Novel, tailored titanium dioxide pigments with controllable nanoscale morphological features were shown to significantly enhance the optical and strength properties of paper. The opacifying power of synthesized polycrystalline TiO2 particles in a cellulose matrix was found experimentally to be superior to that of a commercial rutile pigment, depending on the crystal structure of the synthesized particles. High aspect ratio polycrystalline rutile pigments composed of a linear linkage of several individual rutile crystals gave 6% more opacity than the commercial rutile pigment. Theoretical light scattering calculations using the T-Matrix Method showed the light scattering efficiency of linearly arranged polycrystalline rutile particles to depend on number and size of crystals composing the particle and confirmed the higher efficiency of the synthesized polycrystalline rutile pigments over commercial rutile. The opacifying power of hollow polycrystalline rutile particles was found experimentally to be superior to that of a commercial rutile pigment in a highly pressed bleached fiber matrix, depending on cavity size, while the opacifying power of silica-rutile titania core-shell particles was found comparable to commercial rutile at constant titania loading. The light scattering efficiency of titania core-shell particles was shown to be dependant on the light scattering efficiency of the core material. The overall particle shape and aspect ratio of titania core-shell and hollow nanoparticles were shown to be tunable by choosing an appropriate template and coating thickness in layer-by-layer or sol-gel templating synthesis. Inorganic-cellulose core-shell and hollow cellulose nanoparticles were prepared by self-encapsulation with regenerated cellulose via precipitation of cellulose in a polyacrylic acid hydrogel layer surrounding inorganic particle templates in 4-Methylmorpholine N-oxide (NMMO) monohydrate solution. This discrete encapsulation of inorganic pigments with a thin, uniform cellulose shell was found to increase the bondability improvement between the particles and a polysaccharide substrate. The crystallinity of several carbohydrate polymers was shown to significantly affect the bondability of encapsulated core-shell particles.

O cimento Portland (CP) é um produto industrializado que não é só consumidor de energia e de matérias-primas, mas também responsável por grandes emissões de CO2. Além do impacto ambiental, a presença de alguns compostos hidratados que em contato com os sulfatos, produzem fases expansivas que reduzem a vida útil das estruturas. Adições minerais, como as escórias de alto-forno, têm sido adicionadas para reduzir o clínquer e aumentar a resistência aos sulfatos, porém nem todas as escórias conferem empregabilidade como adição devido a sua composição química. Cimentos com adições apresentam ganho de resistência muito lento nas primeiras idades, tornando-se desinteressante para a cadeia produtiva da construção civil. Assim, as limitações que o CP apresenta, somada ao aumento dos resíduos, incentivaram a busca por aglomerantes isentos de clínquer. A álcali ativação proporcionou a possibilidade de reaproveitamento de diversos subprodutos, pois a cinética de reação é similar ao CP, devido à semelhança química e liberação de calor. Pesquisas ligadas à durabilidade dos cimentos álcali ativados (CAT) ainda são bastante reduzidas, principalmente a eficácia dos métodos empregados para avaliação da resistência aos sulfatos em ambientais laboratoriais. Portanto, este trabalho teve como objetivo investigar o comportamento das pastas de escórias ativadas com 5% de NaOH e CP resistente a sulfatos (CPIV-RS) em ambientes sulfatados através do método NIST e comparar com o método acelerado em argamassas proposto pela NBR 13583:2014. As avaliações incluíram as análises microestruturais (DRX/MEV/DTG) e macroestrutural através de inspeções visuais, variação dimensional, variação de massa e resistência à compressão. Os resultados indicaram que nas condições ensaiadas, os métodos acelerados de avaliação da resistência aos sulfatos não apresentaram diferenças significativas entre as pastas e argamassas. Os CATs apresentaram desempenho superior antes e depois da exposição ao Na2SO4 comparados aos CPIV-RS, favorecendo a hidratação e a