Propriedades ópticas, magnéticas e elásticas de duas liomesofases nemáticas tipo I (decilsulfato de sódio/água/ n-decanol e laurato de potássio/água/cloreto de potássio) e urna tipo II (decilsulfato de sódio/água/n-decanol /sulfato de sódio) são estudadas. Nas investigações de tais propriedades as medidas realizadas e instrumentação/meios utilizados foram os seguintes: medidas de sinais ópticos, texturas e temperaturas de transições de fases foram obtidas com auxilio de um microscópio petrográfico com temperatura controlada na platina; medidas de índices de refração e birrefringências obtiveram- se com adaptações do refratômetro de Pulfrich; medidas de susceptibilidades diamagnéticas direcionais foram realizadas com adaptações ao magnetômetro de amostra vibrante; medidas de constantes elásticas foram obtidas com auxilio de uma montagem especial. São realizados cálculos para as susceptibilidades diamagnéticas direcionais e respectivas anisotropias moleculares para alcanos, álcoois e anfifilicos de interesse em liornesofases . Da comparação entre as anisotropias moleculares calculadas e as medidas em liomesofases correspondentes, infere-se que o ordenamento molecular de anfifilicos, nas mesofases, deve ser alto. O método de Kirkwood, que permite correlacionar polarizabilidade elétrica com a susceptibilidade diamagnética molecular média em substâncias puras, é estendido e adaptado a misturas complexas, criando assim urna promissora perspectiva de correlação entre as medidas ópticas e magnéticas em liomesofases. Evidências experimentais diretas, da aplicabilidade da teoria do continuo para termo trópicos às liomesofases, são apresentadas. / The optical, magnetic and elastic properties of three nematic lyomesophases are studied. Two are type I (Na decyl sulfate/ water/n- decanol and K laurate/water/K chloride) and one type II (Na decyl sulfate/water/n- decano l/Na sulfate). To measure these properties we used the following equipment : texture and optical sign were observed by optical microscopy with temperature controlled, hot and cold, stages; refractive indices were measured in an adapted Pulfrich refratometer; the individual elements of the diamagnetic susceptibility tensor were measured with a vibrating sample magnetometer; the elastic constants were measured using the Frederikzs transition in a special experimental set-up. Starting from the concept of localized magnetic susceptibilities, molecular anisotropies were calculated for saturated hydrocarbons , alcohols and amphiphilic compounds, which are of interest for lyomesophases. Comparing these results with the experimentally measured anisotropies of the lyomesophases it is possible to conclude that a high degree of molecular order is present in the nematic amphiphilic systems. The Kirkwood method is extended and adapted for complex mixtures. The use of this method opens new perspectives for exploring the correlation between the molecular polarizability and the mean diamagnetic susceptibility.

A di-2-piridil cetona benzoilhidrazona (DPKBH) é um reagente solúvel em uma série de solventes orgânicos mas pouco solúvel em água. Vem sendo utilizado para a determinação de metais, (principalmente do grupo de transição) como Fe(II), Fe(III), Ni(II), Cu(II), entre outros e como ligante de referência para estudar o comportamento dos íons Fe(II) e Fe(III) em presença de espécies orgânicos encontrados em águas naturais. Com o objetivo de entender melhor as propriedades do DPKBH em meio de etanol, foi necessário determinar as constantes de dissociaçãolionização em diferentes porcentagens desse solvente orgânico (10, 19, 29 e 48 %). Nestas porcentagens de etanol, através de medidas absolutas de pH determinaram-se os pKs do DPKBH utilizando-se a técnica potenciométrica e em 10 e 48 % de etanol através de medidas absolutas de pH associadas às absorbâncias das espécies presentes nos equilíbrios, utilizando-se a técnica espectrofotométrica. Nas devidas porcentagens de etanol, o comportamento do eletrodo foi previamente determinado. Os valores de pK1 3,210; 3,342; 3,398 e 3,360 e de pK2 10,834; 11,013; 11,793 e 11,382 foram obtidos respectivamente para 10, 19, 29 e 48 % de etanol, utilizando-se a técnica potenciométrica. Através da técnica espectrofotométrica os valores de pK1 foram 3,257 e 3,322 e pK2 10,880 e 11,820, em 10 e 48 % de etanol, respectivamente. / The di-2-pyridyl ketone benzoylhydrazone (DPKBH) is a soluble reagent in different organic solvents but slightly soluble in water. It has been used for metal determinations, (mainly transition metals) such as for Fe (II), Fe(III), Ni(II), Cu(II) and also like a reference ligand to study the behavior of Fe(II) and Fe(III) ions in the presence of organic species found in natural waters. So as to better understand the DPKBH properties In ethanol, it was necessary to determine the dissociation/ionization constant in different percentages of ethanol (l0, 19, 29 and 48%). In these ethanol percentages, through absolute pH measurements, pKs of DPKBH could be the found by using the potentiometric technique, and in 10 and 48% of ethanol the pKs of DPKBH were determined with pH measurements associated to absorbance of the species present in the equilibria by using the spectrophotometric technique. In appropiate percentage of ethanol the behavior of the glass electrode was previously determined. The pK1 values 3.210; 3.342; 3.398 and 3.362, and pK2 10.834; 11.013; 11.793 and 11.382 were found for 10,19,29,48 % of ethanol, by using the potentiometric technique. The spectrophotometric technique led to pK1 values 3.257 and 3.322, and the pK2 ones 10.880 and 11. 820 in 10 and 48 % of ethanol respectively.

