L’objectif de cette thèse a consisté en la synthèse d’un polymère à empreinte moléculaire (MIP) permettant l’extraction du phosmet, un pesticide organophosphoré largement utilisé en oléiculture. La recherche du monomère fonctionnel (MF) disposant de la meilleure capacité à interagir de manière non-covalente avec le phosmet en présence du solvant porogène le plus approprié a été réalisée pour la toute première fois au moyen d’un capteur à acétylcholinestérase. Cette stratégie innovante a permis une meilleure compréhension des mécanismes cinétiques à l’œuvre lors de l’interaction MF-molécule cible. De par l’importance de son rôle dans la détermination de la structure d’un MIP, le choix d’un agent réticulant aux caractéristiques physico-chimiques adéquates a permis de sélectionner le meilleur MIP en s’appuyant sur l’étude des isothermes d’adsorption selon les modèles de Freundlich et Langmuir. La procédure d’extraction du phosmet selon la procédure MISPE (Molecularly Imprinted Solid Phase Extraction) a été effectuée par le biais d’une cartouche SPE dont la capacité a été évaluée à partir d’une solution standard. La validation du choix des réactifs de MIP sélectionnés a été confortée par la réalisation d’une expérience de réactivité croisée appliquée à une molécule analogue au phosmet. L’extraction du phosmet de l’huile d’olive a pu être effectuée avec succès selon un protocole d’extraction en flux inverse optimisé. Cette étude ouvre ainsi la voie à la recherche de nouvelles interactions MFs-molécules cibles au moyen de biocapteurs enzymatiques inhibant des composés toxiques tels que les herbicides, fongicides et autres pesticides. / The objective of this thesis has been the synthesis of a molecularly imprinted polymer (MIP) for the extraction of phosmet, an organophosphorus pesticide widely used in olive growing. The search for the functional monomer (FM) having the best ability to interact non-covalently with phosmet in the presence of the most suitable pore-forming solvent was carried out for the first time by means of an acetylcholinesterase sensor. This innovative strategy allowed us to better understand the kinetic mechanisms of FM-template interaction. Because of the importance of its role in determining the structure of a MIP, the selection of a crosslinking agent with adequate physicochemical characteristics made it possible to select the best MIP, whose adsorption isotherms were studied according to Freundlich and Langmuir models. Extraction of phosmet using a Molecularly Imprinted Solid Phase Extraction (MISPE) procedure was carried out via an SPE cartridge, whose capacity was evaluated from a standard solution. The choice of reagents and experimental conditions were validated by carrying out selectivity assays using another organophosphorus insecticide. Extraction of phosmet from olive oil was successfully carried out according to an optimized reverse flow extraction protocol. This work opens new opportunities for studying new FM-template interactions by means of enzymatic biosensors capable of detecting other inhibitors such as herbicides, fungicides and other pesticides.

Cette recherche vise à analyser et à identifier, par des essais, le comportement au fluage d'une argile de type kaolinite sous un état de contraintes triaxial. Une investigation fine de l’état microstructural, avant et après fluage, a par ailleurs été réalisée. Les résultats macroscopiques ont permis de constater que des phénomènes de dilatance et de contractante s’amplifient pendant le fluage. Les résultats montrent également que la position, sur le plan des contraintes (p'-q), du niveau de contrainte vis-à-vis des différents domaines volumétriques, contrôle le développement de la déformation au fluage et du taux de déformation. Les résultats de MEB ont montré que l'évolution microstructurale de l'argile, après le chargement mécanique, dépend fortement de l'histoire du chargement. / The objective of this research is to analyze the creep behavior of a typical clay along triaxial tests, moreover, to analyze the microstructural mechanisms of creep. Analysis on the macroscopic results ascertained that both dilatancy and contractancy phenomena could occur during creep. The magnitude of the dilatancy/contractancy during creep was guided by the test conditions: stress level and the over consolidation ratio, which specifically governed the direction of the volumetric strain variations. The results of SEM indicated that the microstructural evolution of the clay after the mechanical loading depend on the stress history. Afterwards, the structural evolution in creep phase depends on the structural pattern developed in monotonic loading

