The crystal structures of two thermostable carboxylesterase Est30 and Est55 from Geobacillus stearothermophilus were determined to help understand their functions and applications in industry or medicine. The crystal structure of Est30 was determined at 1.63 Å resolution by the multiple anomalous dispersion method. The two-domain Est30 structure showed a large domain with a modified alpha/beta hydrolase core including a seven, rather than an eight-stranded beta sheet, and a smaller cap domain comprising three alpha helices. A 100 Da tetrahedral ligand, propyl acetate, was observed to be covalently bound to the side chain of Ser94 in the catalytic triad. This ligand complex represents the first tetrahedral intermediate in the reaction mechanism. Therefore, this Est30 crystal structure will help understand the mode of action of all enzymes in the serine hydrolase superfamily. Est55 is a bacterial homologue of the mammalian carboxylesterases involved in hydrolysis and detoxification of numerous peptides and drugs and in prodrug activation. Est55 crystals were grown at pH 6.2 and pH 6.8 and the structures were determined at resolutions of 2.0 and 1.58 Å respectively. Est55 folds into three domains, a catalytic domain, an α/β domain and a regulatory domain. This structure is in an inactive form; the side chain of His409, one of the catalytic triad residues, is pointing away from the active site. Moreover, the adjacent Cys408 is triply oxidized and lies in the oxyanion hole, which would block the entry of substrate to its binding site. This structure suggested a self-inactivation mechanism, however, Cys408 is not essential for enzyme activity. Mutation of Cys408 showed that hydrophobic side chains at this position were favorable, while polar serine was unfavorable for enzyme activity. Both Est30 and Est55 were shown to hydrolyze the prodrug CPT-11 into the active form SN-38. Therefore, Est30 and Est55 are potential candidates for use with irinotecan in cancer therapy. The catalytic efficiency (kcat/Km) of Est30 is about 10-fold lower than that of Est55. The effects of the Cys408 substitutions on Est55 activity differed for the two substrates, p-NP butyrate and CPT-11. Mutant C408V may provide a more stable form of Est55.

In this thesis, we present the spectral and timing variabilities of anomalous X-ray pulsar 1E 2259+586 observed with European Photon Imaging PN Camera (EPIC PN) on board X-ray Multi Mirror Mission (XMM), Proportional Counter Array (PCA) on board Rossi X-ray Timing Explorer (RXTE) and Advanced CCD Imaging Spectrometer (ACIS) on board Chandra X-ray Observatory. We presented the results of spectral analysis of 2000 January 11 ACIS observation. Pulse phase spectroscopy was performed on two XMM observations before and after the outburst. Pulse profiles of two XMM observations before the outburst and three XMM observations after the outburst were studied. Results are consistent with the those presented by Patel et al. (2001) and Woods et al. (2004). We searched for the spectral variations versus spin rate during the outburst. Long-term spectral, frequency and spin-down rate variations are presented between 1996 and 2006 including 98 RXTE and 4 XMM observations. However, except outburst region (Woods et al. 2004) no significant spectral and spin rate variabilities were seen. Around the outburst region we confirmed the spectral hardening with increasing spin rate and flux.

Transition metal and related compounds have been extensively studied over the past several decades. These investigations revealed a wide range of behavior, encompassing colossal magnetoresistance (CMR), high-TC superconductivity, and magnetic semiconductivity, all of which continue to present fundamental challenges to the understanding of such phenomena. There is, however, a close correlation between such characteristics and the appearance of magnetic order. This correlation underlies the present study, which focuses on the magnetic and transport behavior of various Manganese (Mn), Iron (Fe) and Cobalt (Co) containing materials, with particular emphasis on the nature of the magnetic order they display and the critical exponents that characterize the accompanying phase transition. The magnetic and transport properties of two specific systems will be covered: first various doped manganites from the series (La,Pr)1-x(Ca,Ba)xMnO3, and second the magnetic semiconductors Fe0.8Co0.2Si and Ga0.98Mn0.02As. In the manganites, the influence of doping on; (i) the evolution of the metal-insulator transition (MIT) with composition; (ii) the universality class of the magnetic critical behavior associated with the paramagnetic to ferromagnetic transition, which occurs in the vicinity of a MIT with which CMR is associated; (iii) the mechanisms underlying ferromagnetism across the MIT; (iv) the correlation between the appearance of a Griffiths-like phase and CMR, and (v) the origin of Griffiths-like phase have been investigated. Four different systems have been studied: La1-xCaxMnO3 (0.18 ≤ x ≤ 0.27), La1-xBaxMnO3 (x ≤ 0.33), (La1-yPry)0.7Ca0.3Mn16/18O3 (y ≤ 0.85), and Pr1-xCaxMnO3 (x = 0.27, 0.29). In Fe0.8Co0.2Si and Ga0.98Mn0.02As, the scaling between magnetization and conductivity has been the subject of ongoing debate. In bulk Fe0.8Co0.2Si, a novel scaling between the anomalous Hall effect (AHE) and the magnetization enables the anomalous Hall coefficient to be accurately determined. In turn, this enables the universality class for the transition to ferromagnetism to be established independently from the anomalous Hall conductivity. In an epitaxial (metallic) Ga0.98Mn0.02As microstructure, the magnetization has been indirectly determined from the AHE. Subsequent analysis yields magnetic critical exponents consistent with the Mean-Field model, direct support for which had previously been lacking.