Propriedades ópticas, magnéticas e elásticas de duas liomesofases nemáticas tipo I (decilsulfato de sódio/água/ n-decanol e laurato de potássio/água/cloreto de potássio) e urna tipo II (decilsulfato de sódio/água/n-decanol /sulfato de sódio) são estudadas. Nas investigações de tais propriedades as medidas realizadas e instrumentação/meios utilizados foram os seguintes: medidas de sinais ópticos, texturas e temperaturas de transições de fases foram obtidas com auxilio de um microscópio petrográfico com temperatura controlada na platina; medidas de índices de refração e birrefringências obtiveram- se com adaptações do refratômetro de Pulfrich; medidas de susceptibilidades diamagnéticas direcionais foram realizadas com adaptações ao magnetômetro de amostra vibrante; medidas de constantes elásticas foram obtidas com auxilio de uma montagem especial. São realizados cálculos para as susceptibilidades diamagnéticas direcionais e respectivas anisotropias moleculares para alcanos, álcoois e anfifilicos de interesse em liornesofases . Da comparação entre as anisotropias moleculares calculadas e as medidas em liomesofases correspondentes, infere-se que o ordenamento molecular de anfifilicos, nas mesofases, deve ser alto. O método de Kirkwood, que permite correlacionar polarizabilidade elétrica com a susceptibilidade diamagnética molecular média em substâncias puras, é estendido e adaptado a misturas complexas, criando assim urna promissora perspectiva de correlação entre as medidas ópticas e magnéticas em liomesofases. Evidências experimentais diretas, da aplicabilidade da teoria do continuo para termo trópicos às liomesofases, são apresentadas. / The optical, magnetic and elastic properties of three nematic lyomesophases are studied. Two are type I (Na decyl sulfate/ water/n- decanol and K laurate/water/K chloride) and one type II (Na decyl sulfate/water/n- decano l/Na sulfate). To measure these properties we used the following equipment : texture and optical sign were observed by optical microscopy with temperature controlled, hot and cold, stages; refractive indices were measured in an adapted Pulfrich refratometer; the individual elements of the diamagnetic susceptibility tensor were measured with a vibrating sample magnetometer; the elastic constants were measured using the Frederikzs transition in a special experimental set-up. Starting from the concept of localized magnetic susceptibilities, molecular anisotropies were calculated for saturated hydrocarbons , alcohols and amphiphilic compounds, which are of interest for lyomesophases. Comparing these results with the experimentally measured anisotropies of the lyomesophases it is possible to conclude that a high degree of molecular order is present in the nematic amphiphilic systems. The Kirkwood method is extended and adapted for complex mixtures. The use of this method opens new perspectives for exploring the correlation between the molecular polarizability and the mean diamagnetic susceptibility.