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This research is inserted in the Biomathematics Research Group of the Programa de Pós-Graduação em Matemática of the Universidade Federal de Santa Maria-RS. It consists in the study of a discrete model for a prey-predator-insecticide system based on the Coupled Map Lattice as basic tool for its formulation. Due to the serious problems that crop pests represent to agriculture, we aproached the Integrated Pest Management (IPM), which is a pest control system that seeks to preserve and enhance the natural mortality factors of pests by integrated use of control methods selected based on technical, economic, ecological and sociological parameters. The objective of this work is to build a model as simple as possible to study the effects of different pests management strategies. These strategies are divided into different treatments which take into account the number of measurements of pest population, establishing control levels (CL) and different control measures (pesticide and biological control). For comparison and to point where the treatment is more efficient to compute the total density of the pest population without any control measure and when each treatment is applied over a certain period of time. The difference between these values is converted into a decreasing percentage of the population of pests. The same is done to obtain the percentage decrease in the number of treated sites. It was found that the sooner you apply the insecticide in the system, the more effective the treatment. Furthermore, it was observed that the presence of predators (biological control) decreases the amount of treated sites and, in some instances, is less effective in controlling pest. / Esta pesquisa está inserida na Linha de Pesquisa Biomatemática, do Programa de Pós-Graduação em Matemática da Universidade Federal de Santa Maria-RS. Configura-se como um estudo sobre um modelo discreto para um sistema praga-predador-inseticida tendo como ferramenta básica para sua formulação a Rede de Mapas Acoplados. Devido aos sérios problemas que pragas de lavoura representam para agricultura, abordou-se o Manejo Integrado de Pragas (MIP), que é um sistema de controle de pragas que busca preservar e aumentar os fatores de mortalidade natural de pragas pelo uso integrado de métodos de controle selecionados com base em parâmetros técnicos, econômicos, ecológicos e sociológicos. O objetivo deste trabalho é construir um modelo tão simples quanto possível, para estudar as consequências de diferentes estratégias de manejos de pragas. Essas estratégias são divididas em tratamentos diferentes nos quais leva-se em consideração o número de medições da população de pragas, estabelecimento de níveis de controle (NC) e diferentes medidas de controle aplicadas (inseticida e controle biológico). Para comparar e apontar qual dos tratamentos é mais eficiente, computou-se a densidade total da população de pragas sem nenhuma medida de controle e quando cada um dos tratamentos é aplicado ao longo de um determinado período de tempo. A diferença entre esses valores é convertida em um percentual de decrescimento da população de pragas. O mesmo é feito para se obter o percentual de decrescimento do número de sítios tratados. Foi possível constatar que quanto mais cedo se aplica o inseticida no sistema, mais efetivo é o tratamento. Além disso, observou-se que a presença dos predadores (controle biológico) diminui a quantidade de sítios tratados e, em alguns momentos, é menos eficiente no controle da praga.

Au cours des dernières années, les matériaux énergétiques, tels que le 2,4,6-trinitrotoluène (TNT) et le 1,3,5-trinitro perhydro-1,3,5-triazine (RDX), ont été utilisés lors des activités d’entrainement militaire, ayant un impact potentiel sur l’environnement, les bases militaires, la population environnante, la faune et la flore. Sur les champs de tir, les sols à proximité des cibles et autour des positions de tir nécessitent une surveillance particulière, puisqu’il est possible de trouver une importante quantité de résidus d’explosif qui peuvent être transportés vers les eaux de surface et des eaux souterraines avec les précipitations. Toutefois, la procédure actuelle pour détecter des matériaux énergétiques dans l'eau naturelle est complexe, longue, nécessite un personnel hautement spécialisé et augmente le risque de contamination croisée. Par conséquent, il est difficile d'assurer un contrôle rapide et continu des contaminants. En fait, l'objectif des travaux présentés dans ce mémoire est de développer une technique pour identifier et quantifier les explosifs et leurs produits de dégradation dans les eaux naturelles. En outre, ce test doit être in situ, en continu, peu coûteux et rapide. La résonance des plasmons de surface (SPR) a été donc utilisée pour quantifier les matériaux énergétiques. Une matrice de bis-aniline réticulée avec des nanoparticules d’or (AuNPs) est utilisée en tant que polymère à empreinte moléculaire (MIP) sur le film d'or pour capturer sélectivement le composé d’intérêt. L'association de la molécule d’intérêt, tel que le TNT ou RDX, au MIP par interactions