Una de las características más importantes del polipropileno (PP) es su versatilidad, la que hace posible, por ejemplo, su modificación mediante distintos métodos físicos y químicos ampliando su rango de aplicaciones. Entre las modificaciones que se le pueden hacer al PP se encuentra el mezclado con cargas, y en particular con nano-cargas, las que tienen al menos una dimensión en escala nanométrica. Las arcillas, y sobre todo, la montmorillonita (MMT), son una de las nano-cargas más usadas para la preparación de nanocompuestos de PP, aun cuando deben ser tratadas para darles un carácter organofílico (o-MMT). El método más usado hasta el momento para generar las mezclas de PP y o-MMT es el mezclado en fundido ya que es un proceso pos-reactor que resulta fácil de implementar con equipamiento de procesamiento habitual. Sin embargo, la aplicación de este método suele requerir el uso de un agente compatibilizante con cierto grado de polaridad, como es el PP modificado con anhídrido maleico. Los avances logrados en la preparación de nanocompuestos de PP y o-MMT han sido muchos desde que se comenzaron a estudiar hace un par de décadas. Sin embargo, los materiales que se han obtenido usando mezclado en fundido con compatibilizantes no presentan el nivel de mejora en sus propiedades que se observan en otros nanocompuestos poliméricos. Una técnica similar, aun casi no explorada y de fácil implementación a nivel industrial, es aquella que no utiliza compatibilizante sino que trata de generarlo in-situ, durante el mezclado, mediante la modificación química del polímero. Se plantea así el objetivo de esta tesis, que es obtener nanocompuestos basados en PP y MMT por mezclado reactivo en fundido, con buen grado de desagregación y exfoliación de las partículas de arcilla de manera de mejorar propiedades físicas del PP. Durante el desarrollo del trabajo se ha explorado el efecto del funcionalizante durante el procesamiento reactivo con intención de generar el compatibilizante in-situ, se han analizado distintas políticas de incorporación de componentes al medio de reacción, y se han evaluado las propiedades de flujo, térmicas y de barrera de los materiales obtenidos en función de sus características estructurales, concentración de componentes y procedimiento de mezclado. Los resultados obtenidos muestran que: es posible obtener nanocompuestos de PP y arcilla por funcionalización in-situ usando tanto anhídrido maleico (AM) como acrilato de n-butilo (BA). Se ha encontrado, además, que el mezclado secuencial, en el que se funde el PP y se agrega la arcilla a mitad del tiempo total de procesamiento durante el mezclado reactivo, es el procedimiento que genera mayor intercalación y/o grado de exfoliación de la arcilla tanto al usar AM como BA. Este mecanismo produce materiales en los que la permeabilidad al oxígeno y la velocidad de degradación oxidativa del PP son disminuidas significativamente sin afectar de manera notable la transparencia del polímero o sus procesos de cristalización y fusión. Además, la disminución del peso molecular de la matriz polimérica hace que las propiedades de flujo de los compuestos obtenidos no superen las del PP, lo que es otra consecuencia beneficiosa desde el punto de vista tecnológico. / One of the most important features of polypropylene (PP) is its versatility, which makes it possible, for example, the modification using different physical and chemical methods increasing its range of applications. Among the modifications that can be made to PP, one is the mixing with fillers, and particularly, with nano-fillers, which have at least one dimension in the nanoscale. The clays, and especially montmorillonite (MMT), are one of the nano-fillers more used in preparing nanocomposites of PP, even though they must be treated to give them organophilic characteristics (o-MMT). The method most used so far to produce the mixing of PP and o-MMT is melt mixing, since it is a post-reactor process that may be easily implemented with standard processing equipment. The application of this method generally requires the use of a compatibilizing agent with some degree of polarity, such as maleic anhydride grafted PP (PPgA). In the last decades there have been many advances in the preparation of compatibilized nanocomposites of PP and o-MMT using melt mixing. However, the materials that have been obtained so far using this methodology do not show the level of improvement in properties that have been observed in other polymeric nanocomposites. A similar technique, still almost unexplored and that can be easily implemented on an industrial level, is the one that does not use a compatibilizer but rather generates it in-situ during mixing by chemical modification of the polymer. This raises the goal of this thesis, which is to obtain nanocomposites based on PP and MMT using reactive melt mixing, with good degree of delamination and disintegration of the clay particles in order to achieve improved physical properties. During the development of the work, the effect of the functionalization of the polymer during the reactive processing has been explored trying to generate the compatibilizer in-situ. Also, different policies of incorporating components to the reaction medium have been considered, and the flow, thermal and barrier properties of the obtained materials have been evaluated as a function of the structural characteristics of the composites, the concentration of the components, and the type of mixing process. The obtained results show that: it is possible to obtain nanocomposites of PP and MMT using in-situ functionalization with both, maleic anhydride (AM) and n-butyl acrylate (BA). It has been found also that the sequential mixing, which begins by melting the PP and contemplates the addition of the clay half the way during the reactive mixing, is the procedure that generates the greater intercalation and/or the largest degree of exfoliation of the clay, both with AM and BA. This mechanism produces materials that display oxygen permeability and oxidative degradation rate that are significantly smaller than in PP without affecting considerably the transparency of the original polymer and its crystallization and melting processes. Moreover, the reduction of the molecular weight of the polymeric matrix makes that the flow properties of the obtained compounds are smaller than those of the original PP, which is another beneficial result from the technological point of view.