resistência à compressão. Por outro lado, a formação da gipsita parece ser o principal produto de degradação dos CATs na solução de MgSO4, originado pela descalcificação do C-S-H, afetando fortemente as propriedades físicas, químicas e mecânicas dos cimentos álcali ativados. / Portland cement (PC) is an industrialized product that is not so consuming of energy and raw materials, but also responsible for large CO2 emissions. Besides the environmental impact, the presence of some hydrated compounds that in contact with the sulfates, produce expansive phases that reduce the useful life of the structures. Minerals additions, such as blast furnace slag, have been added to reduce clinker and increase resistance to sulphates, but not all slags confer employability as addition because of their chemical composition. Cements with additions show very low resistance gain in the early ages, making it uninteresting for the productive chain of civil construction. Thus, the limitations that PC presents, together with the increase of residues, have encouraged the search for clinker-free binders. Alkali-activation provided the possibility of reuse of several by-products, because the reaction kinetics is similar to PC, due to chemical similarity and heat release. Researches related to the durability of alkaliactivated cements (AAC) are still very low, mainly the efficacy of the methods used to evaluate the resistance to sulfates in laboratory environments. Therefore, the objective of this work was to investigate the behavior of slag pastes activated with 5% NaOH and sulfate resistant PC (PCIV-SR) in sulphated environments using the NIST method and to compare with the accelerated mortar method proposed by NBR 13583:2014. The evaluations included microstructural analysis (XRD/SEM/DTG) and macrostructural analysis through visual inspection, dimensional variation, mass variation and compressive strength. The results indicated that under the conditions tested, the accelerated methods of sulfate resistance evaluation did not present significant differences between pastes and mortars. The AACs presented better performance before and after exposure to Na2SO4 compared to PCPIV-SR, favoring hydration and compressive strength. On the other hand, the formation of gypsum appears to be the main degradation product of the AACs in the MgSO4 solution, caused by the C-S-H decalcification, strongly affecting the physical, chemical and mechanical properties of the activated alkali cements.

Com o surgimento da tecnologia da pré-fabricação, a construção civil tem adquirido elevada agilidade, reduzindo os prazos de construção e maior qualidade no controle de execução. Dentre as diversas peças pré-fabricadas, a telha em concreto protendido autoportante tem por característica cobrir vãos de até 25 m, sem a existência de estrutura de apoio intermediária. Sendo um produto esbelto, exige um aprimoramento constante para aumentar a durabilidade da estrutura quanto à corrosão da armadura e manter sua adequação ao uso. O objetivo desse trabalho é reduzir a permeabilidade das telhas pré-fabricadas, além de analisar a influência desse parâmetro na durabilidade do concreto frente às classes de agressividade da norma NBR 9062/2006. A norma estabelece um fator a/c máximo de 0,45 e resistência característica à compressão mínima de 40 MPa, enquadrando-se como classe de agressividade ambiental II - Urbana. Para tal, foram escolhidas algumas adições minerais existentes na região da grande Curitiba (metacaulim e filler), além de um aditivo impermeabilizante interno, comparando com o traço de referência preexistente em linha de produção. As dosagens foram definidas com base no empacotamento de partículas e caracterizadas quanto à resistência mecânica à compressão, absorção de água por imersão e por capilaridade e, penetração de água sob pressão, além dos ensaios de porosimetria por intrusão de mercúrio (PIM), carbonatação e penetração de íons cloreto. Em termos de resistência mecânica à compressão, a dosagem referência apresentou os melhores resultados (em função da menor relação água/cimento e maior consumo de cimento), seguido pelo concreto com aditivo impermeabilizante e com metacaulim. Para a absorção de água, todas as dosagens apresentaram-se como concretos duráveis, com destaque para o metacaulim