π-donneur-accepteur permet la détection d'explosifs suite aux changements d’indice de réfraction sur la sonde. Le couplage entre les plasmons des AuNPs et de la couche d'or peut également augmenter les signaux SPR. Le test optimisé a ensuite été utilisé sur une base militaire canadienne. L'utilisation de cet essai à base de MIP fournit un outil pour l'extraction et la pré-concentration de TNT ou RDX à la surface d’une sonde SPR et permet leur détection en continu de faibles concentrations dans les eaux naturelles. / Over the last few years, energetic materials such as 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) have been used and show a probable environmental impact on military bases, the surrounding population, fauna and flora, caused by military training involving munitions. On shooting ranges, soils near the firing positions and around targets require special monitoring, since the quantities of explosives residues found can be significant, and these compounds can be transported to surface water and groundwater by precipitation. However, the current procedure to detect energetic materials in natural water is complex, long and poorly adapted to. These operations require highly specialized personnel and increase the risk of cross contamination. Therefore, it is difficult to ensure a fast and continuous monitoring of the contaminants. Here, the objective is to develop a technique for identifying and quantifying explosives and their degradation products in natural water. Also, this test has to be in-situ, inexpensive and fast. Surface plasmon resonance (SPR) has been proposed to probe energetic materials. A bis-aniline-cross-linked gold nanoparticles (AuNPs) matrix is used as a molecular imprinted polymer (MIP) on gold film to selectively capture the target compound. The association of the target such as TNT or RDX to the MIP with π-donor-acceptor interactions have allow the detection of explosives by following SPR refractive changes. Plasmon coupling effects between the AuNPs and the gold film could also increase the SPR signals. The optimal sensor was then used on site to detect RDX in underground water of a Canadian military base. The utilisation of MIP based assay will provide a tool for the extraction and pre-concentration of TNT or RDX on the detector’s surface and will allow the detection of lower concentrations in natural water.

Cette thèse décrit l'état de l'art des sondes et nanoparticules fluorescents traditionnels utilisés en imagerie de fluorescence ainsi que le développement de nouveaux nanomatériaux à base de polymère à empreinte moléculaire, aussi dénommé ‘anticorps plastique’, pour le ciblage et la bioimagerie. En biologie et en médecine, il y a un besoin constant de diagnostiquer diverses maladies pour leur éventuel traitement et prévention. Une distribution anormale et un taux élévé de glycosylation (e.g. acides hyaluronique et sialique) à la surface ou dans les cellules sont indicateurs d’une infection ou d’un cancer. Généralement, l’imagerie par fluorescence permet de visualiser, localiser et quantifier les biomarqueurs de pathologie mais à l’heure actuelle, il n’existe pas d’outil analytique fiable pour cibler spécifiquement les molécules de glycosylation car les anticorps et les lectines vendus dans le commerce ont une faible affinité et sélectivité vis-à-vis de ces cibles. Dans ce contexte, les polymères à empreintes moléculaires (MIPs) pourraient apporter une solution. Les MIPs sont des récepteurs synthétiques possédant des affinités et sélectivités comparables à ceux des anticorps, mais exhibant une stabilité physique, thermique et chimique bien plus accrue. De plus, leur fabrication est peu coûteuse et ne nécessite pas de tuer des animaux comme pour l’obtention des anticorps biologiques. Dans cette thèse, nous avons optimisé et synthétisé des MIPs biocompatibles pour leur utilisation en bioimagerie afin de détecter et quantifier l’acide hyaluronique et l’acide sialique sur les cellules et les tissus de peau humaine. L’acide glucuronique, une composante de l’acide hyaluronique et l’acide N-acétylneuraminique, l’acide sialique le plus commun, ont été utilisés comme molécules ‘patron’, générant des MIPs très sélectifs envers leur cible en milieu aqueux. Deux types de nanoparticules de MIPs fluorescents ont été synthétisés: (1) en incorporant un colorant rhodamine polymérisable dans la solution de pré-polymérisation et (2) en encapsulant des boîtes quantiques InP/ZnS générant ainsi des MIPs de type cœur-coquille. Pour cela, nous avons adopté une stratégie innovante qui consiste à synthétiser les coquilles de MIPs directement autour des boîtes quantiques en utilisant l’énergie de l’onde fluorescente émise par l’excitation des points quantiques, pour initier la polymérisation. Un protocole d'immunocoloration standard a ensuite été optimisé afin d’imager des kératinocytes humains fixés et vivants ainsi que des tissus