Creep compliance of Hot Mix Asphalt (HMA) is an important property to characterize the material's viscoelatic behavior. It is used to predict HMA thermal cracking at low temperature and permanent deformation at high temperatures. There are several experimental methods to measure the creep compliance. Two of these methods were used in this thesis; uniaxial compressive and indirect tension (IDT) creep compliance. The tests were conducted at five temperatures (-15, 5, 20, 30, and 40°C) with a static loading for 1000-sec to characterize two typical HMA mixes used in Virginia, a base and a surface mix. Creep compliance master curves (CCMC) were developed by shifting the curves to a reference temperature using time-temperature superposition. Three mathematical functions, Prony series, power and sigmoidal, were fitted to the experimental data using regression analysis. Uniaxial CCMC were also predicted based on dynamic modulus measurements using method for interconversion of vicoelastic properties recommended in the literature. Finally, the susceptibility of the mixes to thermal cracking was evaluated based on the creep compliance measurements at low temperature. The regression analysis showed that the three mathematical models considered are appropriate to model the CCMC over a wide ranger of reduced times. The sigmoidal model provided the best fit over the entire range of reduced times investigated. This model also produced the best results when used in the interconversion procedures. However, there were noticeable differences between the CCMC predicted using interconversion and the experimental measurements, probably due to nonlinearity in the material behavior. The m-values for the base mix were higher using the creep results measured with both configurations. / Master of Science

L'utilisation de nouveaux vecteurs énergétiques comme alternative aux combustibles fossiles et nucléaires est nécessaire pour la transition vers les énergies renouvelables. Ces sources d'énergie intermittentes peuvent être stockées dans des carburants, tels que le dihydrogène qui se distingue par sa densité énergétique. L'oxydation contrôlée de H2 peut être effectuée dans des piles à combustible, qui oxydent l'hydrogène à l'anode et réduisent l'oxygène à la cathode pour former de l'eau et de la chaleur comme seuls produits de la réaction. Ces technologies, matures, emploient des métaux du groupe du platine comme catalyseurs à l'anode et à la cathode. Cependant, alors que les demandes énergétiques mondiales ne cessent d'augmenter, ces ressources limitées ne seront pas suffisantes pour une adoption mondiale de l'hydrogène comme vecteur énergétique. Dans ce travail, des matériaux contenant des catalyseurs bio-inspirés, sans métaux nobles pour l'oxydation de H2 sont optimisés et intégrés dans des piles à combustible fonctionnelles. Leur comportement dans des conditions technologiques est étudié et comparé à celui de l'état de l'art des catalyseurs au platine. Les matériaux les plus performants sont caractérisés en détail par diverses techniques, donnant des pistes pour une optimisation future ainsi qu'un aperçu de ce que requièrent les tests de performance de nouveaux matériaux catalytiques. / The use of new energy vectors as alternatives to the fossil and nuclear fuels is necessary for the transition to renewable energies. These intermittent energy sources can be stored in fuels, such as hydrogen gas which stands out for its energy density and participation in the virtuous water splitting cycle. Controlled H2 oxidation can be done in so-called fuel cells, which oxidize hydrogen at the anode and reduce oxygen at the cathode to form water and heat as the sole products of the reaction. Those mature technologies employ platinum group metals as catalysts at both the anode and cathode. However, as worldwide energy demands keep increasing, these limited resources will not be sufficient for a worldwide adoption of H2 as an energy vector. In this work, materials containing noble metal free, bio inspired catalysts for H2 oxidation are optimized and integrated in functional fuel cells. Their behaviour in technologically-relevant conditions is studied and compared to that of state of the art platinum catalysts. The best performing materials are thoroughly characterized with various techniques including advanced electrochemistry, yielding leads for further optimization as well as insight on the benchmarking of novel catalytic materials.

This thesis presents a method to correct for non-positive-definiteness in linear viscoelastic material functions. Viscoelastic material functions for anisotropic materials need to be interconverted in a matrix coefficient prony series form, with a requirement of positive definiteness. Fitting is usually done as a uniaxial prony series, resulting in scalar coefficients. When these uniaxial coefficients are placed in a coefficient matrix, the required positive definiteness cannot be guaranteed. For those matrices that do not meet this requirement, finding the nearest symmetric semi-positive definite form of the matrix results in a viable prony series matrix coefficient with the required positive definiteness. These corrected prony series coefficients allow for material functions to be interconverted with minimal changes to experimental data.