The objective of this study was to determine if the method of incorporation of a silicate layered nanoclay into a polymer matrix can affect the barrier properties of the pristine polymer in order to decrease the transport of volatile organic compounds (VOC) in indoor air. Building materials are a primary source for VOCs. These emissions are a probable cause of acute health effects and discomfort among occupants and are known to diminish productivity. The predicted concentrations of several of the VOCs emitted by structural insulated panels (SIP) are of concern with respect to health and comfort of occupants. The main issue related to the barrier membranes is the dispersion properties of the nanoclays in the polymer matrix, and the generation of a tortuous pathway that will decrease gas permeation. The tortuous pathway is created by a nanoclay filler, whose ideal exfoliated structure has high surface area, and high aspect ratio. By choosing the appropriate surfactants, the nanoclays can be modified to allow improved molecular interactions between the nanoclay and the polymer matrix. Several studies were performed in order to evaluate the dispersion properties of the nanoclay in the polymer matrix. Polymer/clay nanocomposites barrier membranes were generated via different synthesis methods. In the first study, barrier membranes were composed of a polyurethane, Estane ® 58315, and different nanoclays, Cloisite ® 10A, Cloisite ® 20A, Cloisite ® 30B. The interaction of the polyurethane and the different surfactants used to organically modify the nanoclay was evaluated. The dispersion of the clay platelets was analyzed by varying the pre-processing method; sonication vs stirring. The decrease in gas permeability results was enhanced by the effect of pre-processing via sonciation in comparison to plain stirring. These results also suggest that nanoclay platelets modified with alkylammonium groups with one tallow tail Cloisite ® 10A and Cloisite ® 30B, allow better dispersion and penetration of the polymer within the basal spacing of the nanoclays. Once the decrease in gas permeability was confirmed, the next challenge was to study and evaluate the performance of the polyurethane/clay nanocomposites barrier membranes in the determination of diffusivity coefficients for volatile organic compounds (VOCs). This was achieved via gravimetric sorption characterization. This method allowed for characterization of the sorption and desorption phenomena of VOC in barrier membranes. Barrier membranes pretreated with sonication demonstrated lower diffusivity coefficients than those only treated with stirring. At high clay loadings, 50 wt% of nanoclay in the polymer, the decrease in diffusivity coefficients for VOCs such as butanol and toluene, was found to be one order of magnitude. Other VOCs such as decane and tetradecane also showed a significant decrease in diffusivity coefficient. The results for VOC sorption studies suggest that there is some variability. In order to enhance the exfoliation of the clay, we decided to examine in situ polymerization of poly (n-butyl methacrylate) in the presence of nanoclay. In this study the clay wt% was kept at a low concentration of 1-5 wt%. The surface modification of natural montmorillonite, Cloisite ® Na+, was achieved via ion exchange, and the effect of pre-processing was also explored. The modification rendered a tethered group on the surface of the clay that was able to react with the monomer/oligomer chains and thus expand and exfoliate the clay platelets. Gas permeation data suggest that sonication also produced better barrier properties than its counterpart stirring. XRD diffractograms also confirmed exfoliation of the clay platelets in the poly (n-butyl methacrylate) polymer matrix. Thermogravimetric analysis (TGA) suggested that exfoliation of the clay platelets led to improved thermal stability by increasing the decomposition temperature of the membranes. A small increase in Tg also suggested restricted segmental chain motion within the clay platelets. Overall gas permeation decreased even at low clay content. Phenomenological models such as those of Cussler and Nielsen were used to model the experimental permeation results. These models suggest that although the aspect ratio of the clay platelets is within the specifications provided by the manufacturer, it does