Neste trabalho estudou-se a encapsulação de proteínas com diferentes pesos moleculares na sílica mesoporosa ordenada SBA-15 para avaliar sua aplicação como adjuvante imunológico. Para tanto, as proteínas IgG (150 kDa) e BSA (66,5 kDa) foram incorporadas à sílica mesoporosa com poros expandidos. Primeiramente estudou-se a dilatação dos poros utilizando-se um agente dilatador de estrutura no processo de síntese, através da preparação de amostras com diferentes quantidades de triisopropilbenzeno (TIPB). Resultados de isoterma de adsorção de nitrogênio (NAI) e espalhamento de raios X a baixo ângulo (SAXS) revelaram um aumento no diâmetro médio de poros da ordem de 23% e uma rede de poros mais desordenada. Para se ter uma estimativa das dimensões das proteínas, medidas de SAXS foram feitas e indicaram que ambas têm dimensões que permitiriam sua incorporação nos poros da SBA-15. As amostras com poros dilatados foram então utilizadas para a incorporação das proteínas IgG e BSA em solução tampão fosfato salina (PBS). Os resultados indicaram o preenchimento dos microporos pela solução de PBS com valor superior a 95%. Quanto ao preenchimento de mesoporos, observou-se maior variação no volume de poros e área superficial, para o material com maior diâmetro médio de poros, atingindo valores em torno de 80 % e 90%, respectivamente. Não houve diferença significativa nestas porcentagens entre a incorporação das duas proteínas, indicando que as proteínas devem estar encapsuladas na macroporosidade da sílica, obstruindo a entrada dos mesoporos. Um modelo teórico foi utilizado para analisar as medidas de SAXS e ele confirmou o preenchimento dos microporos e a presença da proteína nos mesoporos da sílica. Utilizando a técnica analítica de Particle Induced X-ray Emission (PIXE), o conteúdo de silício em fezes de camundongos isogênicos foi avaliado em função do tempo, com o intuito de analisar a liberação de sílica pelo organismo dos camundongos. Observou-se que após a primeira administração de sílica os camundongos inoculados por via oral liberaram uma quantidade de silício similar à liberada pelos camundongos controle, que receberam apenas a solução de PBS. Após a segunda administração os camundongos inoculados com sílica por via oral liberaram uma quantidade de silício superior à dos camundongos controle, devido à morte dos macrófagos e outras células que atuam na resposta imunológica, evidenciando a eliminação de silício pelo organismo. Um estudo paralelo de controle de qualidade foi realizado em amostras de SBA-15 preparadas pela Cristália Produtos Químicos Farmacêuticos Ltda. a fim de garantir a reprodutibilidade deste material, que será comercialmente utilizado para a formulação de vacina oral contra Hepatite B, produzida pelo Instituto Butantan. Os resultados mostraram propriedades texturais reprodutíveis das amostras produzidas pela Cristália indústria farmacêutica. / In this work we studied the encapsulation of proteins with different molecular weights into SBA-15 ordered mesoporous silica to evaluate its application as immunological adjuvant. Hence, the IgG protein (150 kDa) and BSA (66.5 kDa) were incorporated into the mesoporous silica with expanded pores. First we studied the expansion of the pores using a structure swelling agent in the synthesis process, by preparing samples with different amounts of triisopropylbenzene (TiPB). Results of Nitrogen Adsorption Isotherm (NAI) and Small Angle X-Ray Scattering (SAXS) showed an increase in average pore diameter of the order of 23% and a more disordered pore network. To provide an estimate of the size of proteins, SAXS measurements were performed and indicated that both have dimensions that allow its incorporation in the pores of SBA-15. These samples were used for the incorporation of IgG and BSA proteins in phosphate buffered saline (PBS) solution. The results indicated a filling of the micropores by PBS solution larger than 95%. Concerning the filling of mesopores, we observed a larger variation in pore volume and surface area for the material with highest average pore diameter, reaching values around 80% and 90%, respectively. There was no significant difference in these percentages between the incorporation of the two proteins, indicating that the proteins could be encapsulated in the silica macroporosity, blocking the entry of mesopores. A theoretical model was used to analyze the SAXS measurements and it confirmed the filling of micropores and the presence of protein in the silica mesopores. Using the analytical technique \"Particle-Induced X-ray Emission\"(PIXE), the silicon content in mice feces was evaluated as a function of time, in order to analyze the release of silica from the organism of the mice. We observed that after the first silica administration the isogenic mice inoculated by oral administration released a similar amount of silicon compared with the amount released by the isogenic control mice, which received only PBS solution. After the second oral administration, the mice inoculated with silica released a higher amount of silicon than the control mice, due to the death of macrophages and other cells that act on the immune response, indicating the elimination of silicon by the organism. A parallel study about quality control was performed on SBA-15 samples prepared by Cristália Produtos Químicos Farmacêuticos Ltda., to ensure the reproducibility of this material which will be used commercially for the formulation of an oral vaccine against hepatitis B, produced by the Butantan Institute. The results showed reproducible textural properties of the samples produced by the Cristália pharmaceutical industry.