The third generation camptothecin analog, AR-67, is undergoing early phase clinical trials as a chemotherapeutic agent. Like all camptothecins it undergoes pH dependent reversible hydrolysis between the lipophilic lactone and the hydrophilic carboxylate. The physicochemical differences between the lactone and carboxylate could potentially give rise to differences in transport across and/or entry into cells. In vitro studies indicated reduced intracellular accumulation and/or apical to basolateral transport of AR-67 lactone in P-gp and/or BCRP overexpressing MDCKII cells and increased cellular uptake of carboxylate in OATP1B1 and OATP1B3 overexpressing HeLa-pIRESneo cells. Pharmacokinetic studies were conducted in rats to study the disposition and oral bioavailability of the lactone and carboxylate and to evaluate the extent of the interaction with uptake and efflux transporters. A pharmacokinetic model accounting for interconversion in the plasma was developed and its performance evaluated through simulations and in vivo transporter inhibition studies using GF120918 and rifampin. The model predicted well the likely scenarios to be encountered clinically from pharmacogenetic differences in transporter proteins, drug-drug interactions and organ function alterations. Oral bioavailability studies showed similarity following lactone and carboxylate administration and indicated the significant role ABC transporters play in limiting the oral bioavailability.

Within the exciting current trend to explore novel low-dimensional systems, the possibility to inject pure spin currents in graphene and other two-dimensional crystals has attracted considerable attention in the past few years. The theoretical prediction of large spin relaxation times and experimentally observed mesoscopic-scale spin diffusion lengths places graphene as a promising base system for future spintronics devices. This is due to the unique characteristics intrinsic to the two-dimensional lattice of carbon atoms forming graphene, such as the lack of nuclear spins and weak spin-orbit coupling of the charge carriers. Interestingly for some spintronic applications, the latter can be chemically and physically engineered, with large induced spin-orbit couplings found in functionalized graphene sheets. Understanding spin injection, spin current and spin dynamics in graphene is of a great interest, both from the fundamental and applied points of view. This thesis presents an experimental study of dynamical generation of spin currents in macroscopic graphene sheets by means of spin pumping from the precessing magnetization of an adjacent ferromagnet. The spin pumping characteristics are studied by means of ferromagnetic resonance (FMR) measurements in Permalloy/graphene (Py/Gr) bilayers. Changes in the FMR linewidth induced by the presence of graphene (when compared to studies with only Py films) correspond to an increase in the Gilbert damping in the ferromagnetic layer (proportional to the FMR linewidth) and interpreted as a consequence of spin pumping at the Py/Gr interface driven by the Py magnetization dynamics (i.e., magnetic induced by the microwave stimulus). FMR experiments are performed on different FM/Gr interfaces, completing a set of studies designed to systematically identify and eliminate damping enhancement arising from processes other than spin pumping. Remarkably, a substantial enhancement of the Gilbert damping observed in Py/Gr strips with graphene protruding a few micrometers from the strip sides is univocally associated to spin pumping at the quasi-onedimensional interface between the Py strip edges and graphene. This increase in the FMR linewidth compares with observations in other bilayer systems, in where thick (thicker than the spin diffusion length) layers of heavy metals with strong spin-orbit coupling are employed as the non-magnetic layer, indicating that spin relaxation in chemically grown graphene must be greatly enhanced in order to account for the losses of angular momentum lost by the ferromagnet. The fundamental implications of the results presented in this thesis point to a non-trivial nature of the spin pumping mechanism owing to the two-dimensionality of the non-magnetic layer (i.e., graphene). In addition, a spintronics device designed to interconvert charge and spin currents has been designed. A high-frequency microwave irradiation lock-in modulation technique is employed to detect the small electrical voltages generated by the inverse spin Hall effect (ISHE). As a proof of principle, a successful spin-charge interconversion in Py/Pt-based devices is experimentally demonstrated in this thesis. The challenges associated with the spin-charge interconversion in twodimensional devices are discussed and systematically addressed, and a potential device geometry for measuring the ISHE in Py/Gr-based systems is provided.

No description available.