not reflect the ideal behavior of the models. The last step of this work was to achieve exfoliation of the modified nanoclay platelets via emulsion polymerization of poly (n-butyl methacrylate). The clay concentration in the emulsion was kept the same as in the in situ polymerization. DLS results suggest a uniform distribution of the polymer/clay nanocomposites particles in the emulsion. Permeation data indicated higher permeation values than the in situ method of synthesis of the nanocomposite membranes. This led us to explore the use of glassy co-polymer of poly(n-butyl methacrylate)-poly(methyl methacrylate) as the matrix. The addition of a more glassy component in the polymer matrix led to improved barrier properties of the nanocomposite membranes. As expected, the copolymer had a higher Tg than the PMMA polymer. Analysis via phenomenological models, also suggested that the chemistry of the co-polymer played an important role in decreasing gas permeability within the polymer/clay nanocomposite membranes, although the effect of the glassy component in the matrix was not quantified by the phenomenological models. / Ph. D.

The chicken yolk sac and small intestine are connected through the yolk stalk and share many biological similarities. During the embryonic stage, the extra-embryonic yolk sac helps the embryo to absorb nutrients primarily in the last two weeks of incubation. The chicken yolk sac physically moves yolk contents from the yolk sac to the small intestine at the end of embryogenesis. This is the time when the small intestine replaces the yolk sac in assimilating nutrients for the embryo and later for the posthatch chicken. Additionally, both chicken small intestinal epithelia and the yolk sac secrete beta defensins for promoting intestinal health. Since there are heterogeneous cell types along the mammalian intestinal villus, which are derived from the intestinal stem cells in the crypts, we investigated if cells of the chicken yolk sac and small intestine have the same ontogeny as mammalian intestinal epithelial cells. In this dissertation, we mainly focused on the spatial expression of nutrient transporters (PepT1 and SGLT1), intestinal stem cell markers (Lgr5 and Olfm4), and avian beta defensins in the chicken yolk sac and small intestine during the embryonic and early posthatch stages. RNAscope in situ hybridization was used to identify the distribution of cells expressing PepT1 mRNA in both the chicken yolk sac and small intestine. PepT1 mRNA was found to be expressed by epithelial cells in both the yolk sac and small intestine. In the yolk sac, PepT1 mRNA was uniformly distributed in each endodermal epithelial cell along the villus-like structure. The pattern of PepT1 mRNA expression observed in the chicken yolk sac during the last 10 days of incubation revealed that PepT1 mRNA was increased from e11 to e13, and decreased from e15 to day of hatch. The peak of PepT1 mRNA expression was between e13 and e15, when the yolk sac reaches maximum absorptive area and the growth of the chicken embryo is at its fastest rate. However, the expression of PepT1 mRNA in the intestine was only detected in columnar enterocytes along the villus and not in goblet cells or cells in the crypts. The immunofluorescence assay confirmed that PepT1 protein was located at the brush border membrane of the enterocytes and that protein expression of PepT1 was restricted to the intestinal epithelial cells from approximately the middle to the tip of the villus. In order to identify intestinal stem cells, we used the known mammalian stem cell markers, Lgr5 and Olfm4. Both Lgr5 and Olfm4 are specifically expressed by cells in the chicken intestinal crypts, suggesting that they can be used as biomarkers for chicken intestinal stem cells. Dual labelling of PepT1 and Olfm4 mRNA on the same chicken intestinal sample revealed that there was a gap between PepT1-expressing enterocytes and Olfm4-expressing intestinal stem cells. The cells in this gap were presumably transit amplifying (TA) cells. Additionally, we also found that the TA cell zone along the intestinal villus was reduced during chicken growth. This TA cell population could be clearly detected at day of hatch and d1 posthatch but not later. The expression of SGLT1 mRNA was localized to yolk sac endodermal epithelial cells and showed a sharp increase