Anhydrous proton conducting polymers are highly sought after for applications in high temperature polymer electrolyte membrane fuel cells (PEMFCs). N-heterocycles (eg. imidazole, triazole, and benzimidazole), owing to their amphoteric nature, have been widely studied to develop efficient anhydrous proton transporting polymers. The proton conductivity of N-heterocyclic polymers is influenced by several factors and the design and development of polymers with a delicate balance among various synergistic and competing factors to provide appreciable proton conductivities has been a challenging task. In this thesis, the proton transport (PT) characteristics of polymers functionalized with two diverse classes of functional groups - N-heterocycles and phenols have been investigated and efforts have been made to develop the molecular design criteria for the design and development of efficient proton transporting functional groups and polymers. The proton conduction pathway in 1H-1,2,3-triazole polymers is probed by employing structurally analogous N-heterocyclic (triazole, imidazole, and pyrazole) and benz-N-heterocyclic (benzotriazole, benzimidazole, and benzopyrazole) polymers. Imidazole-like pathway was found to dominate the proton conductivity of triazole and pyrazole-like pathway makes only a negligible contribution, if any. Polymers containing benz-N-heterocycles exhibited higher proton conductivity than those with the corresponding N-heterocycles. Pyrazole-like functional groups, i.e. the molecules with two nitrogen atoms adjacent to each other, were found not to be good candidates for PT applications. A new class of proton transporting functional groups, phenols, has been introduced for anhydrous PT. One of the highlighting features of phenols over N-heterocycles is that the hydrogen bond donor/acceptor reorientation can happen on a single -OH site, allowing for facile reorientational dynamics in Grotthuss PT and enhanced proton conductivities in phenolic polymers. Unlike the case of N-heterocycles, comparable conductivities were achieved between poly (3,4,5-trihydroxy) styrene and the corresponding small molecule, pyrogallol. This observation suggests that reorientation should be considered as a crucial design parameter for PT functional groups. The PT characteristics of phenol-based biaryl polymers are studied and compared with the analogous phenol-based linear styrenic polymers. The two-dimensional disposition of -OH moieties in biaryl polymers, although resulted in lower apparent activation energies (Ea), did not improve the net proton conductivity due to the accompanying increase in glass transition temperature (Tg). Thus, the ease of synthesis and lower Tg values of phenol-based styrene polymers make the styrenic polymer architecture preferable over the biaryl architecture. Finally, the synthesis of a series of poly(3,4-dihydroxy styrene)-b-polystyrene block copolymers has been demonstrated via anionic polymerization. These block copolymers will provide an opportunity to systematically investigate the effect of nanoscale morphology on proton transport.

This paper examines the integration of geometric and feature cues in spatial memory with a modified version of the spatial reorientation task. Proponents of the geometric module position argue that there is an encapsulated reorientation module, and that true reorientation is accomplished only via geometry (Lee & Spelke, 2010). Features can be used in a second and separate step, but only to locate a goal rather than as a reorientation cue. In contrast, proponents of the adaptive combination approach argue that geometry and feature cues are integrated in spatial memory and that both cues can be used to facilitate reorientation (Newcombe & Ratliff, 2007). The present experiment provides support for the adaptive combination position. The first phase of the experiment was a reorientation task in a trapezoid enclosure (unambiguous geometry) with a narrow feature strip (unambiguous feature). During training, participants started facing a set direction, were disoriented, and then were asked to return to the original facing direction using the geometry, the feature, or both. During these training trials, participants were biased in the direction of the feature, indicating that both features and geometry might be integrated in a Bayesian fashion in spatial memory. The test trials provided additional support for integration and the adaptive combination position. There were four conflict test conditions where the feature moved in relation to the geometry present in training. When the feature moved a small distance in the direction of the geometry, when the feature moved to a novel wall, or when the feature moved a small distance away from the geometry of an acute corner angle, participants selected the correct geometric position. In contrast, when the feature moved a small distance