PURPOSE: To determine, under flow conditions, whether reduced connections between Schlemm’s canal (SC) inner wall (IW) and juxtacanalicular tissue (JCT) cells play a role in giant vacuole (GV) formation; and whether decreased amount of cell margin overlap between adjacent IW cells promotes paracellular pore formation using serial block-face scanning electron microscopy (SBF-SEM). METHODS: Normal human eyes were immersion-fixed (0 mmHg, N=2) or perfusion-fixed (15 mmHg, N=1). Frontal and radial sections of SC were processed for SBF-SEM. IW and JCT cells, GVs, and pores were 3D-reconstructed. In each IW cell, total number of connections with underlying JCT cells/matrix was determined. Total cell margin length (TCML) and zero-overlap length (ZL) of each IW cell were measured to calculate percent zero-overlap length (PZL=ZL/TCML). All data were compared between the eyes fixed at 0 and 15 mmHg. RESULTS: Total number of IW/JCT connections in individual IWs significantly decreased in the eye fixed at 15 mmHg (33±5, N=5 cells) compared to those fixed at 0 mmHg (189±12, N=4 cells, p<0.001). The summed GV volume in individual cells significantly increased in the eye fixed at 15mmHg (218.03±19.65 μm3) compared to those fixed at 0 mmHg (82.33±27.22 μm3, p=0.0043). PZL increased 26.68% (p=0.001) in the eye fixed at 15mmHg vs. those fixed at 0mmHg, and all paracellular pores were found only in regions where the overlap length was 0 μm. CONCLUSIONS: Cellular connections between IW/JCT and IW/IW cells play a role in GV and pore formation in normal human eyes under flow conditions. Our results provide a baseline for future comparison with primary open angle glaucoma eyes.

Selective electron beam melting (SEBM) is a promising powder bed Additive Manufacturing technique for near-net-shape manufacture of high-value titanium components. An extensive research program has been carried out to characterise in 3D the size, volume fraction, and spatial distribution of the pores in model samples, using X-ray computed tomography (XCT), and correlate them to the SEBM process variables. The average volume fraction of the pores (97.5 %) where fatigue cracks would initiate based on the relative stress intensity factor of all the pores. In contrast, crack growth was found to be insensitive to porosity, which was attributed to the much higher stress concentration generated by the crack in comparison to the pores. Some crack diversion was associated with the local microstructure, with prior β grain boundaries often coincident with crack diversion.

