de pressão e potencial de superfície para os álcoois e ésteres praticamente não se modificam pela alteração do pH da subfase na faixa de 1 a 13. Porém para a amina e ácido há grandes alterações, principalmente nas curvas de potencial de superfície, em virtude da contribuição da dupla camada elétrica. Foram produzidos, também, filmes de Langmuir-Blodgett (LB) a partir de monocamadas de ácido esteárico que foram caracterizados através de medidas de potencial de superfície, com o objetivo de comprovar a importância da contribuição dipolar para o potencial desses filmes. Os resultados indicam que além da contribuição dipolar, há uma contribuição negativa (em tomo de -200 mV) da interface substrato/filme. O potencial de superfície se confirma como uma técnica de caracterização bastante sensível, tanto para filmes de Langmuir como para filmes LB. / Old surface potential data in the literature were not reproducible, because of impurities in the aqueous subphase where the monolayers were formed. Recent data for stearic acid, however, show a reproducible behavior. In this work, a recharacterization of surface presssure (II) and surface potential (&#916V) for Langmuir monolayers of simple aliphatic compounds (alcohols, esters, acid and amine), fabricated over conveniently pure subphases, were successfully carried out. These new results show that the surface potential is zero for large areas per molecule and only increased below a critical area per molecule, Acr. Surface potential models for Langmuir films are in good agreement with the data obtained. There is almost no change in the surface pressure and surface potential for alcohols and esters for a subphase pH range of 1 to 13. However, for amine and acid large changes are observed, mainly in the surface potential curves, because of the electric double layer contribution Langmuir-Blodgett (LB) films were deposited from stearic acid monolayers. They were characterized by surface potential measurements in order to confirm the importance of the contribution from dipole moments of the film-forming molecules. The results also point towards a negative contribution (around - 200 mV) due to the film/substrate interface. The surface potential technique has been demonstrated to be a very sensitive characterization technique for Langmuir monolayers as well as for LB films.

Filmes de Langmuir e Langmuir-Blodgett (LB) foram produzidos a partir da polianilina não substituída, que se tornou processável e solúvel em clorofórmio apos ser dopada com ácidos funcionalizados. Para atingir condições otimizadas de formação e deposição dos filmes, foi realizado um estudo criterioso empregando vários ácidos funcionalizados: canfor sulfônico (CSA), dodecilbenzeno sulfônico (DBSA) e tolueno sulfônico (TSA); e também os solventes e plastificantes N-metilpirrolidinona (NMP) e m-cresol. Soluções de polianilina de alta massa molar processada com estes ácidos foram depositadas sobre subfases aquosas ácidas (pH = 2), formando os chamados filmes monomoleculares de Langmuir. Através de um estudo dos parâmetros que influenciam a formação dos filmes de Langmuir conseguimos obter monocamadas estáveis. Desta forma os filmes puderam ser transferidos para substratos sólidos (vidro bk7), usando a técnica de Langmuir-Blodgett. Os filmes LB produzidos são do tipo Z, ou seja, a deposição só é bem sucedida na retirada do substrato, o que significa que mesmo no filme de Langmuir alguns grupos hidrofílicos se encontravam na interface filme/ar. Os filmes LB foram caracterizados por espectroscopia de UV-vis., medidas de condutividade usando o método de quatro pontas, voltametria cíclica e medidas do potencial de superfície. Os filmes LB apresentam propriedades óticas e eletroativas semelhantes as dos filmes de polianilina fabricados por centrifugação. A absorbância da banda polarônica aumenta linearmente com o número de camadas depositadas, o que demonstra que cada camada contribui com a mesma quantidade de material para o filme. A condutividade dos filmes e da ordem de 10-4 S/cm, inferior aos valores medidos para filmes obtidos por centrifugação de soluções de polianilina com CSA e DBSA, mas é maior do que a de alguns outros filmes LB de polianilina relatados na literatura / Langmuir-Blodgett (LB) films were fabricated from parent polyaniline (PANI), which was made soluble in chloroform by being doped with functionalized acids. Optimized conditions for LB film deposition were only reached after a systematic processability study in which use was made of camphor sulfonic acid (CSA), dodecylbenzene