away from the geometry of an obtuse corner angle or when the feature moved a moderate distance away from the geometry of either an acute or an obtuse angle, participants integrated their response and selected and area between the training geometry and feature. The modularity position predicts choices exclusively at the geometry position. This was not found. The adaptive combination position predicts that features and geometry will sometimes be used independently and crucially can be integrated. The data support this position. In sum, the present research provides the first evidence for integration of geometric and feature cues in adult spatial memory during reorientation, and supports the adaptive combination position. Additionally, a mini spatial battery was administered to participants. Correlations of individual differences in spatial skills with reorientation in this paradigm are discussed. / Psychology

Au lendemain de la Seconde Guerre mondiale, la politique d'occupation américaine de l'Allemagne prévoit la mise en place d'un programme de « réorientation » dont l'objectif est d'éliminer toute influence nazie et militariste au sein de la société allemande et d'encourager le développement de pratiques démocratiques. Instauré durant le conflit, le programme hebdomadaire d'information des troupes américaines a pour objectif, non plus d'éveiller l'envie de combattre, mais de faire des soldats des « ambassadeurs » des États-Unis. L'armée déploie une multitude de moyens d'information afin de former les soldats à leur nouvelle mission, celle de promouvoir le modèle américain de démocratie en Allemagne. L'Army Assistance to German Youth Activities, mis en place par l'armée américaine en 1946, vise à projeter une image positive des États-Unis et à transmettre, notamment à travers la pratique d'activités sportives, les valeurs et les idéaux de la démocratie américaine. Cette volonté de guider et d'influencer la population civile allemande témoigne de l'intention des responsables américains de développer le pouvoir d'attraction des États-Unis en Allemagne dans un contexte d'occupation quadripartite et de montée des tensions Est-Ouest. / After World War II, the American occupation policy of Germany provided for an "affirmative program of reorientation ... designed completely to eliminate Nazi and militaristic doctrines and to encourage the development of democratic ideas". The American soldiers, as "ambassadors of democracy" became key actors in the reorientation process. The troop information program encouraged servicemen to promote democracy in their informal contacts with Germans. Soldiers and dependents had to display a friendly face of hard power. In 1946, the Army devised a comprehensive program for German youth designed to teach them democratic principles: the Army Assistance to German Youth Activities, (GYA). Sports activities were regarded as an effective tool to reach and influence German children's thinking. Sports also promoted American traditions while serving as a cultural instrument against the growing influence of communism. In the context of occupation and Cold War, members of the U.S. armed forces exerted soft power influence in order to promote the American model of democracy in Germany

Made available in DSpace on 2016-08-10T11:21:36Z (GMT). No. of bitstreams: 1 MARCIA APARECIDA VIEIRA ANDRADE.pdf: 2704145 bytes, checksum: 9d7d137a07353f225d0032b7c8e811de (MD5) Previous issue date: 2011-08-12 / This paper is a study of the proposed curricular reorientation of Goiás, noting the design and teaching of history present in this. An analyse that follows theory of cultural history trying to approach teaching the history of reality for the students to have a significant learning this. Prioritizing the different readings of the world and the different local experiences, the learning process is a network built through these various knowledges. Within the historical perspective, the first chapter include a resumption of the curriculum guidance provided that education has become institutionalized in contemporary society. This overview is intended to contextualize and clarify the present situation. / Esse trabalho faz um estudo da proposta de reorientação curricular de Goiás, observando sua concepção de ensino e de história. Fazemos uma análise a partir da história cultural, buscando aproximar o ensino de história da realidade dos estudantes e obter uma aprendizagem significativa. Priorizamos as diferentes leituras de mundo e as diversas experiências locais, concebendo o processo de aprendizagem como uma rede construída por meio desses saberes diversos. Seguindo a perspectiva histórica, os primeiros capítulos compreendem uma retomada da orientação curricular desde que a educação passou a ser institucionalizada até a sociedade contemporânea. Este panorama tem o intuito de contextualizar e esclarecer a situação presente.