O presente trabalho começa por uma apresentação monográfica do fenômeno de adsorção, que dá acesso à bibliografia existente sobre o assunto. Numa extensa parte experimental desenvolveu-se um eletrodo de amálgama gotejante e um eletrodo de gota pendente mercúrio capaz de gerar gotas com área reprodutível dentro de ± 0,1%. Fez-se, também, a implantação da técnica da cronocoulometria, com os recursos disponíveis neste Instituto de Química. Realizou-se um estudo polarográfico preliminar onde se observaram diversos efeitos inibitivos sobre a reação de eletrodo do Cd(II), ligados á presença dos fenantrolino complexos de Cd(II) e de Fe(II), com participação de ânions. O sistema cádmio(II)/piridina/cloreto foi estudado potenciometricamente, tendo sido avaliadas as seguintes constantes globais de estabilidade βij = ‌CdpyiClj‌/‌Cd‌ ‌py‌ i‌Cl‌j (i, número de ligantes piridina, e j, de cloreto): β01 = 25,36, β02 = 96,0, β03 = 48,3, β04 = 65,8, β10 = 23,5, β11 = 550, β12 = 2600, β13 = 550, β14 = 1100, β20 = 690, β21 = 9740, β22 = 9400, β30 = 270, β31 = 3500, β32 = 37400, β40 = 8450, β41 = 54400. Para chegar às constantes de equilíbrio usou-se um processo iterativo de cálculo. As medidas foram realizadas com um eletrodo de amálgama gotejante, após comprovar-se que o eletrodo íon-seletivo de cádmio de estado sólido é inadequado para esta finalidade. Empregou-se um novo tipo de diagramas para representar a contribuição percentual das espécies formadas, em função dos dois ligantes. Estudou-se, através da cronocoulometria, a adsorção do sistema Cd(II)/py/Cl-, em diversas condições, fixando a concentração do metal e do cloreto e variando-se a concentração de py. Ficou estabelecido que a adsorção dos complexos é um processo competitivo com a dos ligantes. Há sempre um máximo de adsorção na faixa de 0,1 a 0,5 M de py. Encontraram-se evidências de que as espécies mistas neutras são preferencialmente adsorvidas. / The present thesis starts with the monographic discussion of the adsorption phenomena, with several references. There is an extensive experimental part referred to the development of a simple dropping amalgam electrode, a hanging mercury drop electrode whose area is reproductible within 0,1%, and the introduction of the double step chronocoulometric method w1th the resources of this Chemistry Institute, was done. In a preliminary polarographic study, several inhibiting effects on the Cd(II) electrode reaction, due to the presence of cadmium(II) and iron(II) complexes of phen participation of some anions has been observed. A potentiometric study of the cadmium(II)/pyridine//chloride system lead to the evaluation of the overall stability, βij = ‌CdpyiClj‌/‌Cd‌ ‌py‌ i‌Cl‌j (i, number of py ligands and j of chloride ones): β01 = 25,36, β02 = 96,0, β03 = 48,3, β04 = 65,8, β10 = 23,5, β11 = 550, β12 = 2600, β13 = 550, β14 = 1100, β20 = 690, β21 = 9740, β22 = 9400, β30 = 270, β31 = 3500, β32 = 37400, β40 = 8450, β41 = 54400. To obtain the equilibrium constants from the experimental data, an iterative calculation process was used. The measurements has been made with an amalgam electrode, after unsucessfull tests with a solid state cadmium ion selective electrode. A new type of diagram was used to present the percent distribution of the species with the change in the concentration of the ligands, in substitution to the predominance area diagram. In add1tion, the chronocoulometric study of the Cd(II)/ /py/Cl- system was done at several experimental conditions, by fixing the concentration of the metal and the chloride, and changing in wide extension the pyridine concentration. The adsorption of the complexes is a competitive process with the free ligands, and allways exhibits a maxima between .1 and .5M pyridine. There are strong evidences indicating that the neutral mixed species are preferabbly adsorbed.

Neste trabalho, apresentamos uma fórmula da variação das constantes para EDOs generalizadas lineares em espaços de Banach. Mais especificamente, estamos interessados em estabelecer uma relação entre as soluções do problema de Cauchy para uma EDO generalizada linear \'dx SUP. d \'tau\' =D[A(t )x], x(\'t IND. 0\') = \'x SOB. ~\' e as soluções do problema de Cauchy perturbado \'dx SUP. d \'tau\' =D[A(t )x +F(x, t )], x(\'t IND. 0\') = x(\'t IND. 0\') = \'x SOB. ~\' , em que as funções envolvidas são Perron integráveis e, portanto, admitem muitas descontinuidades e oscilações. Também provamos a existência de uma correspondência biunívoca entre o problema de Cauchy para uma EDF linear da forma { \' y PONTO\' =L(t )\'y IND. t\' , \'y IND. t IND. 0 = \\varphi\', , em que L é um operador linear e limitado e \'varphi\' é uma função regrada, e uma certa classe de EDOs generalizadas lineares. Como consequência, obtemos uma fórmula da variação das constantes relacionando as soluções da EDF linear e as soluções do problema perturbado { \'y PONTO\' = L(t )\'y IND.t\' + f (\'yIND. t\' , \'y IND. t IND. 0\' = \'\\varphi \', em que a aplicação \'t SETA \' f (\'y IND. t\' , t) é Perron integrável, com t em um intervalo de R, para cada função regrada y / In this work, we present a variation-of-constants formula for linear generalized ordinary differential equations in Banach spaces. More specifically, we are interested in establishing a relation between the solutions of the Cauchy problem for a linear generalized ordinary differential equation \'dx SUP. d \\tau\' =D[A(t )x], x(\'t IND. 0\') = x (\'t IND. 0\') = \'x SOB. ~\' and the solutions of the perturbed Cauchy problem \'dx SUP. \'d \\tau\' =D[A(t )x +F(x, t )], x(\'t IND. \'0) = \'x SOB.~\', where the functions involved are generalized Perron integrable and, hence, admit many discontinuities and oscillations. We also prove that there exists a one-to-one correspondence between the Cauchy problem for a linear functional differential equations of the form { \'y PONTO\' = L(t) \'y IND. t, \'y IND> 0 = \\varphi, where L is a bounded linear operator and \" is a regulated function, and a certain class of linear generalized ordinary differential equations. As a consequence, we are able to obtain a variation-of-constants formula relating the solutions of the linear functional differential equation and the solutions of the perturbed problem { \'y PONTO\' = L(T)\'y IND.t´+ f (\'y IND. t\', t), \'y IND.t IND. 0\' = \\varphi, where the application t \'ARROW\' f(\'y IND. t\', t) is Perron integrable, with t in an interval of R, for each regulated function y