at the end of incubation. This increase of SGLT1 mRNA coincided with the increase in glucose in the yolk, indicating that the chicken embryo needs glucose as energy for hatching. The mRNA expression profiles of various avian beta defensins have been examined by qPCR and in situ hybridization to investigate the immune function of the yolk sac and small intestine. We found that AvBD10 mRNA showed the highest expression level in the yolk sac and was expressed predominantly in the yolk sac endodermal epithelial cells. Additionally, the expression of AvBD10 mRNA showed a development-specific pattern, which increased from e9 to e11, and decreased from e13 towards day of hatch. The expression patterns of AvBD1, 2, and 7 mRNA were similar to each other. These three genes were found to be expressed by chicken heterophils distributed in the yolk sac blood islands and small intestinal blood vessels. Only a subset of heterophils, which might be activated, were able to express AvBD1, 2, and 7 mRNA. In the intestine, the expression of AvBD10 mRNA was localized to cells along the villus at e19 and day of hatch, but later to only a few cells located above the intestinal crypts. In summary, the endodermal epithelial cells are responsible for the absorptive and immune functions of the chicken yolk sac. The yolk sac mesoderm is critical for embryonic hematopoiesis and innate immunity. The chicken small intestinal epithelial cells are derived from the intestinal stem cells in the crypts. These epithelial cells have different cell types, which are functioning to absorb nutrients and secrete antimicrobial peptides. / Ph. D. / The chicken yolk sac and small intestine are connected to each other and share many biological similarities. Both chicken small intestinal and yolk sac epithelia play critical roles for nutrient absorption and immune defense. In this dissertation, the mRNA for nutrient transporters such as the peptide transporter, PepT1 and the sodium-glucose co-transporter, SGLT1 were found to be expressed by absorptive epithelial cells in both the yolk sac and small intestine. Additionally, both intestinal and yolk sac epithelial cells expressed avian beta defensins (AvBDs), which are important chicken host defense peptides. In the small intestine, there are a number of differentiated cell types that originate from stem cells in the crypt that express the known mammalian stem cell markers, Olfm4 and Lgr5 mRNA. However, in the chicken yolk sac, only the stem cell marker Lgr5 mRNA was expressed by endothelial cells. In summary, the yolk sac epithelial cells are responsible for the absorptive and immune functions for the embryonic stage. The chicken small intestinal epithelial cells are derived from the intestinal stem cells in the crypts. These epithelial cells have different cell types, which function to absorb nutrients and secrete antimicrobial peptides.

No description available.

Corrosion of iron and copper pipes can produce leaks and loss of efficiency in the water distribution system, elevate levels of contaminants at the tap, and cost billions of dollars annually in pipe replacement or rehabilitation. In situ pipe rehabilitation using cement mortar, polyurethane, and epoxy is a commonly employed method of dealing with aging yet structurally sound pipes because it is less expensive and less invasive than replacing pipe infrastructure. Although epoxy has been shown to be an effective solution to pipe corrosion, little research has been conducted regarding its impact on a comprehensive list of water quality parameters. This research addressed that gap in the literature by conducting short-term immersion tests in which new epoxy linings were exposed to reference tap waters containing one of three disinfectant treatments: no disinfectant, free chlorine, or chloramines. As a comparison, an aged epoxy-lined field sample was also tested. Water exposed to the liners under stagnant conditions was analyzed for the following water quality parameters: pH, ammonia, alkalinity, hardness, metals, disinfectant consumption, total organic carbon (TOC), semi-volatile organic compounds (SVOCs), disinfectant byproduct (DBP) formation, and odor. Results of the study showed relatively low impacts on water quality, as all USEPA drinking water regulations were met. Impacts were highest during the first 24 hour exposure period