de peau, par microscopie à épifluorescence et confocale. Les résultats étaient similaires à ceux obtenus par la méthode de référence utilisant une protéine biotinylée reconnaissant l'acide hyaluronique. L'imagerie multiplex en combinant deux MIPs couplés à deux couleurs de boîtes quantiques et l’imagerie des cellules cancéreuses ont également été démontrées. Bien que les MIPs n’étaient pas cytotoxiques aux concentrations utilisées pour la bioimagerie, la toxicité des différentes composantes du MIP pourrait être un frein à leur utilisation dans le domaine biomédical. Afin de rendre ces MIPs plus ‘inoffensifs’, nous avons supprimé l’amorceur de polymérisation, une molécule considérée comme toxique. Les MIPs ont été synthétisés en employant des monomères qui s’auto-initient sous l’effet de l’UV ou de la chaleur. La spécificité et la sélectivité des MIPs obtenus étaient similaires à ceux préparés avec des amorceurs. En conclusion, cette thèse décrit la première utilisation des MIPs comme anticorps synthétique pour la bioimagerie de fluorescence. Ce travail ouvre la voie à de nouvelles applications en détection, diagnostique et thérapie par des MIPs. / This thesis describes the state of the art in nanomaterials-based targeted bioimaging and introduces molecularly imprinted polymers, also termed ‘plastic antibodies’ as novel biorecognition agents for labeling and imaging of cells and tissues. In fundamental biology and medical diagnostics, there is a constant need to localize and quantify specific molecular targets. Abnormal glycosylation levels or distributions of hyaluronan or sialic acids on cells are indicators of infection or malignancy. In general, bioimaging with fluorescent probes enables the localization and qualitative or quantitative determination of these pathological biomarkers. However, no reliable tools for the recognition of glycosylation sites on proteins exist, because the commercially available antibodies or lectins have poor affinity and selectivity for these targets. In this context, tailor-made molecularly imprinted polymers (MIPs) are promising synthetic receptor materials since they present a series of advantages over their natural counterparts such as the ease and low cost of preparation and their physical and chemical stability. Thus, MIPs could provide a robust and specific imaging tool for revealing the location/distribution, time of appearance and structure of glycosylation sites on/in cells, which would lead to a better insight of the tremendously diverse biological processes in which these molecules are involved. Herein, we describe the synthesis of water-compatible MIPs for the molecular imaging of hyaluronan and sialylation sites on cells and tissues. Since molecular imprinting of entire biomacromolecules like oligosaccharides is challenging, we opted for what is commonly called the ‘epitope approach’, which was inspired by nature. The monosaccharides, glucuronic acid and N-acetylneuraminic acid were imprinted, and the resulting MIPs were able to bind these molecules when present and accessible on the terminal unit of hyaluronan and sialylation sites. Fluorescent MIPs were synthesized as rhodamine-labeled nanoparticles and as MIP-coated InP/ZnS core-shell quantum dot (QD) particles. For the coating of the QDs, a novel versatile solubilization and functionalization strategy was proposed, which consists of creating polymer shells directly on QDs by photopolymerization using the particles as individual internal light sources. A standard immunostaining protocol was then successfully adapted for the application of the fluorescently labeled MIPs to image fixed and living human keratinocytes and skin tissues, by epifluorescence and confocal fluorescence microscopy. The results were comparable to those obtained with a reference method where staining was done with a biotinylated hyaluronic acid binding protein. Multiplexed and cancer cell imaging were also performed, demonstrating the potential of molecularly imprinted polymers as a versatile biolabeling and bioimaging tool. Although the MIPs were not cytotoxic at the concentrations used for bioimaging, in order to render them generally applicable in biomedicine, where toxicity of the polymerization precursors is a matter of concern, we suppressed the initiator, a toxic chemical. Initiator-free MIPs were thus synthesized by using monomers that can self-initiate under UV irradiation or heat. The specificity and selectivity of the obtained MIPs were as good as the ones prepared with initiators. In conclusion, we have demonstrated for the first time the great potential of MIPs as synthetic antibody mimics for bioimaging. The possibility to associate other functionalities such as QDs and additionally attach drugs to the same material appears rather straightforward due to the synthetic polymeric nature of MIPs, which paves the way to new potential applications in theranostics.