e filler+aditivo impermeabilizante. Quanto à absorção capilar, todas as dosagens apresentaram baixa permeabilidade. Para a penetração de água sob pressão todas se apresentam como impermeáveis em condições agressivas, com destaque para o uso do metacaulim e do aditivo impermeabilizante. O ensaio de PIM mostra que a dosagem com filler possui uma concentração maior de poros e que a dosagem com metacaulim apresenta o menor diâmetro máximo de poros, com uma tendência ao refinamento em diâmetros menores. Quando analisado o resultado de carbonatação, o metacaulim apresentou o melhor resultado, possibilitando um menor cobrimento da armadura para uma vida útil de 50 anos. Quanto à penetração de cloretos, a dosagem com metacaulim, apresentou uma redução maior em relação às demais dosagens pela sua atividade pozolânica, contribuindo para a durabilidade do concreto. Em linhas gerais, é possível melhorar a impermeabilidade do concreto com o acréscimo de 8% do metacaulim sobre o peso do cimento, ainda com uma redução de 5,2% de cimento, com bons resultados também para o uso de 1% de aditivo impermeabilizante. Quanto à durabilidade, a otimização da curva granulométrica dos agregados e o uso do metacaulim possibilitam a utilização de telhas pré-fabricadas em regiões de classe de agressividade III - Industrial ou Marinha, observando o cobrimento mínimo da armadura. / With the emerging precast concrete technology, the civil construction has acquired high agility, reducing construction time and greater quality control in execution. Among several precast pieces, tile in prestressed concrete is characterized by selfsupporting spans of up to 25 m, without the existence of an intermediate support structure. Being a slim product, requires an improvement in increasing the durability of the structure because of the steel corrosion and maintain their fitness for use. The objective of this research is to reduce the permeability of the precast tiles, and analyzing their influence in the durability of the concrete face of the aggressiveness classes constants in the NBR 9062/2006, that establish the a/c ratio up to 0,45 and minimum compressive strength characteristic of 40 MPa, positioning themselves as a class of environmental aggressiveness II - Urban. For this, were selected a few mineral admixture from Curitiba/Paraná and a waterproof internal admixture, comparing with the concrete mix pre-existing in production line. The concrete dosages were defined by packing particles and were analysed for mechanical compressive strength, water absorption by immersion and by capillarity and water penetration under pressure, in addition to tests of mercury intrusion porosimetry (MIP), carbonation and chloride ion penetration. About the mechanical compressive strength, the dosage reference showed the best results (due to lower water / cement ratio and higher cement consumption), followed by concrete with waterproofing admixture and metakaolin. For water absorption, all measurements fall as durable concrete, especially the metakaolin additive and filler + waterproofing. For the water absorption, all dosages presented low permeability. For the water penetration under pressure all fall as impervious to several conditions, especially with metakaolin and waterproofing admixture. The MIP test shows that the dosage with filler has a higher concentration of pores and the dosage with metakaolin has the smallest maximum diameter of pores, with a tendency towards refinement in smaller diameters. When analyzing the carbonation, the metakaolin showed the best results, allowing a smaller reinforcement cover for a lifetime of 50 years. As the penetration of chlorides ions, the metakaolin, showed a greater reduction comparing with other dosages for its pozzolanic activity, contributing to the concrete durability. In general, it is possible to improve the concrete impermeability with the addition of 8% of metakaolin by weight of cement, with 5,2% of cement reduction, showing good results also using 1% of waterproofing admixture. As for durability, the optimizing of aggregates granulometric curve and the use of metakaolin enables the use of prefabricated tiles in regions of class of environmental aggressiveness III - Industrial or Marine, observing the minimum concrete cover of reinforcement.

