O presente trabalho trata da análise da dinâmica de um pêndulo simples excitado em seu suporte por um mecanismo biela-manivela de forma ideal e não-ideal. No caso ideal, verifica-se que o resultado da excitação por este tipo de mecanismo se aproxima do resultado da excitação harmônica de suporte do pêndulo quando o raio da manivela é suficientemente pequeno em comparação com o comprimento da biela. A equação diferencial do sistema é resolvida numericamente e resultados do comportamento pendular são obtidos através de mapas de fase, histórico no tempo e seções de Poincaré. Expoentes de Lyapunov são, também, obtidos para a análise de casos caóticos posteriormente comparados com diagramas de bifurcação. Bacias de atração são desenhadas para os resultados estáveis do pêndulo: oscilatórios ou rotativos. Os resultados obtidos para a excitação por biela-manivela são dos mesmos tipos de movimento observados no caso do pêndulo excitado harmonicamente no suporte, entre eles: ponto fixo, oscilação, rotação pura, oscilação-rotação e o caos. Para a frequência de ressonância principal observam-se resultados caóticos em faixas mais largas de amplitude quando o raio de manivela se aproxima do comprimento da biela. Em frequências ressonantes menores nenhuma relação desse tipo pôde ser estabelecida. Uma análise utilizando o mesmo mecanismo é também feita com excitação por potência limitada de um motor elétrico linear de corrente contínua onde se investigou o efeito de feedback dado pelo pêndulo sobre o motor. Esses resultados são comparados com o caso ideal com a manivela acionada com rotação constante. Observa-se uma supressão do caos no caso não-ideal em casos de menor potência no motor. Entretanto, quando a potência de motor é maior, o modelo ideal coincide com o não-ideal. / In this analysis it was studied the dynamics of a simple pendulum excited by a crank-shaft-slider mechanism in the support ideally and non-ideally. In the ideal case, it was verified the result for an excitation by a crank-shaft-slider approaches to the result of the harmonically excited pendulum when the radius of the crank is sufficiently small in comparison with the length of the shaft. The resultant differential equation is solved numerically and the results of pendulum behavior are obtained by phase portraits, time histories and Poincaré sections. It is also calculated the Lyapunov exponents for the chaotic cases in analysis and a comparison is performed with bifurcation diagrams in the same regions. Basins of attractions are plotted for stable results like oscillatory and rotational solutions. In the results observed for the crank-shaft-slider excitation there are kinds of motion similar to those observed in the harmonic excitation: fixed points, oscillation, pure rotations, oscillation-rotations and chaos. However, in the principal resonance zone, chaotic results were more frequent when the radius of crank approaches the shaft length. A brief analysis is done concerning the same mechanism, but considering the excitation by limited power supply of a linear DC motor. In the sequence it is checked the feedback effect from the pendulum over the motor and comparison with the respective ideal excitation is accomplished where differences are commonly observed. With greater power the ideal model coincides with the nonideal model. In cases of lower power, the two models diverge in the results.

As vibrações em máquinas estão relacionadas à transferência de energia associada a dois efeitos devido ao atrito: a dissipação de energia e a auto-excitação. A dissipação de energia reduz e a auto-excitação aumenta a quantidade de energia de um sistema. Na dinâmica dos sistemas com atrito ocorrem os ciclos limite adere-desliza e movimentos caóticos que podem prejudicar o funcionamento das máquinas. Para o controle desses sistemas torna-se necessária uma estratégia de compensação do atrito. Em geral, não considera-se a influência da dinâmica do sistema oscilante sobre sua fonte de energia ou excitação externa. Em problemas práticos de engenharia, a representação mais realista dessa influência é denominada de sistema não-ideal ou de potência limitada (máquina não-ideal). Neste trabalho, considera-se a dinâmica e o controle de um sistema auto-excitado pelo atrito interagindo com sua fonte de energia. O comportamento dos sistemas ideal e não-ideal são investigados através de simulação numérica e apresentam-se resultados de uma estratégia de controle chaveado para posicionamento e para seguimento de trajetórias periódicas, com compensação robusta do atrito, e a análise de estabilidade pelo método de Lyapunov. / The vibrations of machines are related to energy transference associate to two effects due to the friction: the energy dissipation and the self-excitation. The energy dissipation decrease and the self-excitation increase the system energy quantity. In dynamics of systems with friction occurs the stick-slip limit cycles and chaotic motion that can damage the machine working. For the control of that systems become necessary an compensation strategy of friction. In generally, are not considering the dynamical influence of oscillating system undergo their energy source or external excitation. In engineering practice problems, the more realistic representation of this influence is called non-ideal system or limited power supply (non-ideal machine). This work considers the dynamics and control of a self-excited system due to the friction interacting with their energy source. The behavior of ideal and non-ideal systems are investigated through numerical simulation and results of a switching control strategy for positioning and periodic trajectories tracking, with robust compensation of friction, and the stability analysis by the Lyapunov method are presented.