A NMR study of the structure-dynamics relationships in heterogeneous materials is presented. In the first part, transport in soft-matter systems is studied using the pulsed field gradient NMR technique (PFG NMR). The molecular crowding effect in biological matter has been addressed using polymer solutions as model systems. By performing ensemble-based diffusion studies, the earlier obtained data on anomalous diffusion have been complemented. The transition to normal diffusion on a larger time scale has been shown. Taking advantages of the NMR approach, transport properties of microemulsions consisting of micellar colloids dissolved in liquid crystals have been investigated. The self-diffusivities measured under equilibrium conditions have shown weak correlations with microscopic ordering and macroscopic phase transitions occurring in the systems under study. The formation of micelles is shown to be decisive for macroscopic separation at the isotropic-nematic transition. The second part of the thesis covers heterogeneous effects in diffusion for fluids in porous solids, as probed using a combination of NMR diffusometry and structure characterization methods. Ionic liquids have been investigated, revealing a complex behavior under confinement. The attempts to correlate the observed characteristics of the ionic liquids with their internal chemical structure were undertaken. Finally, the series of nanoporous glasses with tunable pore structure characteristics were studied. Strong correlations between their structure and the preparation conditions as well as between the resulting transport properties have been shown.

Transition metal and related compounds have been extensively studied over the past several decades. These investigations revealed a wide range of behavior, encompassing colossal magnetoresistance (CMR), high-TC superconductivity, and magnetic semiconductivity, all of which continue to present fundamental challenges to the understanding of such phenomena. There is, however, a close correlation between such characteristics and the appearance of magnetic order. This correlation underlies the present study, which focuses on the magnetic and transport behavior of various Manganese (Mn), Iron (Fe) and Cobalt (Co) containing materials, with particular emphasis on the nature of the magnetic order they display and the critical exponents that characterize the accompanying phase transition. The magnetic and transport properties of two specific systems will be covered: first various doped manganites from the series (La,Pr)1-x(Ca,Ba)xMnO3, and second the magnetic semiconductors Fe0.8Co0.2Si and Ga0.98Mn0.02As. In the manganites, the influence of doping on; (i) the evolution of the metal-insulator transition (MIT) with composition; (ii) the universality class of the magnetic critical behavior associated with the paramagnetic to ferromagnetic transition, which occurs in the vicinity of a MIT with which CMR is associated; (iii) the mechanisms underlying ferromagnetism across the MIT; (iv) the correlation between the appearance of a Griffiths-like phase and CMR, and (v) the origin of Griffiths-like phase have been investigated. Four different systems have been studied: La1-xCaxMnO3 (0.18 ≤ x ≤ 0.27), La1-xBaxMnO3 (x ≤ 0.33), (La1-yPry)0.7Ca0.3Mn16/18O3 (y ≤ 0.85), and Pr1-xCaxMnO3 (x = 0.27, 0.29). In Fe0.8Co0.2Si and Ga0.98Mn0.02As, the scaling between magnetization and conductivity has been the subject of ongoing debate. In bulk Fe0.8Co0.2Si, a novel scaling between the anomalous Hall effect (AHE) and the magnetization enables the anomalous Hall coefficient to be accurately determined. In turn, this enables the universality class for the transition to ferromagnetism to be established independently from the anomalous Hall conductivity. In an epitaxial (metallic) Ga0.98Mn0.02As microstructure, the magnetization has been indirectly determined from the AHE. Subsequent analysis yields magnetic critical exponents consistent with the Mean-Field model, direct support for which had previously been lacking.