sulfonic acid (DBSA), toluene sulfonic acid (TSA) and of N-methyl pyrrolidinone (NMP) and m-cresol as plasticizers. Solutions of high molecular weight PANI were spread on acidic, aqueous subphases (pH = 2), thus forming the so-called Langmuir monolayer. These monolayer were transferred onto solid substrates (bk7 glass) in the form of Z-type films, i.e. deposition was successful only in the upstrokes. This means that hydrophilic groups must protrude from the water surface in the Langmuir film. The LB films were characterized using UV-vis spectroscopy, cyclic voltammeter, surface potential and conductivity measurements. The optical and electroactive properties of the deposited LB films were essentially the same as those obtained with spin-coated PANI films. The absorbance of the polaronic peak increases linearly with the number of deposited layers, demonstrating that each layer contributed an equal amount of material to the LB film. The films conductivity was of the order of 10-4 S/cm, which is below the values of spin coated PANI films processed with CSA or DBSA, but higher than some published values for LB films from polyaniline

Neste projeto estudou-se a interação da enzima peroxidase de raiz forte (HRP) em interfaces nanoestruturadas e sua possível aplicação em biossensores de peróxido de hidrogênio. Foram utilizadas as técnicas de Langmuir, Langmuir-Blodgett (LB) e automontagem por adsorção física para formar filmes nanoestruturados. A interação da enzima com espécies em interfaces foi investigada com materiais que serviram de matrizes de adsorção, ou seja, a quitosana (Ch) e o fosfolipídio 1,2-dipalmitoil-sn-glicero-3-[fosfatidil-rac-(1-glicerol)] (sal de sódio) (DPPG). Os filmes de Langmuir foram caracterizados com medidas de pressão e potencial de superfície, espectroscopia no infravermelho, e tensão superficial dinâmica. Para os filmes LB e automontados, empregaram-se espectroscopias de fluorescência, ultravioleta-visível e infravermelho e microgravimetria por cristal de quartzo. A peroxidase de raiz forte apresentou forte interação com DPPG, confirmada em filmes de Langmuir por medidas de pressão de superfície, elasticidade dinâmica e de espectroscopia de reflexão e absorção no infravermelho, com modulação por polarização (PM-IRRAS). A massa de peroxidase transferida em filmes Langmuir-Blodgett (LB) mistos com DPPG foi de aproximadamente 200 ng, de acordo com medidas com uma microbalança de cristal de quartzo. A atividade da HRP foi mantida no filme LB, inclusive com atividade catalítica maior do que em meio homogêneo e nos filmes automontados com quitosana. As medidas de atividade não afetaram a morfologia dos filmes LB, estudada com microscopia de força atômica (AFM), ao contrário dos filmes automontados. Conclui-se que a imobilização de HRP é mais eficiente num filme LB, com matriz fosfolipídica, apresentando boas perspectivas de emprego em biossensores de peróxido de hidrogênio. / A study has been performed on the interaction of the enzyme horseradish peroxidase (HRP) in nanostructured interfaces and their possible application in biosensors for hydrogen peroxide. The nanostructured films were obtained with the Langmuir, Langmuir-Blodgett (LB) and layer-by-layer (LbL) methods. The interaction between HRP and species at interfaces was investigated using materials that served as matrix for immobilization, viz. chitosan (Ch) and the phospholipid 1,2-dipalmytoil-sn-glycero-3-[phosphatidyl-rac-(1-glycerol)] (sodium salt) (DPPG). The Langmuir films were characterized with surface pressure, surface potential, elasticity measurements and polarization-modulation reflection and absorption infrared spectroscopy (PM-IRRAS). For LB and LbL films, use was made of fluorescence, absorption in the UV-vis. and infrared spectroscopy. HRP displayed strong interaction with DPPG, which was confirmed in Langmuir films with measurements of surface pressure, dynamic elasticity and PM-IRRAS. The mass of HRP transferred onto a solid support in a mixed LB film with DPPG was 200 ng, according to data from a quartz crystal microbalance. The HRP activity was preserved in the mixed LB film, with a catalytic activity that was even higher than in solution or in LbL films of HRP/Ch. The catalytic activity measurements did not affect the morphology of the LB films, studied with atomic force microscopy (AFM), in contrast to the LbL films. The main conclusion is that HRP immobilization is more efficient in an LB film with a phospholipid matrix, with good prospects for developing biosensors for hydrogen peroxide.