This thesis aims to investigate the controllability and observability of the discrete fractional linear time-invariant state-space model. First, we will establish key concepts and properties which are the tools necessary for our task. In the third chapter, we will discuss the discrete state-space model and set up the criteria for these two properties. Then, in the fourth chapter, we will attempt to apply these criteria to the discrete fractional model. The general flow of our objectives is as follows: we start with the first-order linear difference equation, move on to the discrete system, then the fractional difference equation, and finally the discrete fractional system. Throughout this process, we will develop the solutions to the (fractional) difference equations, which are the basis of our criteria.

Les dépôts effectués sur substrats de silicium sont très courants notamment dans le domaine de la microélectronique. Les propriétés physiques recherchées pour ce type de structures dépendent fortement de celles de la couche. Il apparaît donc essentiel de connaître les paramètres élastiques ainsi que l’épaisseur des films considérés. De plus, la détection de certains défauts concernant la couche est souvent recherchée. L’objectif de ce travail a été de contribuer à la caractérisation de structures du type couche sur substrat. Pour cela, les ultrasons-lasers présentent de nombreux avantages puisqu’ils autorisent entre autres leur contrôle non destructif sans contact. Les ondes acoustiques de surface dans une gamme de fréquence s’étendant jusqu’à 45 MHz ont été utilisées. Nous avons développé différents modèles analytiques et les résultats expérimentaux ont aussi été comparés à certaines simulations par éléments finis. Plus particulièrement, nous avons montré qu’il était possible d’obtenir l’ensemble des paramètres élastiques du substrat et de la couche ainsi que l’épaisseur de cette dernière. Par ailleurs, nous nous sommes aussi intéressés à la détection de certains défauts en régime impulsionnel mais aussi quasi-monochromatique. Des résultats originaux concernant l’effet d’une absence de couche de forme déterminée sur le premier mode de Rayleigh ou bien encore de problèmes d’adhésion ont été présentés. Sur ce dernier point, une méthode innovante permettant de distinguer un fort niveau d’adhésion d’un faible a aussi été introduite. / Thin films deposited on silicon substrates are very common especially in microelectronic applications. The physical properties expected for these types of structures depend on the properties of the layer. Therefore, it is essential to know elastic parameters and thickness of the films considered. Furthermore, some layer defects detection is often required. The aim of this work was to contribute to the characterization of structures composed of a single layer deposited on a substrate. For this, laser ultrasonics offers many advantages since it is nondestructive and non-contact method. Surface acoustic waves excited in a frequency range up to 45 MHz are used. Analytical models have been developed and experimental results have also been compared with some finite element simulations. More specifically, we have shown that it was possible to obtain the thickness of the layer and all elastic parameters of both substrate and layer. In addition, we have been interested in the detection of various defects with a broadband and quasi-monochromatic excitation. Original results concerning the effect of a lack of layer with a specific geometry on the first Rayleigh mode or even adhesion problems were presented. Concerning this last point, an innovative method to tell difference between high and low adhesion was introduced.