The purpose of this work is to reveal the governing mechanisms responsible for the magnetic field-induced i) martensite reorientation in Ni2MnGa single crystals, ii) stress-assisted phase transformation in Ni2MnGa single crystals and iii) phase transformation in NiMnCoIn alloys. The ultimate goal of utilizing these mechanisms is to increase the actuation stress levels in magnetic shape memory alloys (MSMAs). Extensive experimental work on magneto-thermo-mechanical (MTM) characterization of these materials enabled us to i) better understand the ways to increase the actuation stress and strain and decrease the required magnetic field for actuation in MSMAs, ii) determine the effects of main MTM parameters on reversible magnetic field induced phase transformation, such as magnetocrystalline anisotropy energy (MAE), Zeeman energy (ZE), stress hysteresis, thermal hysteresis, critical stress for the stress induced phase transformation and crystal orientation, iii) find out the feasibility of employing polycrystal MSMAs, and iv) formulate a thermodynamical framework to capture the energetics of magnetic field-induced phase transformations in MSMAs. Magnetic shape memory properties of Ni2MnGa single crystals were characterized by monitoring magnetic field-induced strain (MFIS) as a function of compressive stress and stress-induced strain as a function of magnetic field. It is revealed that the selection of the operating temperature with respect to martensite start and Curie temperatures is critical in optimizing actuator performance. The actuation stress of 5 MPa and work output of 157 kJm−3 are obtained by the field-induced variant reorientation in NiMnGa alloys. Reversible and one-way stress-assisted field-induced phase transformations are observed in Ni2MnGa single crystals under low field magnitudes (<0.7T) and resulted in at least an order of magnitude higher actuation stress levels. It is very promising to provide higher work output levels and operating temperatures than variant reorientation mechanisms in NiMnGa alloys. Reversible field-induced phase transformation and shape memory characteristics of NiMnCoIn single crystals are also studied. Reversible field-induced phase transformation is observed only under high magnetic fields (>4T). Necessary magnetic and mechanical conditions, and materials design and selection guidelines are proposed to search for field-induced phase transformation in other ferromagnetic materials that undergo thermoelastic martensitic phase transformation.

The purpose of this work is to reveal the governing mechanisms responsible for the magnetic field-induced i) martensite reorientation in Ni2MnGa single crystals, ii) stress-assisted phase transformation in Ni2MnGa single crystals and iii) phase transformation in NiMnCoIn alloys. The ultimate goal of utilizing these mechanisms is to increase the actuation stress levels in magnetic shape memory alloys (MSMAs). Extensive experimental work on magneto-thermo-mechanical (MTM) characterization of these materials enabled us to i) better understand the ways to increase the actuation stress and strain and decrease the required magnetic field for actuation in MSMAs, ii) determine the effects of main MTM parameters on reversible magnetic field induced phase transformation, such as magnetocrystalline anisotropy energy (MAE), Zeeman energy (ZE), stress hysteresis, thermal hysteresis, critical stress for the stress induced phase transformation and crystal orientation, iii) find out the feasibility of employing polycrystal MSMAs, and iv) formulate a thermodynamical framework to capture the energetics of magnetic field-induced phase transformations in MSMAs. Magnetic shape memory properties of Ni2MnGa single crystals were characterized by monitoring magnetic field-induced strain (MFIS) as a function of compressive stress and stress-induced strain as a function of magnetic field. It is revealed that the selection of the operating temperature with respect to martensite start and Curie temperatures is critical in optimizing actuator performance. The actuation stress of 5 MPa and work output of 157 kJm−3 are obtained by the field-induced variant reorientation in NiMnGa alloys. Reversible and one-way stress-assisted field-induced phase transformations are observed in Ni2MnGa single crystals under low field magnitudes (<0.7T) and resulted in at least an order of magnitude higher actuation stress levels. It is very promising to provide higher work output levels and operating temperatures than variant reorientation mechanisms in NiMnGa alloys. Reversible field-induced phase transformation and shape memory characteristics of NiMnCoIn single crystals are also studied. Reversible field-induced phase transformation is observed only under high magnetic fields (>4T). Necessary magnetic and mechanical conditions, and materials design and selection guidelines are proposed to search for field-induced phase transformation in other ferromagnetic materials that undergo thermoelastic martensitic phase transformation.