The synthesis of materials with molecular recognition properties has become a topic of great technological and scientific interest. Molecular imprinting is one of the most effective strategies in preparing highly selective synthetic receptors. The technique of molecular imprinting involves the copolymerization of functional and cross-linking monomers in the presence of a molecular template. Following polymerization and subsequent removal of the template, the molecularly imprinted polymer (MIP) retains a “molecular memory” of the template. During rebinding, the resultant polymer shows higher affinity and selectivity towards the molecular template when compared to other structural analogs. Ease of preparation and high thermal and chemical stability of this class of materials offers a broad range of potential applications. Promising areas of application include separation, chromatography, catalysis, sensors, antibody mimics, and drug delivery etc. The thesis entitled “Molecularly Imprinted Polymers based on Fluorescent and Template binding Cross-linker” deals with the design and synthesis of several molecularly imprinted polymers (MIPs) using different functional and cross-linking monomers, the main focus being use of preformed template-monomer complex, use of fluorescent cross-linker and development of functional group containing cross-linker. Chapter 1: An Introduction to Molecularly Imprinted Polymers. The first chapter provides an introduction to the field of molecularly imprinted polymers. It presents an overview of molecular imprinting process including a brief history of its discovery and its evolution to the present form. This chapter further elaborates on the principle of molecular imprinting with an emphasis on different parameters that directly affect their performance. It also provides a brief review of the applications of molecularly imprinted polymers. Chapter 2: Highly Cross-linked Metal Ion Imprinted Polymers. The second chapter deals with the synthesis of series of highly cross-linked metal-ion imprinted polymers. The process of metal ion-imprinting usually involves carrying out the polymerization and cross-linking directly in presence of the appropriate metal ion. In the present study, chemical-immobilization method was adopted which involves the use of preformed metal complexes with polymerizable group for the imprinting. Acrylate complexes of various metal-ions, such as Cu2+, Zn2+, Co2+, Ni2+, Pb2+ and Cr3+, were synthesized prior to polymerization. These pre-assembled complexes were then used to prepare MIPs, in the anticipation that this would lead to enhanced selectivity. Ethyleneglycol dimethacrylate (EGDMA) was used as the cross-linking monomer. As a control, the respective non-imprinted polymers (NIPs) were also made in absence of the template metal ion. Following polymerization, the template metal ion was extracted from the resultant metal ion-imprinted polymer. The selectivity of the metal ion-imprinted polymers was examined by a batch process using analytical tools, such as, Atomic Absorption Spectroscopy (AAS) and Inductively Coupled Plasma Spectroscopy (ICP). The spectroscopic studies revealed significant selectivity of all the MIPs towards the template metal ion. Among all six metal ion-imprinted polymers, Pb2+ and Cr3+ ion-imprinted polymer showed remarkable selectivity, followed by Cu2+ and Zn2+ ion-imprinted polymers. The Co2+ and Ni2+ ion-imprinted polymers exhibited comparatively poor selectivity. Representative plots depicting the selectivity exhibited by Pb2+ and Cr3+ ion-imprinted polymers are shown in Figure 1. These observations were rationalized based on the size and geometric preferences imposed by the imprinted site on the ion that binds to it. Figure 1. Selectivity study for (a) Pb2+ ion-imprinted polymer, (b) Cr3+ ion-imprinted polymer. Chapter 3. Molecularly Imprinted Fluorescent Chemosensor for Copper (II). Cu(II) is a source of important pollutant and therefore, the development of sensors that can detect Cu(II) selectively as well as remove Cu(II) from contaminated samples is an important objective. The use of molecular imprinting technique is an appealing approach in this regard. For this, a fluorophore containing cross-linker, namely 9,10-bis-(acryloyloxymethyl)anthracene (BAMA) was synthesized. This fluorescent cross-linker was used along with the standard cross-linker, EGDMA, for preparing Cu2+ ion-imprinted polymer. The complex of copper methacrylate (Cu-MAA) was prepared prior to polymerization used for the preparation of MIP. The resultant imprinted polymer exhibited quenching of the fluorescence in presence of Cu2+ ion, both in organic and aqueous