La pharmacocinétique (PK) des anticorps monoclonaux (mAbs) est sujette à d’importantes variations interindividuelles. Le récepteur néonatal au Fc des IgG (FcRn) et le statut immun à l’encontre de ces mAbs sont des déterminants de cette PK. La bioconjugaison des mAbs à des cytotoxiques entraîne une altération de leur PK. Nous montrons que le taux de couplage modifie l’affinité de ces espèces pour le FcRn à pH6. La proportion d’agrégats au sein des solutions d’anticorps armés augmente avec le taux de couplage et pourrait entraîner une altération de leur PK. Par ailleurs, cette agrégation est impliquée dans l’immunogénicité des mAbs, et nous avons donc cherché à identifier des acides aminés impliqués dans l’agrégation de mAbs indiqués en clinique. Il apparait que la nature biochimique de résidus des paratopes pourrait augmenter cette agrégation. Les anti-TNF- présentent très peu d'agrégats et figurent pourtant parmi les plus immunogènes chez l’Homme. Nous avons donc exploré le rôle des complexes immuns dans leur immunogénicité chez la souris. Il apparait que la présence du FcRn n’est pas à l’origine de l’immunisation contre ces mAbs, contrairement à celle des complexes immuns. Ces résultats donnent des pistes pour la production de mAbs plus efficients et mieux tolérés. / The pharmacokinetic (PK) profile of monoclonal antibodies (mAbs) shows interindividudal variability. The neonatal Fc receptor (FcRn) and the immounogenicity of these mAbs are determinative factors of mAb PK. Generation of antibody-drug-conjugates alters their PK profile. We show that the the affinity for FcRn at pH6 increases with the drug-to-mAb ratio, as does the amount of aggregates inside the mAb-drug-conjugate. The amount of aggregates could be responsible for an avidity effect towards FcRn. These aggregates are known to cause immunogenicity, so we studied biochemical determinants inside the aminoacid sequence of marketed mAbs. We show that the biochemical nature of some aminoacids inside the paratope has an impact on the amount of aggregation. Anti-TNF- mAbs show very little aggregation but are very immunogenic in humans. We studied the role of the formation of immune complexes in the immunization against anti-TNF- mAbs in mice, and showed that immune complexes, but not FcRn are essential in the immunization process against anti- TNF- mAbs. These results give leads towards the generation of more efficient, better tolerated mAbs.

This thesis analyses the impact of granular aggregates with structures using experiments and numerical simulations. Original contributions include an insight into multiple factors affecting the loading and damage to the structures, along with study of numerical parameters important for realistic prediction of the interaction between the granular media and structures. It extends the current understanding related to such interactions, with an underlying motivation to guide strategies in order to reduce the structural damage. The response of structures impacted by granular media (sand or soil) is of significant research interest for many applications. One of the applications is for landmine explosions which causes ejection of soil from ground and damage to structures impacted by this ejected soil. Experimentation is done in a laboratory setting where the cylindrical sand slugs are generated at high speed using an impulse provided by a piston. This induces a velocity gradient along the slug, because of which the slug expands during the flight before impacting the target. Deformable as well as rigid flat targets are considered in two orientations relative to the incoming slug: perpendicular (i.e. normal orientation) and inclined at an angle of 45°. The targets are supported by force transducers to capture the loading from the slug. Simulations are performed using a combination of discrete particle and finite element schemes, which enables the analysis of the fully coupled interaction between the flowing granular media and the structure. A contact model involving multiple parameters is used for inter-particle and particle-target contact. Firstly, a numerical analysis is performed to characterise the temporal evolution of slugs and their impact on monolithic beams constrained at the ends. Out of all the parameters used for inter-particle contact definition in discrete particle method, only the contact stiffness is found to effect the velocity gradient in the slug before it impacts the target. Other factor influencing the gradient is the acceleration provided by the piston. A strong dependence of beam deflection on the stand-off distance is observed due to the velocity gradient in the slugs. As the second step, the effect of target surface properties on the transmitted momentum is analysed. Experiments are done by applying coatings of different hardness and roughness on the target surface impacted by sand slugs. For normally oriented targets, the transmitted momentum is observed to be insensitive to the change in surface coating. In contrast, for inclined targets, a significant influence of coatings is observed. Additionally, the momentum transmitted to the inclined targets is always less than that for normal targets. Numerical analysis of this surface effect reveals that assuming the slug particles to be spherical shape in simulations does not capture the particle/target interactions accurately and under-predicts the frictional loading on the target. Following this, a detailed numerical study is done to understand the effect of the shape of particles in the slug. Simple shaped non-spherical particles are constructed by combining spherical sub-particles. With increasing angularity