The translational self-diffusion, the librations, and the reorientational motions of guest water molecules in the zeolite chabazite are examined by Molecular Dynamics (MD) computer simulations at different temperatures and loadings, including at room temperature, at which the experiments are carried out. Satisfactory agreement is found between the computed and measured translational self-diffusion coefficients. It is, however, furthermore found that the way in which the long-range electrostatic interactions are computed has an effect on the self-diffusion at high loadings and temperatures. The spectral densities of the librational motions of water are found to be similar to those in aqueous salt solutions. The reorientations of the water molecules, on the other hand, are much slower than in the liquids, and very anisotropic. The vector in direction of the molecular dipole moment reorients only very slowly, at the time scale of the simulations, due to the attraction to the almost immobile Ca++-ions and the walls of the zeolite. The other two vectors seem to undergo jump-reorientations rather than reorientations by a diffusion process. Hyper dynamics boost potential method has been applied to the MD simulations to estimate the self-diffusion coefficients of Ca++ ions in dehydrated chabazite. Because of our system is very complicated, the self-diffusion of Ca++ ions can only be roughly estimated. The Ca++ ions diffusion is small enough to confirm that the cation motion can be neglected in the normal MD simulation.

Orientador: Flávio César Guimarães Gandra / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-19T11:06:30Z (GMT). No. of bitstreams: 1 Monteiro_JoseCarlosBotelho_M.pdf: 5466679 bytes, checksum: 3148a9c0487d05fa44922d063e525114 (MD5) Previous issue date: 2011 / Resumo: Neste trabalho apresentamos os resultados das medidas de magnetização e calorimetria em policristais da série RZn (R= Tb, Gd, Er e Ho). Através da análise das curvas de magnetização em função da temperatura, obtidas em campos de até 5 T, avaliamos e obtemos o efeito magnetocalórico (EMC) para os compostos da série, expresso através da variação isotérmica da entropia. O composto GdZn é o mais simples da série sendo o único que não apresenta efeitos inerentes à anisotropia magnética. Pelas medidas de magnetização observamos uma transição de ordenamento magnético em 260 K. Para este composto utilizamos um hamiltoniano simples, considerando apenas as contribuições devido à interação de troca e ao efeito Zeeman para simular curvas de calor específico e magnetização. Com os dados obtidos observamos uma variação de entropia máxima de 3,49 mJ/gK para um campo de 5 T em torno de Tc. O ErZn apresenta transição ferromagnética em 18 K e uma queda na magnetização em temperaturas abaixo de Tc, que é resultado de uma transição de reorientação de spin (TRS) induzida por campo. Essa transição é um efeito da anisotropia do sistema e é observada apenas em curvas obtidas em baixos campos magnéticos. Para simular as curvas de magnetização do ErZn e dos demais compostos da série adicionamos ao hamiltoniano utilizado a contribuição devido ao campo cristalino. Ao avaliarmos o EMC do ErZn vemos que existe uma pequena anomalia, resultado da TRS, em torno de 11K para variações em até 2 T de campo. Em campos maiores a anomalia desaparece e obtemos um ?S de até 14,83 mJ/gK em campos de 5 T. Os compostos TbZn e HoZn apresentam transições ferromagnéticas em 195 e 66 K, respectivamente, e ambos apresentam transições de reorientação de spin em temperaturas abaixo de Tc. Diferentemente do ErZn, porém, nesses compostos as TRS não são induzidas por campo, sendo resultado apenas da anisotropia do sistema, mostrando efeitos muito mais pronunciados nas curvas de magnetização e calor específico. Ao calcularmos o EMC desses compostos, observamos dois picos pronunciados relativos à mudança da entropia no material, um devido ao ordenamento magnético em Tc e outro devido à reorientação de spin no material. Essa característica faz com que o EMC nesses compostos tenha uma área de atuação muito maior do que em materiais que só apresentam um ?Smax em Tc, tornando materiais desse tipo fortes candidatos à refrigeração magnética / Abstract: This work presents the results of calorimetric and magnetization measurements on polycrystalline RZn series (R = Tb, Gd, Er and Ho). By analyzing the curves of magnetization as a function of temperature, obtained under fields