medium. The efficiency of quenching of NIP (prepared in absence of Cu2+ ion) was significantly lower than that of MIP. A typical stack spectra showing the quenching process, along with a comparison of the quenching efficiency of MIP and NIP is shown in Figure 2. The imprinted polymers showed significant selectivity over other non-template metal ions, thereby reaffirming the importance of the imprinting process. The sensitivity of the fluorescence detection could be enhanced by increasing the level of the fluorophore incorporation. The increased sensitivity in detecting Cu2+ ion, demonstrated by the MIP suggests that a statistically random incorporation of the fluorophore into MIP matrices could be a useful approach for imparting a sensing element to MIPs. Figure 2. Fluorescence spectra of the (a) imprinted (MIP-1) and (b) non-imprinted (NIP-1) polymers in the presence of various concentration of Cu(OAc)2 in methanol. (c) Comparison of quenching efficiency of MIP-1 and NIP-1. Data were collected 3 h after addition of copper solution. I0 and I are the fluorescence intensities at 399 nm of the polymers in the absence presence of copper respectively. Two individual runs are presented in (c). Chapter 4. Molecularly Imprinted Turn-Off-On Sensor. This chapter describes the design and synthesis of molecularly imprinted fluorescent turn-off-on sensor utilizing the same fluorescent cross-linker, BAMA. Combining the process of fluorescence resonance energy transfer (FRET) with molecular imprinting technique, a novel turn-off-on sensor was developed. A molecularly imprinted polymer was prepared using a fluorescent template Coumarin-30 (C-30). C-30 was chosen as the template to ensure a significant overlap of the emission spectra of BAMA and the absorption spectra of C-30, thereby optimizing for FRET. Figure 3. Structures of relevant molecules. The C-30 imprinted polymer exhibited simultaneous quenching in fluorescence (turn-off) of BAMA and enhancement in fluorescence (turn-on) of C-30 (Figure 4). The imprinted polymer showed significantly better performance over the non-imprinted polymer (NIP). Figure 4. Fluorescence spectra of the (a) imprinted (MIP) and (b) non-imprinted (NIP) polymers with increasing concentration of the template Coumarine-30 in methanol. The UV-vis studies revealed that the more effective quenching is indeed due to the affinity for C-30 exhibited by the higher binding imprinted polymer. The imprinted polymer also showed significant selectivity over structurally analogous molecules. Therefore, both high sensitivity and selectivity were realized in such novel off-on sensor. Extension of this concept to other biologically relevant fluorescent templates could lead to potentially useful applications. Chapter 5. Design of New Template Binding Cross-linker. In molecularly imprinted polymers (MIP), high cross-linking density (~80 to 90 mole percent) is essential to ensure high selectivity, which limits the functional (binding) monomer to about 10-20 mole percent. Methacrylic acid (MAA) and ethyleneglycol dimethacrylate (EGDMA) are the most common combination of functional monomer and cross-linker, respectively, used in molecular imprinting. Generally a molecularly imprinted polymer made with this combination, contains only 10-20% binding sites. This limitation of binding site density is an aspect that has largely been overlooked. In order to improve the efficiency of MIP materials by enhancing the number of binding sites, a new cross-linking monomer (CYDI, 1) with two carboxylic acid groups was designed and synthesized by coupling itaconic anhydride with cyclohexane dimethanol (Figure 5). Figure 5. Structures of relevant molecules. The new functional group bearing cross-linking monomer (1) Itaconate ester of cyclohexanedimethanol (CYDI), the template (2) theophylline (Theop) and the structural analogue of template (3) caffeine (Caff). This new cross-linking monomer was then employed for preparing molecularly imprinted polymer using a drug molecule, theophylline (Theop 2, a bronchodilator) as the template. Seven molecularly imprinted polymers were synthesized with different ratios of CYDI and EGDMA, keeping the cross-linking density constant. The binding efficiency and the selectivity of these imprinted polymers were thoroughly investigated. It was seen that while saturation binding values for theophylline increased continuously with functional cross-linker (CYDI) content, the optimum selectivity with respect to analogous substrate, caffeine, was attained at 40 mol% CYDI. These studies suggest that the approach of using functional group containing cross-linkers could lead to improved MIP performance.