L'intégration des sources d'énergies renouvelables sur le réseau électrique est complexe en raison de leur nature intermittente et décentralisée. Le micro-réseau est une approche prometteuse pour interconnecter des générateurs distribués (DGs) locaux, alimenter des charges locales et également échanger de l'énergie avec le réseau électrique de manière contrôlée. Ce mode de production/consommation locales permet d'éviter la transmission d'électricité sur de longues distances, et implique donc une plus grande efficacité. Ces travaux se concentrent sur l'analyse et le contrôle du micro-réseau continu afin que les DGs se répartissent l'alimentation des charges et qu'ils maintiennent également la tension du bus continu. À l'équilibre, les contraintesde la commande du statisme classique (droop control) pour un système comportant de multiples DGs sont analysés, et une méthode de compensation mixte est proposée pour améliorer simultanément le maintien en tension et le partage du courant de charge. En dynamique, le modèle global du système est construit en introduisant une inductance virtuelle dans le circuit équivalent du DG, puis plusieurs modèles d'ordre réduit sont examinés pour vérifier leur efficacité dans l'analyse de la stabilité du système. Un modèle multi-échelle d'ordre réduit (RMM) est proposé afin de conserver les contraintes temporelles ainsi que de réduire la complexité du système. Enfin, une méthode basée sur le contrôle de rejet de perturbation active (ADRC) est présentée afin de mettre en oeuvre le contrôle local de la tension des DG en prenant en compte l'échelle de temps. Cette méthode permet d'améliorer la dynamique du système de contrôle en ajustant la largeur de bande passante de la commande et de l'observateur. Les analyses et les méthodes de contrôle proposées sont vérifiées par des essais expérimentaux dans notre plateforme au laboratoire. / The direct integration of renewable energy resources to the utility grid is pretty tough due to their intermittent feature and dispersed nature. Microgrid is one promising approach to gather the local distributed generators (DGs), supply local loads as well as exchange power with the utility grid as a controllable unit. This local-generation-localconsumption mode is able to avoid the long distance power transmission, thus can benefit a higher efficiency. The control aim of DC microgrids is to make the multiple DGs share the load properly as well as maintain the DCbus voltage stable. In steady state, the constrains of the classic droop control in multiple DGs environment are analyzed, and a mixed compensation method using common current is proposed to improve the voltage and load sharing performance simultaneously. In dynamic state, the system comprehensive model is constructed by the introduction of virtual inductor in the equivalent circuit of the DG, then several reduced-order models are examined to check their effectiveness for the system stability analysis. A reduced-order multi-scale model (RMM) is proposedto keep major time scale information as well as reduce the system complexity. Finally, an active disturbance rejection control (ADRC) based control method is proposed to realize the time scale droop control. It can effectively adjust the dynamic of the local control by adjusting the bandwidth of the Linear Extend State Observer or/and the controller. The proposed analysis and control methods are verified by experimental tests in our laboratory platform.

<p>This thesis reports the results of a twofold study on the recently proposed phenomenon of &lsquo / stellar pulsations&rsquo / in young brown dwarfs by the seminal study of Palla and Baraffe (2005) (PB05, thereafter). The PB05 study presents results of a non-adiabatic linear stability analysis showing that young brown dwarfs should become pulsationally unstable during the deuterium burning phase of their evolution.</p>

In this thesis a computational complement to experimental observables will be presented. Computational tools such as molecular dynamics and quantum chemical tools will be used to aid in the interpretation of experimentally (NMR) obtained structural data. The techniques are applied to study the dynamical features of biologically important carbohydrates and their interaction with proteins. When evaluating conformations, molecular mechanical methods are commonly used. Paper I, highlights some important considerations and focuses on the force field parameters pertaining to carbohydrate moieties. Testing of the new parameters on a trisaccharide showed promising results. In Paper II, a conformational analysis of a part of the repeating unit of a Shigella flexneri bacterium lipopolysaccharide using the modified force field revealed two major conformational states. The results showed good agreement with experimental data. In Paper III, a trisaccharide using Langevin dynamics was investigated. The approach used in the population analysis included a least-square fit technique to match T1 elaxation parameters. The results showed good agreement with experimental T-ROE build-up curves, and three states were concluded to be involved. In Paper IV, carbohydrate moieties were used in the development of prodrug candidates, to “hide” peptide opioid receptor agonists. Langevin dynamics and quantum chemical methods were employed to elucidate the structural preference of the compound. The results showed a chemical shift difference between hydrogens across the ring for the two isomers as well as a difference in the coupling constant, when taking the dynamics into account. In Paper V, the interaction of the Salmonella enteritidis bacteriophage P22 with its host bacterium, involves an initial hydrolysis of the O-antigenic polysaccharide (O-PS). Docking calculations were used to examine the binding between the Phage P22 tail-spike protein and the O-PS repeating unit. Results indicated a possible active site in conjunction with NMR measurements.