up to 5 T (6 T for TbZn), we obtain and evaluate the magnetocaloric effect (MCE) for compounds of the series, expressed by the isothermal entropy change. The GdZn compound is the simplest of the series being the only one that has no inherent magnetic anisotropy effects. Through magnetization measurements we observe a magnetic ordering transition at 260 K. For this compound we use a simple Hamiltonian, considering only the contributions due to exchange interaction and the Zeeman Effect to simulate curves of specific heat and magnetization. With the data obtained, GdZn presented a maximum entropy change of 3.49 mJ/gK for a magnetic field of 5 T around Tc. The ErZn presents a ferromagnetic transition at 18 K and a drop in magnetization at temperatures below Tc, which is the result of a spin reorientation transition (SRT) induced by magnetic field. This transition is an effect of the system¿s anisotropy and is observed only in curves at low magnetic fields. To simulate the magnetization curves of ErZn and the other compounds of the series we added to the Hamiltonian the contribution due to the crystalline field. In evaluating the MCE of ErZn we find that there is a small anomaly, the result of SRT, around 11K for field variations up to 2 T. In larger fields the anomaly disappears and we get ?S up to 14.83 mJ / gK at fields of 5 T. The compounds HoZn and TbZn have ferromagnetic transitions at 195 and 66 K, respectively, and both have spin reorientation transitions at temperatures below Tc. Unlike the ErZn compound, however, those SRT are not field-induced, being the sole result of anisotropy of the system and showing effects much more pronounced in the curves of magnetization and specific heat. In calculating the EMC of these compounds, we observe two pronounced peaks on the entropy change in the material, one due to a magnetic ordering at Tc and the other due to spin reorientation in the material. This feature shows that the MCE in these compounds act in a much wider range than the usual materials that shows a peak only in Tc, making them strong candidates for magnetic refrigeration / Mestrado / Física da Matéria Condensada / Mestre em Física

En condition de stress, les organismes photosynthétiques réorientent leur métabolisme vers la production de métabolites d’intérêt. Cette thèse vise à fournir de nouvelles informations sur ces processus chez les algues et les plantes supérieures. La 1ère partie est consacrée aux effets de 3 éclairements différents sur le métabolisme du carbone de la diatomée Phaeodactylum tricornutum. L'impact d’un éclairement supérieur à 300 µmol photons m-2 s-1 (ML) est tout à fait différent de celui obtenu pour un éclairement de 30 µmol photons m-2 s-1 tant au niveau physiologique que moléculaire. Dans nos conditions, la carence en carbone constitue la cause principale de l'apparition de la phase stationnaire. La synthèse des lipides est plus élevée sous un éclairement inférieur à ML. En revanche, la synthèse des protéines et de chrysolam-inarine augmente respectivement sous fort et faible éclairements. Les changements d’expression génique suggèrent que la conversion réversible du phosphoénol-pyruvate en pyruvate constitue une étape clé de l’orientation des intermédiaires dans les différentes voies de biosynthèse des molécules d’intérêt. L'état physiologique des cellules doit être considéré pour la comparaison d’échantillons. La 2ème partie du mémoire est consacrée aux effets de la quantité et de la qualité de la lumière délivrée par des LED (bleu, rouge, 70% de lumière rouge+30% de bleu et blanc) sur la régulation de la synthèse de métabolites secondaires chez 3 espèces de menthe prélevées dans la nature. La qualité de la lumière influence la stratégie d’utilisation du carbone par les plantes. Par exemple, la lumière rouge stimule le mieux la production de la synthèse de l'huile essentielle chez la menthe alors que le taux de fixation du carbone est similaire à celui trouvé dans les autres conditions d’illumination. Glomus mossae est le seul champignon mycorhizien à arbuscules à induire une augmentation supplémentaire de la production d’huile essentielle. / Under stress, photosynthetic organisms reoriente their metabolism toward the production of high added value molecules. Regarding the importance of this process, it is surprising that the processes on which the reorientation relies are still not better understood. This thesis aims to provide new information