This master´s thesis deals with processing and analysis of data, acquired from experimental examination performed with functional magnetic resonance imaging technique. It is an oddball type experimental task and its goal is an examination of cognitive functions of the subject. The principles of functional magnetic resonance imaging, possibilities of experimental design, processing of acquired data, modeling of a response of organism and statistical analysis are described in this work. Furthermore, particular parts of preprocessing and analysis are carried out using real data set from experiment. The main goal of this work is suggestion and realization of model, which enables advanced categorization of stimuli, considering the type of previous rare stimulus and the number of frequent stimuli within them. With its in-depth categorization, this model enables detail exploration of cerebral processes, associated mainly with attention, memory, expectancy or cognitive closure. The second point of that work is an evaluation of models of hemodynamic response, which are applied in statistical analysis of data from fMRI experiment. Comparison of basis functions, the models of hemodynamic response to experimental stimulation used for general linear model, is performed in this work. The result of this comparison is an evaluation of detection efficiency of activated voxels, false positivity rate and computational and user difficulty.

The first part of this project is focused on theoretical analysis of methods for rendering volume data. Both methods are analyzed showing the volume data using triangle mesh, and methods for direct volume rendering. Ray Casting is presented in detail. Possible way of its realization using graphics card is the subject of implementation part. The paper presents several methods that could be applied to ray casting and achieve different results of visualization of the same data. The work also aims to create a  graphical user interface that allows interactive visualizations.

No description available.

El hormigón armado compuesto de cemento Portland fue inventado hace algo más de un siglo aproximadamente y se ha convertido en el material más utilizado en la construcción. La durabilidad de este hormigón es una de las consideraciones más importantes a ser tenidas en cuenta en el diseño de nuevas estructuras y en la evaluación estructural de las ya existentes. Cuando un hormigón sujeto a un ambientes o cargas que puede degradarlo, como puede ser su uso en puentes y ambientes marinos o si contiene grandes cantidades de alúmina o áridos reciclados, el conocimiento o predicción de su durabilidad es una aspecto crítico para su comportamiento en servicio. Los ensayos no destructivos se han mostrado como unos de los ensayos preceptivos con una importancia económica y social más relevante desde que se han aplicado para la auscultación de la durabilidad de las estructuras de hormigón pertenecientes a la ingeniería civil, donde estos materiales son ampliamente utilizados. En cualquier caso, el uso de las técnicas no destructivas en estos materiales no está suficientemente implementado, hecho este motivado por las características heterogéneas de su microestructura. De todos los métodos no destructivos aplicables para el hormigón, el uso de pulsos ultrasónicos es de gran interés para la caracterización de la microestructura y las propiedades de materiales heterogéneos. El objetivo del presente trabajo es obtener un procedimiento de evaluación del ciclo de vida del hormigón preparado y puesto en servicio para ambientes marinos. Además, será estudiado y analizado la incorporación de varias metodologías (destructivas y non destructivas) para caracterizar el proceso de degradación de morteros y hormigones expuestos a disolución de sulfato de sodio y a exposición en disolución de nitrato amónico. Con esta finalidad, una integración adecuada de diferentes técnicas será usada para la caracterización de propiedades y el seguimiento del proceso de degradación que afectan al hormigón. Como objetivos adicionales, destaca que fueron estudiadas las relaciones entre los parámetros destructivos y no destructivos, así como la relación entre los distintos parámetros no destructivos entre sí. Muchos de los estudios anteriores que han usado la inspección ultrasónica las cuáles fueron utilizadas para determinar la relación