Le transport réactif des NPs en milieu poreux regroupe trois principaux processus : l’agrégation, le dépôt et le transport des NPs. Le système réel est caractérisé par la complexité et l’interdépendance de ces trois processus. En plus, ces derniers ne possèdent pas forcément la même échelle propre d’étude ou de modélisation. Cela explique la difficulté majeure pour décrire simultanément tous ces processus couplés et interdépendants dans un seul modèle aisément utilisable. Au départ, nous avons simplifié ce système en séparant les différents processus. Ensuite, nous résolvons le problème d’échelle, par l’approche d’homogénéisation ou par l’approche multi-échelles. La séparation du problème, en plusieurs processus et sur plusieurs échelles d’espace, facilite la résolution numérique et la compréhension des processus élémentaires. Dans cette étude, une approche multi-échelles a été développée pour modéliser ces trois processus (l’agrégation, le dépôt et le transport des NPs), chacun dans sa propre échelle. Nous avons considéré deux échelles de taille, l’échelle microscopique ou d’interface (nanométrique), et l’échelle mésoscopique correspondant à la taille des pores (micrométrique). A l’échelle microscopique, les processus d’agrégation et de dépôt ont été modélisés, de manière similaire, avec la théorie DLVO. Les propriétés électrostatiques de surface des NPs ou de la roche sont décrites par un modèle de complexation de surface développé sous PhreeqC. Ce modèle d’interface est testé pour deux types de matériaux, le titane pour les NPs et la silice pour la roche. A l’échelle mésoscopique, le dépôt est quantifié par la théorie classique de la filtration (CFT : Classical Filtration Theory) dans la phase initiale où le filtre est propre. Le processus de transport a été simulé par un modèle de réseau de pores (PNM : Pore Network Model) à l’échelle mésoscopique. Ce modèle de transport est couplé avec le modèle d’agrégation-dépôt et indirectement avec le modèle de complexation de surface en un seul modèle appelé PhreeqC Pore Network Transport(PPNT1.0). / Reactive transport of NPs in porous media involves three main processes: aggregation, deposition and transport of NPs. The natural system is characterized by the complexity and interdependence of these three processes. In addition, these processes do not necessarily have the same study or modeling scale. This explains the extreme difficulty to describe simultaneously all these interdependent processes in one easy-tohandle numerical model. We have simplified the system by separating the different processes. Then, we solve the problem of scale by the homogenization or the multi-scale approach. Dividing the initial problem into different processes on different scales facilitates the numerical solution and the understanding of each process separately. In this study, a multi-scale approach has been developed to model, each mechanism at its own scale. We considered two modeling scales, the microscopic or interfacial scale (nanometric scale), and the mesoscopic scale (micrometric scale). At the microscopic scale, the processes of aggregation and deposition have been modeled in a similar manner with the DLVO theory. Surface electrostatic properties of NPs and rocks are described by a surface complexation model implemented in geochemical modeling program (PHREEQC). This surface complexation model was tested for two types of materials, titanium and silica. At the mesoscopic scale, the deposition is quantified by the classic filtration theory (CFT) in the initial phase when the filter is clean. The transport of NPs in porous media was simulated by a pore network model (PNM) at the mesoscopic scale. This transport model was coupled with the deposition-aggregation model and also indirectly with the surface complexation model. These three models are coupled in a single model called: PhreeqC Pore Network Transport (PPNT1.0).

The aim of this study was to quantify the density of taste pores on the anterior region of the tongue, in adult males and 8 to 9 year old boys. Earlier studies had shown that, although 8 to 9 year olds were poorer than adults at sensing the tastant sucrose using a whole mouth procedure, localised regions of the tongue in male children were more sensitive than equivalent regions in adults. This study aims to detemine whether the age differences in sensitivity is related to a difference in taste pore density. Two areas of the tongue, for which children had previously been shown to have higher sensitivity than adults, were examined using a videomicrosocpy technique and the number and diameter of taste pores were measured. Children were found to have a greater density of taste pores, however the number of taste pores per papilla were similar in children and adults. It was found to be likely that the greater sensitivity of localised areas on the children's tongue is due to a greater taste pore density. The reduced sensitivity reported using whole mouth stimulation may be due to a reduced capacity to assimilate taste input from the whole mouth or due to different relative contributions to whole-mouth taste from the various receptive fields in the mouth. / Master of Science (Hons)