of particles in the slug, the frictional loading on the target is shown to increase. This results in an increase of momentum transmitted to inclined targets. For normally oriented targets however, the particle shape does not affect the overall transmitted momentum, which is a behaviour similar to that observed when studying the effect of target surface properties. In addition, effect of fracture of particles in the slug is analysed by using beam connections between sub-particles that break during the impact with the target. If the fracture results in increasing particle angularity, the transmitted momentum increases, whereas the situation reverses if fracture results on more spherical shaped particles. Lastly, a strategy to reduce the loading on the targets is analysed by using sacrificial coating on the target surface. In experiments, this coating is placed on the rigid target surface using a lubricant at their interface. When impacted by the slug, this coating slides on the target surface, resulting in a reduction of frictional loading on the target. If the friction at the coating/target interface vanishes, the transmitted momentum approaches the theoretical minimum value. Simulations are used to first validate the experimental observations and then to extend the concept of sliding coatings using deformable targets. Both the transmitted momentum and deflections depended on the thickness of the target and coating. When a coating is used, the deflections increase due to reduction in target thickness. It is found that the best strategy to reduce the damage to the target is to use least possible thickness of the coating and minimise the friction at the interface between the coating and the target. The presented work examines many of the factors that affect the loading on the target impacted by granular slugs, in addition to characterising the expansion of slugs before the target impact. The analysed factors include those already known such as target stand-off distance, inclination and unveils others such as target surface properties and granular properties. The numerical analysis discloses important parameters and shows the effect of particle shape, highlighting the shortcomings of widely used spherical particle assumption in the numerical studies. A strategy using a sacrificial coating to reduce damage to the target is also analysed.

Dans le lait on peut distinguer les protéines sériques et les caséines. Les protéines sériques sont des protéines globulaires qui se trouvent dans le sérum du lait et elles sont connues pour leurs propriétés fonctionnelles exceptionnelles. Quand une solution de protéines sériques est chauffée, elles perdent leur structure native et peuvent s'agréger. Elles forment des agrégats de différentes formes, tailles et densités : des cylindres, des agrégats fractals, des microgels et des agrégats fibrillaires. De l'autre côté, les caséines sont organisées dans des micelles de caséine d'un rayon environ 100-200 nm stabilisées par du phosphate de calcium colloïdal.Au cours de ce travail, nous avons cherché à comprendre comment les agrégats de protéines sériques pouvaient être utilisés en mélange avec les micelles de caséine pour obtenir et contrôler la texture de produits laitiers. Dans un premier temps, nous avons étudié le processus de « cold gelation » induit par ajout de calcium et/ou acidification d'agrégats et de microgels de protéines sériques seuls. Dans une deuxième partie, nous nous sommes intéressés à la fonctionnalité des agrégats dans les mélanges plus complexes avec les autres protéines laitières et en présence de minéraux. L'addition de petites quantités d'agrégats fractals dans des suspensions de micelles diminuait leur température critique de gélification, augmentait le module élastique et diminuait la synérèse des gels.Les agrégats de protéines sériques peuvent être utilisés pour modifier la viscosité des mélanges, comme gélifiant ou pour enrichir la teneur en protéine du milieu sans en augmenter la viscosité. / The proteins of milk can be divided into whey proteins and caseins. Whey proteins are compact globular proteins that are found in the aqueous phase of milk. They are well-known for their exceptional functional properties. Upon heating, individual whey proteins denature and aggregate, forming aggregates of different morphologies and sizes, such as strands, fractal aggregates, microgels and fibrillar aggregates, depending on the heating conditions. On the other hand, the caseins in milk are organized in complex protein units with a diameter of 100-200 nm called casein micelles stabilized by colloidal calcium phosphate (CCP).The current work is an endeavor to understand how whey protein aggregates might be used in mixtures with other dairy proteins, such as casein micelles, in order to get a particular texture in a dairy product. We first extended the understanding of so-called “cold gelation” of pure WPI aggregates induced by calcium and acidification and then studied how the aggregates work in more complex mixtures of proteins and minerals. Interestingly, addition of small amounts of fractal aggregates to suspensions of casein micelles has been demonstrated to decrease the critical gelation temperature, increase the elastic modulus and decrease the syneresis of the gels.The aggregates are to be used to modify the viscosity of dairy products, as a gelling agent and for protein enrichment. The properties of strands, fractal aggregates and microgels have been studied and compared. WPI aggregates might be considered as “clean label” texturizing ingredients that do not require approval from the European Food Safety Authority (EFSA).