regarding these processes. The 1st part of this thesis is dedicated to the effects of 3 different light intensities on the carbon metabolism of the diatom Phaeodactylum tricornutum. The impact of light intensities higher than 300 µmol photons m-2 s-1 (ML) were different from those obtained with 30 µmol photons m-2 s-1 at the physiological and molecular levels. Carbon deficiency was responsible for the occurrence of plateau phase in cultures. Except lag phase, lipid synthesis was higher under ML In contrast, protein and chrysolaminarin syntheses increased under 1000 and 30 µmol photons m-2 s-1, respectively. Gene expression modifications suggest that the reversible conversion between phosphoenolpyruvate and pyruvate constitutes a key step for the orientation of intermediates to either high value molecules biosynthetic pathways. The physiological state of the cells should be taken into consideration when samples comparison is considered.The 2nd part of the report is dedicated to the effects of light quantity and quality (blue, red, 70% red+30% blue and white light delivered by LED) on the regulation of essential oil synthesis in 3 Mentha species collected in nature. The light quality impacts the strategy of carbon utilization by the plant. Typically, red light was the most effective for stimulating the production of essential oil in Mentha sp. while carbon fixation capacity was similar to that found in other ligthing conditions. Regardless the light intensity, Glomus mossae was the only arbuscular mycorrhizal fungus able to enhance additionally essential oil production.

Le développement de novo de médicaments est un processus long et coûteux. De plus en plus, les développeurs de médicaments cherchent à mettre en oeuvre des stratégies rentables et à moindre risque pour le développement de produits pharmaceutiques. Le processus de trouver de nouveaux usages pour des médicaments existants en dehors de l'indication initiale pour laquelle ils ont été initialement approuvé est couramment désigné comme « repositionnement », « réorientation » ou « reprofilage ». Le développement de formulations différentes pour un même médicament pharmaceutique est communément désigné comme « reformulation » et le processus de trouver une autre utilisation thérapeutique d'un médicament déjà connu est dénommé « repositionnement ». Ces deux stratégies sont devenues un courant dominant dans le développement des médicaments. Les principaux objectifs de la recherche menée dans cette thèse sont de parvenir à proposer une nomenclature et la taxonomie solide et valable pour l'identification et la classification des stratégies de « repurposing » de médicaments ; évaluer les voies de régulation de stratégies de repositionnement et de reformulation, par types de stratégies et dans les 2 régions géographiques étudiées ; et déterminer les paramètres qui ont un impact sur la probabilité d'un résultat positif sur le prix, le remboursement et l'accès au marché vis-à-vis des conditions accordées pour le médicament original dans les deux régions géographiques dans l'étude / De novo drug development is a costly and lengthy process. As a result of such market forces, drug developers are increasingly striving to find cost effective and reduced-risk strategies for developing drug products and to protect existing products from competition, as well as to extend their patent protection time. The process of finding new uses for existing drugs outside the scope of the original indication for which they were initially approved is variously referred as repositioning, redirecting, repurposing, or reprofiling. The development of different formulations for a same pharmaceutical drug is commonly designated as “reformulation” and the process of finding a new therapeutic use for an already known drug is referred to as “repositioning”. Both strategies have become a mainstream in drug development. The main objectives of the research conducted in this thesis are to propose a robust and valid nomenclature and taxonomy for identification and classification of drug repurposing strategies, to evaluate which regulatory pathways and trends are taken by drug repositioning and reformulation, by repurposed types and within the Europe and the US and determine which parameters have the most and least impact on the probability of a successful outcome on pricing, reimbursement and market access in repurposing vis-à-vis the conditions granted for the original drug