Ce travail a pour but de concevoir des outils d'analyse d'image 3D de matériaux poreux, obtenues par microtomographie à rayons X, afin de caractériser géométriquement la structure micronique des pores et de mettre en évidence le lien entre microgéométrie et propriétés de transport macroscopiques. Partant d'une image segmentée, une séquence complète de traitements (filtrage d'artefacts, squelettisation, LPE, etc.) est proposée pour positionner et délimiter les pores. Une comparaison aux techniques existantes est faite, et une méthodologie qualifiant la robustesse des procédures est présentée. Cette décomposition est utilisée, premièrement pour extraire des descripteurs géométriques de la microstructure porale qui sont examinés en rapport avec la perméabilité intrinsèque ; deuxièmement pour aider à la construction d'un réseau de pores permettant d'effectuer des simulations numériques.

Ce manuscrit présente une étude expérimentale et théorique sur les écoulements granulaires immergés le long d'un plan incliné, modèle en<br />laboratoire des avalanches sous-marines. L'étude expérimentale porte sur un<br />écoulement granulaire stationnaire et uniforme, complètement immergé dans<br />de l'eau. Les mesures de vitesse et d'épaisseur montrent que la définition<br />d'un nombre sans dimension dépendant d'un rapport de deux temps caractéristiques permet de comprendre quantitativement de tels écoulements.<br />L'adaptation de ce nombre sans dimension à un écoulement sec ou immergé<br />permet de définir de manière universelle une rhéologie de friction. Intégrée<br />aux équations moyennées dans l'épaisseur, cette rhéologie permet de définir<br />un critère de stabilité entre les écoulements stationnaires et des écoulements<br />instables, en accord qualitatif avec les observations expérimentales. Pour<br />mieux comprendre le rôle du fluide interstitiel, nous avons étudié numériquement<br />la trajectoire d'un bloc poreux en écoulement le long d'une pente rugueuse.<br />Outre la dissipation visqueuse, la présence du fluide peut apporter une lubrification modifiant les trajectoires du bloc poreux, et les angles<br />d'écoulements stationnaires. La dernière partie du manuscrit présente des<br />perspectives sur les écoulements immergés instationnaires ainsi qu'un ensemble<br />de conclusions.

Les aubes de turbine haute pression des turboréacteurs sont des composants soumis à des chargement thermo-mécanique sévères. Ces aubes sont maintenant réalisées en superalliage monocristallin à base nickel car ce matériau possède d'excellentes propriétés à haute température. Le procédé de fabrication de ces aubes monocristalline entraîne des défauts et notamment des pores localisés dans les espaces inter-dendritiques. Sous l'action de sollicitation cyclique, des microfissures se forment sur ces défauts, donnant naissance à une fissure principale pouvant conduire à la rupture de la pièce. L'objet de cette thèse est d'étudier l'amorçage et la micro-propagation de fissure sur défaut. Une étude expérimentale a été menée sur des éprouvettes tubulaires contenant une entaille assimilée à un pore. Nous avons montré que la viscoplasticité et l'activation de l'oxydation induisaient un comportement de type fissure courte. Une analyse numérique par éléments finis sur des maillages d'éprouvettes entaillées a montré l'importance de la plasticité générée par le défaut sur la vitesse de propagation des fissures courtes. Puis nous avons établi un modèle de micro-propagation de fissure permettant d'estimer la vitesse de propagation de fissure s'amorçant sur une entaille. Nous avons opté pour un modèle décrit à l'échelle locale en utilisant les champs de contraintes générées par le défaut. Ce modèle rend compte de la plasticité locale due à l'entaille et de la fragilisation en pointe de fissure par l'oxydation. Le modèle développé ouvre des perspectives prometteuses sur la prédiction de la durée de vie à l'amorçage sur pore de fonderie.