The 2006 International Technology Roadmap for Semiconductors projects that for 2020, interconnects will be as narrow as 14 nm and will operate at frequencies as high as 50GHz. For a wire that operates at ultra-high frequencies, such that skin depth and the mean free path of the electrons are in the same order, skin effect and surface scattering should be considered simultaneously. This is known as the anomalous skin effect (ASE). The objective of this work is to identify the challenges and opportunities for using GSI interconnects in the nanometer and GHz regime. The increase in the resistivity of a thin wire caused by the ASE is studied. The delay of a digital transmission line resulting from this effect is modeled. Compact models are presented for the bit-rate limit of transmission lines using a general form of resistance that for the first time simultaneously considers dc resistance, skin effect, and surface scattering. A conventional low-loss approximation that is only valid for fast rising signals is also relaxed. The impact of size effects on the design of multi-level interconnect networks is studied. For high-performance chips at the 18 nm technology node, it is shown that despite a more than four times increase in the resistivity of copper for minimum-size interconnects, the increase in the number of metal levels is negligible (less than 7%), and interconnects that will be affected most are so short that their impact on chip performance is inconsequential. It is shown that for low-cost applications where very few wiring pitches are normally used, the number of metal levels needed to compensate for the impact of size effects on the average rc delay of a copper interconnect is drastically high. An optimization methodology has been presented for power distribution interconnects at the local level. For a given IR drop budget, compact models are presented for the optimal widths of power and ground lines in the first two metal levels for which the total metal area used for power distribution is minimized.

Metamaterials are humanly engineered artificial electromagnetic materials which produce electromagnetic properties that are unusual, yet can be observed readily in nature. These unconventional properties are not a result of the material composition but rather of the structure formed. The objective of this thesis is to investigate and design smaller and wideband metamaterial-inspired antennas for personal communication applications, especially for WiMAX, lower band and higher band WLAN applications. These antennas have been simulated using HFSS Structure Simulator and CST Microwave Studio software. The first design to be analysed is a low-profile metamaterial-inspired CPW-Fed monopole antenna for WLAN applications. The antenna is based on a simple strip loaded with a rectangular patch incorporating a zigzag E-shape metamaterial-inspired unit cell to enable miniaturization effect. Secondly, a physically compact, CSRR loaded monopole antenna with DGS has been proposed for WiMAX/WLAN operations. The introduction of CSRR induces frequency at lower WLAN 2.45 GHz band while the DGS has provided bandwidth enhancement in WiMAX and upper WLAN frequency bands, keeping the radiation pattern stable. The next class of antenna is a compact cloud-shaped monopole antenna consisting of a staircase-shaped DGS has been proposed for UWB operation ranges from 3.1 GHz to 10.6 GHz. The novel shaped antenna along with carefully designed DGS has resulted in a positive gain throughout the operational bandwidth. Finally, a quad-band, CPW-Fed metamaterial-inspired antenna with CRLH-TL and EBG is designed for multi-band: Satellite, LTE, WiMAX and WLAN.