The interconversion of α- and β-Ni(OH)₂ was studied using cyclic voltammetry and dynamic electrochemical impedance (dEIS). Holding experiments were done at 0.5 V, 0.6 V, 0.8 V and 1.0 V while subsequent cathodic holds were applied in selected experiments at -0.1, -0.2, -0.25 V. The number of thickness of Ni(OH)₂ formed increased with increasing anodic potential. After α-Ni(OH)₂ was formed (< 0.5 V), it was easily reduced by sweeping down to -0.15 V. However, sweeping further (> 0.5 V) resulted in its "irreversible" conversion to β-Ni(OH)₂. Since β-Ni(OH)₂ was not reduced by sweeping to -0.15 V, the current, capacitance and the conductance at the α-Ni(OH)₂ peak (at 0.2 V) decreased as a result. However, β-Ni(OH)₂ was shown to be reducible during potential holds at -0.2 V or lower. In contrast, holding at -0.1 V only resulted in partial reduction. Eventually, a link was established between the reduction of β-Ni(OH)₂ and hydrogen evolution. The relatively slow reduction of the β-Ni(OH)₂ to metallic nickel appears to inhibit the capacitance increase at -0.15 V which occurs when the potential is kept under 0.5 V. The retention of a low capacitance while β-Ni(OH)₂ persists suggests a blocking mechanism. A concerted adsorption-desorption step which generates adsorbed hydrogen prior to hydrogen evolution was proposed. An exponential increase in current and capacitance occurred during the potential hold at -0.2 V. The capacitance increase suggests a reversal of the blocking (low capacitance at -0.15 V) caused by the persistence of β-Ni(OH)₂. Additionally, the exponential current decay during the hold at -0.2 V was significantly slower than the conversion of α- to β-Ni(OH)₂ at 0.8 V. This further demonstrates the possibility of a slow step involving surface blocking during the reduction of β-Ni(OH)₂. These observations provide new information on the mechanism and kinetics of the interconversion of α-Ni(OH)₂ into β-Ni(OH)₂ and the interaction of the latter in the hydrogen evolution reaction. / Graduate

Le parasite intracellulaire Toxoplasma gondii est l'agent pathogène de la toxoplasmose. Cette maladie est gravissime pour le fœtus et pour l'individu immunodéprimé. L'interconversion du parasite de la forme tachyzoïte virulente à la forme bradyzoïte quiescente est au centre de la pathogénèse de cette infection. Ce processus engage une régulation coordonnée des gènes du parasite qui se traduit par une cascade d'évènements moléculaires au niveau de l'ADN. Des études suggèrent un contrôle transcriptionnel de l'interconversion avec l'expression exclusive de certains gènes dans une forme donnée. Cependant, ce parasite et son phyllum se distinguent des autres eucaryotes par une quasi-pénurie des facteurs spécifiques de transcription. Nous avons émis l'hypothèse que le niveau d'expression des gènes du Toxoplasme est étroitement régulé par la structure physique et la nature chimique de la chromatine. Ce manuscrit illustre l'influence majeure du « code histone » sur la différenciation parasitaire. Nous avons identifié plusieurs enzymes en charge de l'écriture de ce code. L'exemple le plus frappant est la découverte d'une methyltransférase TgCARM1 qui méthyle l'arginine 17 de l'histone H3, une marque activatrice de la transcription. Nous avons également identifié le premier complexe co-repressor du Toxoplasme (TgCRC). TgCRC en opposition avec l'acétylase TgGCN5 régule en partie la balance acétylation/déacétylation, qui en retour influe sur la différenciation parasitaire. L'ensemble de nos résultats converge vers l'idée de l'existence d'un « code histone parasitaire » hautement sophistiqué, qui a co-évolué avec celui de la cellule hôte parasitée.