Soil structure influences many chemical, biological and physical processes and it is well established that organic carbon acts as a soil binding agent. However, the precise location of organic matter and carbon in relation to structural features within intact samples is unknown. The sensitivity of organic carbon to decomposition is dependent not only upon its intrinsic chemical recalcitrance, but also its location within the soil structure. Soil structure provides organic carbon with chemical and physical protection, the extent of which varies between structural units. Furthermore soil structure is transient, and is sensitive to both environmental changes and physical disturbance, therefore it is difficult to determine and quantify the impact of this dynamic entity upon the storage of organic carbon. To date the majority of research that has advanced our understanding of the role soil structure plays in the storage of organic carbon, has relied upon some form of fractionation technique to separate aggregates from the bulk soil. However this approach has its disadvantages as much of the soil structure is destroyed; clearly when studying the impact of soil structure upon organic carbon-storage it is advantageous to implement any method that minimises disturbance to the soil structure. This study entails removing intact soil samples (through the use of kubiena tins) from long-term agricultural experimental fields at Rothamsted Research, (Hertfordshire, UK) with the aim of comparing and evaluating the location of organic matter and it’s associated organic carbon, in soils with contrasting organic carbon contents and a well documented land-use history. Thin sections will be analysed by integrating conventional micromorphology, image analysis and sub-microscopy combined with microscale chemical analysis scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). In doing so a new alternative method for analysing the distribution of organic matter and organic carbon is proposed. It was found that agricultural soils, which are the same in all aspects except total-OC content, differ in total organic matter, water release characteristics, aggregate stability and pore size distribution; therefore these differences could be attributed to the relationship between OC and soil structure. The water release curve, aggregate stability and pore size distribution also differed between soils with similar OC-contents but from different land-uses. The analysis of organic matter within intact soil samples provided evidence for the redistribution of organic matter as it is decomposed within the soil structure, for instance, less decomposed organ and tissue forms were located in or near to soil pores while more decomposed amorphous forms were located within the soil matrix. Since the same pattern of redistribution was observed in both agricultural and grassland soil this is likely to be directed by soil macro and micro fauna. It is concluded that since the location of different forms of organic matter is consistent across all soil, organic matter location is not responsible for creating differences in aggregate stability between treatments. Instead the results indicate that the amount and strength of organic carbon bonds and its hydrophobic properties are responsible. Micromorphology results demonstrated an absence of defined aggregation between treatments. Despite the difficulties in the interpretation of aggregation, the results contradict theories of aggregation, which state that aggregates are formed around “fresh” organic matter and it is argued that OM will undergo substantial decomposition before it acts as core for aggregation. Initial SEM-EDS analysis, has shown that in the soil matrix adjacent to organic matter (plant/organ) fragments there is a heightened concentration of C, indicating that these fragments are acting as a source of organic carbon. Interestingly BC, which represent one of the most recalcitrant C forms is also acting as a source of C, although these initial results suggest to a lesser extent than more labile C-sources. This source of organic carbon could stimulate microbial activity thereby enhancing soil structural stability. Alternatively, the release of liable carbon into soil pores may represent one route by which labile carbon enters sub-soil horizons.

In this research work, porous films on aluminum foil, with vertical through and through pores, were fabricated. The films were anodized at different applied voltages and the conditions were reported. In some cases, aluminum foil films were anodized under constant current conditions. Thicker aluminum films, referred to as aluminum tape in this thesis, were also anodized to get good porous films. While the porous alumina films using aluminum tape produced pores with good uniformity, the films did not produce through and through pores. Porous alumina films were also prepared on aluminum evaporated ITO substrate. The films on ITO substrate were different from the porous alumina films using aluminum foil/tape. In case of ITO substrate based films, an additional condition, temperature was also varied. The anodization process on ITO substrate based films was done at lower temperatures in order to reduce the effect of high currents on the process. The SEM images for different anodization conditions were compared and the porosity of films was calculated. CdS was electrodeposited inside porous alumina. D.C as well as a.c. voltages were applied and duration of the process was varied to study their effect on film morphology and the thickness of the deposited CdS. The current-voltage characteristics of the CdS-deposited alumina films were plotted and the phase of the electrodeposited CdS was found to be hexagonal using XRD.