Scanning ion conductance microscopy (SICM) is a technique for non-contact topographic imaging. In this thesis, a biophysical investigation into Alzheimer's Disease (AD) was carried, with toxic oligomers dosed locally and quantitatively on to single astrocytes using SICM and simultaneously monitoring the response of the target cell. Examination of the effectiveness of antibodies that bind to Abeta or alpha-synuclein (Asyn)peptides depends on the measurement of oligomer-induced abnormal calcium homeostasis in single astrocytes. The method was shown to work at physiological concentrations of oligomers. A series of experiments measuring the reduction in calcium inux in mixtures of antibodies and cerebrospinal fluid (CSF) of AD patients suggested that the binding to co-oligomers composed of Abeta and Asyn may be crucial in the treatment of AD. Furthermore, it may be beneficial to test antibodies before the clinical trial using this assay. The mechanism of this entry of calcium is hypothesised to be the result of the formation of oligomer-induced transient pores in the cell membrane. To verify this hypothesis, a new SICM instrument was built with two nanopipettes; one for dosing and one for detection of the adenosine triphosphate (ATP) release from these pores. A variety of different ATP sensors were made. The best had a sensitivity of 10 micro molar and works as a hexokinase-cofunctioned electrolyte-gated organic field-effect-transistor. However no statistically significant results for ATP release have been obtained in the experiments performed to date. Overall this thesis describes new biophysical methods to study the effect of protein aggregates on live cells and the effectiveness of potential therapies, such as antibodies and nanobodies, to reduce these aggregate induced effects. It can be applied to synthetic aggregates of Abeta or the aggregates present in human CSF.

A construção civil consome grande quantidade de recursos naturais, energia e gera 50% do total de resíduos produzidos no mundo. A reciclagem dos resíduos de construção e demolição é uma prática de grande importância para o ambiente, uma vez que ela constitui uma alternativa para reduzir o impacto ambiental causado pelo setor. Nos diversos estudos já desenvolvidos quanto à utilização dos resíduos de construção e demolição em concreto não se observa um consenso com relação ao desempenho destes concretos. Uma das causas dessa diversidade de resultados é a grande variabilidade na composição dos agregados reciclados. Controlando a variabilidade se tornará mais fácil garantir que os concretos produzidos com esses agregados tenham bom desempenho e durabilidade. Assim, este trabalho foi desenvolvido com o objetivo de determinar um parâmetro de controle da variabilidade dos agregados reciclados, comparando a classificação pela composição e pela separação densitária, para utilização em dosagens de concretos. Foram realizadas caracterizações dos agregados reciclados obtidos a partir do beneficiamento de resíduos de construção e demolição coletados em três locais diferentes. Para produção dos concretos foram consideradas três relações a/c (0,50; 0,60 e 0,70) e três níveis de substituição tanto do agregado miúdo reciclado, quanto do agregado graúdo reciclado (0%, 50%, 100%), sendo que as combinações executadas foram definidas através de um projeto estatístico. As propriedades avaliadas foram resistência à compressão, resistência à tração por compressão diametral, módulo de deformação e absorção de água por imersão. A partir dos resultados obtidos foram elaborados modelos matemáticos para cada uma das propriedades avaliadas, e foram estabelecidas as relações entre os resultados de cada coleta e as características dos agregados reciclados de cada uma delas. Concluiu-se que o comportamento do concreto com agregados reciclados não pode ser previsto através da composição ou da densidade dos agregados, uma vez que ambos os aspectos e também outras características dos agregados influenciam na qualidade dos concretos, dependendo da propriedade considerada. / Civil construction consumes a large quantity of natural resources, energy, and it generates 50% of total wastes produced in the world. The recycling of construction and demolition wastes it is an