Le phénomène de blocage de photon est observé lorsqu'un système à deux niveaux est fortement couplé à une cavité, limitant ainsi le nombre d'occupation des photons dans le mode de la cavité à zéro ou un. Ce phénomène est analogue au blocage de Coulomb en physique mésoscopique et a été observé en optique en couplant un atome unique ou une boîte quantique à une cavité. L'efficacité du blocage, mesurée par la fonction d'autocorrélation du deuxième ordre g2(0) augmente d'autant plus que la non-linéarité du système est grande devant la largeur de la cavité. Ce travail de thèse présente l'étude théorique et expérimentale d'un nouveau phénomène de blocage appelé "phénomène de blocage anormal de photon", dans le régime micro-onde. Ce phénomène apparaît dans un système photonique comprenant deux modes couplés, où au moins un des modes est non-linéaire. Par contraste avec le blocage de photon standard, le blocage anormal permet d'obtenir un blocage parfait (g2(0)=0) pour une non-linéarité arbitrairement faible. Nous présentons les propriétés théoriques du blocage anormal, et notamment sa formulation en termes d'états gaussiens. Afin de mettre en évidence ce phénomène, nous avons réalisé deux résonateurs supraconducteurs couplés, dont l'un est rendu non-linéaire et ajustable en fréquence par l'ajout d'un SQUID. Nous montrons les techniques de fabrication employées et la caractérisation des paramètres de notre échantillon. Enfin, nous présentons les techniques mises en œuvre pour mesurer g2(t). Cette mesure nous a permis de mettre en évidence le phénomène de blocage anormal et d'en étudier les propriétés en fonction des différents paramètres expérimentaux. / Photon blockade is observed when a two level system is strongly coupled to a cavity thus limiting the occupation number of the cavity mode to zero or one photon. This phenomenon is analogous to the Coulomb blockade effect in mesoscopic physics and has been observed in optics by coupling a single atom or a quantum dot to a cavity. The efficiency of the blockade, as measured by the second order auto-correlation function g2(0) increases with the non-linearity of the system in comparison to the cavity width. In this thesis, we present a theoretical and experimental study of a new blockade mechanism, called "anomalous photon blockade effect", in the microwave domain. This effect appears in photonics systems consisting of two coupled modes, where at least one of the mode is non-linear. In contrast to the standard blockade effect, perfect blockade (g2(0)=0) can be achieved with an arbitrary weak non-linearity strength. In the first part, we present a theoretical study of the anomalous blockade, and we use, in particular, a description in terms of gaussian states. To experimentally observe this effect, we have micro-fabricated two coupled superconductive resonators, where one of the resonator is frequency tunable and non-linear thanks to a SQUID. In the second part, we present the fabrication process and the characterization of our sample. Finally, we present the different techniques that we use to measure the auto-correlation function g2(τ). This measurement allowed us to demonstrate the anomalous blockade effect and to study its various properties as a function of the experimental parameters.

As Deficiências na Percepção de Cores (DPC) afetam aproximadamente 200 milhões de pessoas em todo o mundo, comprometendo suas habilidades para efetivamente realizar tarefas relacionadas com cores e com visualização. Isto impacta significantemente os âmbitos pessoais e profissionais de suas vidas. Este trabalho apresenta um modelo baseado na fisiologia para simulação da percepção de cores. Além de modelar visão de cores normal, ele também compreende os tipos mais predominantes de deficiências na visão de cores (i.e., protanopia, deuteranopia, protanomalia e deuteranomalia), cujas causas são hereditárias. Juntos estes representam aproximadamente 99.96% de todos os casos de DPC. Para modelar a percepção de cores da visão humana, este modelo é baseado na teoria dos estágios e é derivado de dados reportados em estudos eletrofisiológicos. Ele é o primeiro modelo a consistentemente tratar visão de cores normal, tricromacia anômala e dicromacia de modo unificados. Seus resultados foram validados por avaliações experimentais envolvendo grupos de indivíduos com deficiência na percepção de cores e outros com visão de cores normal. Além disso, ele pode proporcionar a melhor compreensão e um feedback sobre como aperfeiçoar as experiências de visualização por indivíduos com DPC. Ele também proporciona um framework para se testar hipóteses sobre alguns aspectos acerca das células fotoreceptoras na retina de indivíduos com deficiência na percepção de cores. Este trabalho também apresenta uma técnica automática de recoloração de imagens que visa realçar o contraste de cores para indivíduos dicromatas com custo computacional variando linearmente com o número de pixels. O algoritmo proposto pode ser eficientemente implementado em GPUs, e para imagens com tamanhos tipicos ele apresenta performance de até duas ordens de magnitude mais rápida do que as técnicas estado da arte atuais. Ao contrário das abordagens anteriores, a técnica proposta preserva coerência temporal e, portanto, é adequado para recoloração de vídeos. Este trabalho demonstra a efetividade da técnica proposta ao integrá-la a um sistema de visualização e apresentando, pela primeira vez, cenas de visualização recoloridas para dicromatas em tempo-real e com alta qualidade. / Color vision deficiency (CVD) affects approximately 200 million people worldwide, compromising the ability of these individuals to effectively perform color and visualizationrelated tasks. This has a significant impact on their private and professional lives. This thesis presents a physiologically-based model for simulating color perception. Besides modeling normal color vision, it also accounts for the hereditary and most prevalent cases of color vision deficiency (i.e., protanopia, deuteranopia, protanomaly, and deuteranomaly), which together account for approximately 99.96% of all CVD cases. This model is based on the stage theory of human color vision and is derived from data reported in electrophysiological studies. It is the first model to consistently handle normal color vision, anomalous trichromacy, and dichromacy in a unified way. The proposed model was validated through an experimental evaluation involving groups of color vision deficient individuals and normal color vision ones. This model can provide insights and feedback on how to improve visualization experiences for individuals with CVD. It also provides a framework for testing hypotheses about some aspects of the retinal photoreceptors in color vision deficient individuals. This thesis also presents an automatic image-recoloring technique for enhancing color contrast for dichromats whose computational cost varies linearly with the number of input pixels. This approach can be efficiently implemented on GPUs, and for typical image sizes it is up to two orders of magnitude faster than the current state-of-the-art technique. Unlike previous approaches, the proposed technique preserves temporal coherence and, therefore, is suitable for video recoloring. This thesis demonstrates the effectiveness of the proposed technique by integrating it into a visualization system and showing, for the first time, real-time high-quality recolored visualizations for dichromats.