agua/cemento del mortero, de la pasta de cemento y del hormigón, o para monitorizar los cambios estructurales, para diferentes relaciones a/c, en el proceso de curado. En este trabajo de investigación fue analizado el efecto que tiene para diferentes relaciones a/c en los parámetros ultrasónicos durante el proceso de degradación. Para este objetivo, se utilizaron un Cemento Portland tipo II A L 42.5 (LPC), y otro sulforresistente tipo I 42.5R/SR (SRPC) que fueron usados en la fabricación de dos marcos de hormigón, los cuales fueron utilizados como hormigón en servicio (caso real). Para el estudio del efecto de la variación de a/c en los parámetros ultrasónicos durante la degradación se utilizaron muestras de mortero con deferentes relaciones agua cemento 0.525- 0.45- 0.375 and 0.30 a partir de LPC para obtener diferentes niveles de degradación. Para monitorizar el proceso de degradación se utilizó la inspección por pulso/eco (1 y 3.5 MHz) para la obtención del parámetro del área del perfil de atenuaciones (APA) el cual fue estimado por L Vergara et al., 2003 y usado por Fuente et al, 2004. Para seguir el proceso de curado de pasta de cemento y morteros, este parámetro ha demostrado una alta sensibilidad para caracterizar los cambios microestructurales de materiales derivados del cemento a lo largo de su curado. El método de transmisión se ha utilizado para la determinación de las velocidades de ondas longitudinales con la frecuencia de 1MHz y transversales con la frecuencia de 500 kHz. La velocidad ultrasónica también ha demostrado la capacidad para seguir los cambios microestructurales de un modo sencillo porque dicho parámetro está relacionado con la variación de las propiedades mecánicas, y bajo ciertas premisas, con la variación de la porosidad. El análisis con la imagen ultrasónica con 2 MHz fue también usada para la consecución de los mismos objetivos. Como métodos destructivos, los ensayos de resistencia a la compresión y flexión fueron los utilizados para determinar la pérdida de actividad resistente de morteros y hormigones, y la porosidad conectada al agua para analizar los cambios en la matriz porosa por el efecto de la difusión de elementos agresivos que penetran en el material provocando su degradación. La porosimetría de mercurio (MIP) fue usada para observar las variaciones del volumen y tamaño de poro y, por último, la microscopía electrónica de barrido (MEB) que fue utilizada para cuantificar y detectar los cambios en la microestructura por el ataque de elementos agresivos. Los resultados obtenidos muestran que, la degradación producida por exposición a sulfato de sodio, tiene dos etapas, en la primera etapa se forma la etringita que llena los poros pero que no produce microfisuración. En esta etapa se observó una variación en los parámetros obtenidos por ejemplo, incremento de la velocidad de la onda ultrasónica, de las resistencias a compresión y a la flexión o la disminución de la porosidad. Esta variación en los parámetros podría indicar una mejora en las prestaciones mecánicas del material objeto de la investigación, pero en realidad esto no es cierto porque los poros están llenos de etringita, provocando una expansión, que es la causa de la degradación en la segunda etapa. En dicha segunda etapa, se produce una microfisuración generalizada por la expansión de la etringita e incrementando su volumen dentro de los poros. Este hecho produjo un cambio en los parámetros medidos que contrastan con la evolución en la primera etapa, disminución de la velocidad de las ondas ultrasónicas, y de las resistencias mecánicas y consecuentemente un aumento de la porosidad. Por otro lado, la degradación por ataque de nitrato amonio tiene una única etapa debida al proceso de descalificación que comienza desde el principio del proceso de exposición y es lineal durante todo el periodo de exposición. Para ambos casos, la integración de las diversas técnicas se revela como satisfactoria para el seguimiento del proceso de degradación, encontrando buenas correlaciones entre los parámetros no destructivos y los parámetros destructivos de técnicas de análisis físico-químico. / Mahmoud, TI. (2013). Evaluation of the degradation process of cement-based materials exposed to aggressive environment by using ultrasonic techniques and physical characterisation [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/27550