important practice for the environment, being a good way to reduce the environmental impact caused by the sector. In many researches already developed about the use of the construction and demoliton wastes in concrete, there is a diversity of results. One cause of this is the great variability in the composition of recycled aggregates. The control of aggregates variability will become easier to control the properties of concretes with recycled aggregates. Thus, this work was developed with the purpose to find a control parameter of the variability of these aggregates, comparing the analysis by composition and heavy media separation, to use in concretes mix design. Characterizations of recycled aggregates obtained from construction and demolition wastes collected at three differente places were accomplished. Three water/cement ratio – 0,50; 0,60; and 0,70 – and three substitution proportion from fine and coarse recycled aggregate – 0%, 50%, 100% – were considered to produce concrete mixtures. The combinations executed were defined by a statistical project. The properties evaluated were compressive strength, split tensile strength, modulus of elasticity and water absorption. Mathematical models were obtained to estimate the properties evaluated. Relations between the results from each collection and the properties of the recycled aggregates were established. In conclusion, the concrete with recycled aggregates behavior can not be predict through composition or density of aggregates. Both aspects and other aggregates characteristcs have influenced on the quality of concretes, depending of the property evaluated.

This master’s thesis studies the problems of high temperatures on cement concretes, their following diagnostics from pre-treatment to rehabilitation, the emphasis was on the use of high-speed water jet. In the experimental part of the design of a concrete composition with basalt aggregate. Were reviewed the physico-mechanical properties after thermal loading. The influence of pressure water jet on the thermal load on concrete, pull-off test, the volume of the removed concrete with a strength evaluation and comparison.

Cette étude a eu pour objectif de contribuer à une meilleure compréhension du comportement photochimique de certains micropolluants de type antibiotiques vétérinaires (sulfaquinoxaline, pyriméthamine) ou antibactérien (triclosan) en solution aqueuse et à la surface de la kaolinite, utilisée comme un modèle de sol.L’étude du comportement photochimique de la sulfaquinoxaline a été réalisée sous excitation à 254 nm et 365 nm. Dans tous les cas, une dégradation efficace est observée avec un rendement quantique qui dépend de la longueur d’onde d’excitation, du pH et la concentration d’oxygène dissous. De plus, la présence de l’oxygène moléculaire dans le milieu conduit à une inhibition partielle la photodégradation mettant en évidence l’implication partielle de l’état excité triplet. Ce dernier a pu être mis en évidence par photolyse laser nanoseconde à travers un transfert Triplet-Triplet (T-T) en employant le β-carotène comme accepteur. Sur le plan analytique, la phototransformation de la sulfaquinoxaline conduit à la formation d’un grand nombre de produits qui ont été identifiés par HPLC/ESI/MS/MS en identifiant les processus de fragmentation intervenant pour chaque molécule étudiée. L’étude a permis de montrer que les états excités singulet et triplet sont tout les deux impliqués dans la photodegradation et que les processus principaux intervenant sont la photohydrolyse, la désulfonation avec un réarrangement intramoléculaire, l'hydroxylation des motifs aromatiques et l'isomérisation selon un processus de type photo Fries.L’étude de la photoréactivité de la pyriméthamine a montré que la dégradation est plus efficace avec la forme neutre. Le rendement quantique a été évalué à environ 4,0x10-2 en milieu aéré et sous excitation à 254 nm. L’étude par photolyse laser a montré la formation intermédiaire de l’état excité triplet mais également de l’électron solvaté (absorption à 700 nm). Les processus de formation des photoproduits primaires sont la substitution de l’atome de chlore par un groupement hydroxyle ou par un atome d’hydrogène et l’hydroxylation du noyau aromatique.La dégradation