As Deficiências na Percepção de Cores (DPC) afetam aproximadamente 200 milhões de pessoas em todo o mundo, comprometendo suas habilidades para efetivamente realizar tarefas relacionadas com cores e com visualização. Isto impacta significantemente os âmbitos pessoais e profissionais de suas vidas. Este trabalho apresenta um modelo baseado na fisiologia para simulação da percepção de cores. Além de modelar visão de cores normal, ele também compreende os tipos mais predominantes de deficiências na visão de cores (i.e., protanopia, deuteranopia, protanomalia e deuteranomalia), cujas causas são hereditárias. Juntos estes representam aproximadamente 99.96% de todos os casos de DPC. Para modelar a percepção de cores da visão humana, este modelo é baseado na teoria dos estágios e é derivado de dados reportados em estudos eletrofisiológicos. Ele é o primeiro modelo a consistentemente tratar visão de cores normal, tricromacia anômala e dicromacia de modo unificados. Seus resultados foram validados por avaliações experimentais envolvendo grupos de indivíduos com deficiência na percepção de cores e outros com visão de cores normal. Além disso, ele pode proporcionar a melhor compreensão e um feedback sobre como aperfeiçoar as experiências de visualização por indivíduos com DPC. Ele também proporciona um framework para se testar hipóteses sobre alguns aspectos acerca das células fotoreceptoras na retina de indivíduos com deficiência na percepção de cores. Este trabalho também apresenta uma técnica automática de recoloração de imagens que visa realçar o contraste de cores para indivíduos dicromatas com custo computacional variando linearmente com o número de pixels. O algoritmo proposto pode ser eficientemente implementado em GPUs, e para imagens com tamanhos tipicos ele apresenta performance de até duas ordens de magnitude mais rápida do que as técnicas estado da arte atuais. Ao contrário das abordagens anteriores, a técnica proposta preserva coerência temporal e, portanto, é adequado para recoloração de vídeos. Este trabalho demonstra a efetividade da técnica proposta ao integrá-la a um sistema de visualização e apresentando, pela primeira vez, cenas de visualização recoloridas para dicromatas em tempo-real e com alta qualidade. / Color vision deficiency (CVD) affects approximately 200 million people worldwide, compromising the ability of these individuals to effectively perform color and visualizationrelated tasks. This has a significant impact on their private and professional lives. This thesis presents a physiologically-based model for simulating color perception. Besides modeling normal color vision, it also accounts for the hereditary and most prevalent cases of color vision deficiency (i.e., protanopia, deuteranopia, protanomaly, and deuteranomaly), which together account for approximately 99.96% of all CVD cases. This model is based on the stage theory of human color vision and is derived from data reported in electrophysiological studies. It is the first model to consistently handle normal color vision, anomalous trichromacy, and dichromacy in a unified way. The proposed model was validated through an experimental evaluation involving groups of color vision deficient individuals and normal color vision ones. This model can provide insights and feedback on how to improve visualization experiences for individuals with CVD. It also provides a framework for testing hypotheses about some aspects of the retinal photoreceptors in color vision deficient individuals. This thesis also presents an automatic image-recoloring technique for enhancing color contrast for dichromats whose computational cost varies linearly with the number of input pixels. This approach can be efficiently implemented on GPUs, and for typical image sizes it is up to two orders of magnitude faster than the current state-of-the-art technique. Unlike previous approaches, the proposed technique preserves temporal coherence and, therefore, is suitable for video recoloring. This thesis demonstrates the effectiveness of the proposed technique by integrating it into a visualization system and showing, for the first time, real-time high-quality recolored visualizations for dichromats.