during which time significant disinfectant consumption was shown (> 90% free chlorine consumed, 13% chloramines consumed), high TOC was leached (2.6-6.2 mg/L), trihalomethanes and haloacetic acids were formed (both < 15 ug/L), Bisphenol-A, an endocrine disrupter, was detected (< 35 ug/L), and odor was reported by panelists at a moderate intensity and described as sweet/chemical/burning/chlorinous. Impacts were much less after the initial 24 hours, although odor remained noticeable throughout the 30 day study. Overall, water quality impacts were greatest in chlorinated waters and both new and aged epoxy showed slight differences in results. / Master of Science

Introduction : L'hybridation in situ en fluorescence (FISH) est souvent utilisée pour l'étude des populations microbiennes hétérogènes. Toutefois, cette méthode n'est pas adaptée pour détecter des bactéries sous forme de spores, vue leur grande résistance aux traitements de perméabilisation conventionnels. Cependant, les bactéries formant des spores ont un rôle écologique, économique et médical important. Le but de cette étude est de développer des protocoles de perméabilisation rapides afin de détecter des spores de Bacillus par FISH. Méthodes : Un protocole pour les spores de B. megaterium a été adapté et optimisé pour les modèles choisis (B. cereus, B. atrophaeus et B. megaterium). Des sondes universelles et spécifiques ont été utilisées lors de l'hybridation. L'effet du traitement de perméabilisation a été évalué à Laide de la microscopie électronique à transmission et à balayage. Par la suite, les protocoles ont été adaptés pour permettre l'entrée de grosses molécules (comme la streptavidine) afin de permettre l'utilisation de méthode d'amplification de signal. Résultats : Avec les protocoles développés, les spores de Bacillus ont été détectées avec des sondes par FISH. La microscopie électronique à balayage a permis d'observer les différences de surface entre les spores traitées et non traitées. Des spores de Bacillus ont été détectées avec les protocoles adaptés pour la streptavidine. Conclusion : Des protocoles efficaces ont été développés pour détecter rapidement des spores de Bacillus par FISH. En utilisant cette technique, il est possible de détecter des spores de Bacillus en moins d'une heure.

Legal Regulation of Animal Protection Ex Situ in USA and the Czech Republic This thesis aims to compare the legislation of animal protection ex situ in the Czech Republic and USA. The content is systematically divided in two sections. First section focuses on different law systems, which is international, national and local legislation. Second section explains the law used in different institutions that provide ex situ protection, such as zoos, aquariums, wildlife sanctuaries, etc. The thesis describes different legal approaches and uses several examples for a practical comparison. In its conclusion the thesis sums up the negatives and positives of each legislation and their overall quality and efficiency. The thesis also points out some of the desirable solutions to some current problems and a possible development in the area.

15 samples of gem opals were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS). For this study were selected the most representative samples from Slovakia, Australia, Peru, Ethiopia, Mexico, USA and the Czech Republic. These samples were obtained from private collections. The study focuses on the geochemical relationships between various forms of opal originating from igneous and sedimentary environments based on the results from LA ICP-MS and ICP-MS. The major and trace element compositions are unique for each studied opal locality and important for understanding numerous aspects of opal formation. Major element analysis shows that opals are essentially pure SiO2 (77 - 92 wt. %). Al, Fe, Ca, K, Na and Mg are the main elemental impurities. The concentrations of the trace elements vary strongly depending on the opal locality. Differences were found, e.g., in the concentrations of REE and some refractory elements, which might be indicative for determining the provenance of opals. Many studies have been published explaining the origin of luminescence, microstructures and the thermal properties of opals. However, there are very few comprehensive studies comparing gem opals from the most important historical and...