Uma mistura asfÃltica apresenta um comportamento mecÃnico complexo que pode ser idealizado por um modelo viscoelastoplÃstico, que considera a existÃncia de deformaÃÃes recuperÃveis (elÃstico e viscoelÃstico) e nÃo recuperÃveis (plÃstico e viscoplÃstico). No entanto, o estado da arte da pesquisa brasileira tem considerado um modelo mais restrito, o modelo viscoelÃstico linear. Este modelo trata o comportamento mecÃnico do material como dependente do carregamento e da correspondente taxa (temporal) de aplicaÃÃo, que representa um avanÃo considerÃvel na modelagem mecÃnico-computacional de misturas asfÃlticas frente ao modelo elÃstico linear (clÃssico) comumente empregado em projetos nacionais de dimensionamento de pavimentos. Ainda assim, o modelo viscoelÃstico apresenta alguns inconvenientes que dificultam seu uso. Um primeiro inconveniente à que para uma representaÃÃo compatÃvel com os dados experimentais, a caracterizaÃÃo constitutiva viscoelÃstica exige a manipulaÃÃo de uma grande quantidade de coeficientes da sÃrie de Prony, dificultando o processo de ajuste de curva e posterior manipulaÃÃo da sÃrie. AlÃm disso, o processo formal de interconversÃo entre as propriedades viscoelÃsticas fundamentais, comumente necessÃrio por questÃes operacionais, trata-se de um mÃtodo nÃo trivial. Para facilitar o emprego da teoria da viscoelasticidade (linear) na caracterizaÃÃo de misturas asfÃlticas, o presente trabalho se propÃs ao desenvolvimento de um programa computacional especÃfico que facilita o uso do modelo viscoelÃstico linear. Este programa realiza o ajuste de curva de sÃries de Prony e a interconversÃo entre propriedades viscoelÃsticas fundamentais no domÃnio do tempo, quais sejam, a FunÃÃo FluÃncia D(t) e o MÃdulo de RelaxaÃÃo E(t). Como principal resultado, foi possÃvel aplicar este programa computacional na caracterizaÃÃo de duas misturas nacionais tÃpicas, Areia Asfalto (AA) e Concreto AsfÃltico (CA), mostrando de forma detalhada os passos necessÃrios para uma representaÃÃo constitutiva viscoelÃstica adequada. Ainda como parte dos resultados obtidos, foi avaliada a eficÃcia da tÃcnica de ajuste de curva por MÃnimos Quadrados NÃo Linear (MQNL) para sÃries de Prony, sob a expectativa de incorporaÃÃo desta tÃcnica em versÃes futuras do programa computacional desenvolvido. Para explicitar o avanÃo da simulaÃÃo mecÃnica de pavimentos que o modelo viscoelÃstico possibilita frente ao modelo elÃstico (clÃssico), ao final do trabalho foram realizadas anÃlises computacionais utilizando o MÃtodo dos Elementos Finitos (MEF) para estimar os parÃmetros mecÃnicos de projeto de pavimentos (tensÃes de deformaÃÃes) considerando o modelo viscoelÃstico das misturas asfÃlticas investigadas, AA e CA. / An asphalt mixture has a complex mechanical behavior can be idealized by a viscoelastoplastic model that considers the existence of recoverable (elastic and viscoelastic) and non-recoverable deformations (plastic and viscoplastic). However, the state of the art of Brazilian research has considered a more restricted model, the linear viscoelastic model. This model treats the mechanical behavior of the material as dependent on the load and the corresponding (temporal) rate, which represents a considerable advance in mechanical-computational modeling of asphalt mixtures compared to the linear elastic (classic) model commonly employed on projects of national pavement design. But the viscoelastic model has some drawbacks that hinder its use. A first drawback is that for a representation compatible with the experimental data, the constitutive viscoelastic characterization requires handling a large number of Prony series coefficients, which makes difficult the curve fitting process and subsequent handling of the series. Futhermore, the formal process of interconversion between the fundamental viscoelastic properties, commonly required for operational reasons, is a non-trivial task. In order to enable the employment of the theory of (linear) viscoelasticity in the characterization of asphalt mixtures, this study proposed the development of a specific computer program that facilitates the use of the linear viscoelastic model. This program carries out curve fitting of Prony series and interconversion of fundamental viscoelastic properties in time domain, namely, Creep Compliance D(t) and Relaxation Modulus E(t). As a main result, it was possible to use this program in characterization of two national typical mixtures, Sand Asphalt (SA) and Asphalt Concrete (AC), showing in details the steps necessary for a proper viscoelastic constitutive representation. Also as part of the results, it was tested the efficacy of the technique of curve fitting by Nonlinear Least Squares (NLS) for the Prony series, under the expectation of incorporating this technique in future versions of this ongoing software. In order to explain the advances that viscoelastic model can enable in mechanical simulation of pavement, instead of using the elastic (classic) model, at the end of this study it was performed computational analysis using the Finite Element Method (FEM) to estimate the mechanical design parameters of pavements (stress and strains), considering the viscoelastic model of the investigated asphalt mixtures, SA and AC.

Chiral separation systems in capillary electrophoresis are in the scope of interest of many research groups all over the world. Therefore, the need to develop reliable theoretical models, which would help to explain phenomena connected with chiral separations or optimization of separation conditions, is obvious. In this thesis several mathematical models and approaches that can fulfill these requirements are presented. First part of the thesis deals with the determination of rate constants of interconversion of enantiomers by means of dynamic capillary electrophoresis. We focused on mixtures of chiral selectors and formulated a mathematical model, which enables to determine rate constants of interconversion in such systems. Mixtures of chiral selectors are very popular in separation practice due to their enhanced enantioselectivity. The theoretical model established in the thesis is able to explain the separation mechanisms of multi-chiral selector systems and to propose and verify possible ways of their optimization. In addition, the separation mechanism in systems with simultaneous cyclodextrin and borate complexation was revealed. Finally we present the complete mathematical model of electromigration in systems with complexation agents. The model is implemented into our simulation tool Simul 5...