des micropolluants à la surface du sol a pu être abordée en utilisant l’argile kaolinite comme support modèle. Ce système simplifié nous a permis d’étudier la photodégradation sous excitation en Suntest sur le plan cinétique et analytique. L’étude cinétique a été entreprise en fonction de différents paramètres tels que l’épaisseur de la kaolinite et la concentration initiale du substrat. Le premier effet nous a permis de montrer que pour des épaisseurs inférieures à 70 µm, la vitesse de diffusion du composé des zones sombres vers les zones irradiées est très rapide devant la photolyse et de ce fait, elle peut être négligée. Cet aspect a conduit à la détermination du rendement quantique de disparition à la surface de la kaolinite. Sur le plan analytique, les réactions observées sur l’argile sont différentes de celles observées en solution aqueuse. En effet, dans le cas de la sulfaquinoxaline, seul le produit de désulfonation est observé. Au contraire de la sulfaquinoxaline, l’étude complète de la molécule de triclosan a montré la formation de plusieurs produits et notamment des dimères ou des oligomères ce qui suggère la présence du substrat sous forme d’agrégats à la surface de l’argile. Afin de confirmer cette observation expérimentale, nous avons abordé une étude de modélisation par dynamique moléculaire. Celle-ci a donnée des informations très importantes sur l’organisation des molécules à la surface de la kaolinite. Ainsi, l’adsorption du triclosan fait intervenir d'importantes liaisons hydrogène avec la surface de la kaolinite. En présence de plusieurs molécules, la formation d’agrégats est gouvernée par une importante interaction entre les noyaux aromatiques de type π-stacking. / The study undertaken within this thesis concerns the photochemical behavior of the veterinary antibiotics sulfaquinoxaline and pyrimethamine, as well as the antimicrobial triclosan in aqueous solutions and at the surface of kaolin, used as a soil model.The photochemical study on sulfaquinoxaline was performed at 254 and 365 nm. In all cases, an efficient degradation was observed with a quantum yield that depends on the excitation wavelength, pH and the dissolved molecular oxygen concentration. Molecular oxygen acts as an inhibitor which reflects the involvement of the triplet excited state. Sulfaquinoxaline was clearly shown to be a photosensitizer of β-carotene via a triplet-triplet transfer process. From the analytical point of view, several photoproducts were generated and identified by using HPLC/ESI/MS/MS technique through a close analysis of the fragmentation processes. The byproducts that were formed via the singlet as well as the triplet excited states were mainly generated by photohydrolysis, desulfonation, hydroxylation and isomerisation reactions.The photochemical study of pyrimethamine indicates an efficient photoreactivity with the molecular form. The laser flash photolysis study reveals the implication of singlet and triplet excited states. The byproducts were mainly formed through the substitution of the chlorine atom by an hydroxyl group and the hydroxylation of the aromatic moiety.The photochemical study at the surface of soil was undertaken by using kaolin as a model support. Such simple system appears to be a guideline for precise kinetic and analytical studies. The former was performed as a function of several important parameters such as the layer thickness and the initial concentration of the substrate. The first parameter clearly indicates that for a thickness lower than 70 µm, the rate of diffusion is so fast that this process can be neglected when compared to the photochemical process. Thus, the first rate constant at the surface of kaolin was determined. Only the product of desulfonation was observed with sulfaquinoxaline while with triclosan, several byproducts were obtained such as dimers and oligomers suggesting the formation of aggregates at the surface of the solid support. In order to confirm this aspect, molecular dynamics studies were undertaken and indicate that the adsorption of triclosan mainly occurs at the surface of kaolin via hydrogen molecular bonds. The arrangement of the molecules in a cluster is governed by π-stacking type interactions between the aromatic moieties.