La cuisson est un procédé universel de transformation de la matière première carnée en aliment. Le chauffage de la matrice musculaire conditionne diverses qualités organoleptiques, technologiques, sanitaires et nutritionnelles des viandes cuites. La cuisson étant appliquée de plus en plus fréquemment en conditions industrielles standardisées, il est pertinent de modéliser certains mécanismes clés dans le déterminisme de ces qualités afin d’optimiser le procédé. Pour cela, une démarche expérimentale originale a été mise en place fondée sur une analyse quantitative, locale, dynamique et in situ de la viande pendant la cuisson. Cette démarche ne fait pas d’hypothèse réductionniste en étudiant un échantillon intact à l’échelle de l’aliment consommé, ni d’hypothèse simplificatrice en prenant en compte les variations spatiales de la température dans l’échantillon. Elle s’appuie sur des développements originaux en imagerie par résonance magnétique nucléaire à haut champ et en traitement d’images pour cartographier la déformation et la quantité d’eau. Des modèles robustes liant température, déformation et quantité d’eau ont été obtenus pour des muscles de teneur variable en tissu conjonctif. Les résultats montrent principalement une augmentation de la déformation avec la température en plusieurs phases dont les caractéristiques dépendent de la composition du muscle, et une diminution de la quantité d’eau avec la température. Tous ces résultats sont discutés et interprétés au regard du comportement à la température des différents composants du muscle. Ce travail montre d’abord que l’imagerie dynamique, quantitative et multiparamétrique permet de décrypter des mécanismes intervenant lors de la cuisson des viandes sans établir des hypothèses réductrices lors de l’interprétation de ces phénomènes. Elle a conduit de plus, à des développements méthodologiques applicables à d’autres champs et ouvre la voie à d’autres investigations dans le domaine de l’optimisation qualitative des produits carnés transformés. / Cooking is a general process which transforms the meat raw material into food. The heating of muscle matrix influences different organoleptic, industrial, health and nutritional qualities of cooked meat. Cooking being applied more and more frequently in standardized and industrial conditions, it makes sense to model some key mechanisms which determine the latter qualities in order to optimize the process. For this purpose, an original experimental approach has been developed based on a quantitative, local, dynamic and in situ analysis of the meat during cooking. This approach is not based on any reductionist hypothesis by studying an intact sample at the scale of the consumed food, nor by the simplifying assumption of taking into account the spatial variations of temperature in the sample. It is based on original developments in nuclear magnetic resonance imaging at high-field and on image processing in order to map deformation and the water content. Robust models linking temperature, deformation and water content were obtained for muscles differing from their content in connective tissue. The results mainly show a deformation increase with the temperature in several phases whose characteristics depend on the muscle composition, and a decrease in the water content with temperature. All these results are discussed and interpreted thanks to the temperature behavior of the various muscle components. This work first shows that quantitative, multi-parametric and dynamic imaging can decipher the mechanisms involved during meat cooking, without formulating simplifying assumptions in the interpretation of these phenomena. Furthermore, it has led to methodological developments applicable to other fields and paves the way for further investigations in the field of quality optimization of processed meat products.

Les nanostructures ont des propriétés mécaniques qui diffèrent de celles des matériaux massifs. La compréhension des propriétés mécaniques aux échelles nanométriques requièrent la mise en place d’essais mécaniques combinés à des observations structurales. Au cours de cette thèse nous avons développé un microscope à force atomique (AFM) dédié permettant de solliciter mécaniquement un nano-objet unique sur une ligne de lumière synchrotron. Les possibilités offertes par cette nouvelle approche expérimentale sont démontrées sur deux exemples de sollicitation mécanique in situ: (i) la nanoindentation in situ de cristaux d’or combinée à la diffraction cohérente des rayons X; (ii) la flexion trois points de nanofils d’or associée à la micro-diffraction de Laue. Ces expériences permettent d'accéder au comportement élastique ainsi qu’au comportement plastique du nanomatériau et permettent de déterminer la limite d'élasticité et le type de défauts induits par le chargement mécanique. / Nanostructures were found to exhibit different mechanical properties compared to their bulk counterpart. For obtaining further insight into the mechanical behaviour on the nanoscale, mechanical tests are combined with observation techniques allowing for monitoring the structural evolution. Within this thesis a special atomic force microscope has been developed which is compatible with different X-ray diffraction techniques at synchrotron sources for in situ mechanical testing on single nano-objects. The great potential of the new experimental approach is demonstrated on two kinds of in situ mechanical tests: (i) in situ nano-indentation on Au crystals with coherent X-ray diffraction. (ii) In situ three point bending tests on Au nanowires with μLaue diffraction. These experiments give access to the elastic as well as the plastic behavior of the nanomaterial and allows for determining the elastic limit and the type of defects induced by the mechanical loading.