Les activités anthropiques ont apporté des changements majeurs à notre système global. Par ailleurs, la matière organique dissoute(MOD) du littoral a une grande influence sur le cycle global du carbone et donc sur le changement climatique. L'apport côtier enMOD représente la matière organique terrestre. Les rivières urbanisées sont fortement impactées par la MOD anthropiqueprovenant des usines de traitement des eaux usées. La MOD chromophorique est un sous-groupe de la MOD qui peut absorber lalumière. La MOD fluorescente est à son tour un sous-groupe de la MOD chromophore. Le signal de fluorescence de la MODanthropogénique dans la zone côtière n'est pas bien caractérisé et évalué dans la littérature. Les dégradations induites parphotochimie et les changements au niveau moléculaire sont peuvent de plus influencer la MOD. Dans la présente étude, plusieursexpériences d'irradiation solaire ont été menées avec plusieurs modes de filtration de mélange d’eau de rivière, d’eau de mer et d'uneffluent de station de traitement des eaux usées dans le but de trouver un signal spécifique de fluorescence comme un traceur de laMOD anthropique en utilisant les matrices d'émission d'excitation de la spectroscopie de fluorescence (EEMs) couplées à latechnique statistique chimiométrique de l'analyse factorielle parallèle CP/PARAFAC. Un modèle de régression multilinéaire a étédéveloppé entre la contribution des composantes CP/PARAFAC et la composition du mélange. La cinétique des paramètres derégression multilinéaire a également été étudiée. Des suivis géographiques de l'évolution du signal de fluorescence dans la rivièreGapeau jusqu'à la mer ont été menées ainsi qu’une étude temporelle du signal de fluorescence. Le modèle de régressionmultilinéaire développé a été appliqué pour modéliser les résultats des expériences de champs géographiques et temporelles. Lesrésultats ont montré que le modèle de régression multilinéaire est excellent. Par contre la recherche d'un signal ou d'une signaturede fluorescence spécifique pour l'eau de rivière, les stations d'épuration des eaux usées ou l'eau de mer n'a pas pu être réalisée dansce travail. Dans la zone côtière affectée par l'homme, les matières organiques fluorescentes résiduelles proviennent principalementsinon uniquement de l'usine de traitement des eaux usées, et aucun signal spécifique provenant de l'eau de mer n'a pu être détectéprès de la côte. / Anthropogenic activities have done major changes to our global system. The coastal dissolved organic matter has great influenceon the global carbon cycle and hence climate change. The riverine input of dissolved organic matter represents the terrestrialorganic matter. Urbanized rivers is greatly impacted by the anthropogenic dissolved organic matter coming from wastewatertreatment plants . Chromophoric dissolved organic matter is a subgroup of the dissolved organic matter which can absorb light.Fluorescent dissolved organic matter in turn is a subgroup of the chromophoric dissolved organic matter .The fluorescence signalof the anthropogenic dissolved organic matter in the coastal zone is not well characterized and evaluated in the literature.Photochemically induced degradations and changes at the molecular level is considered to be a great process which could influencethe dissolved organic matter . In the present study, Laboratory mixing experiments several sunlight irradiation experiments wereconducted with several modes of filtration of three endmember mixing components ( River water, Sea water , wastewater treatmentplant effluent discharge) with the objective of finding a specific signal of fluorescence which could be a tracer of the anthropogenicdissolved organic matter through using the fluorescence spectroscopy excitation emission matrices (EEMs) coupled with thechemometric statistical technique of Parallel Factor analysis CP/PARAFAC. Moreover, multilinear regression model between thecontribution of CP/PARAFAC components and two content fraction of River water and Seawater endmember was developed. Inaddition the kinetics of the multilinear regression parameters were investigated. On top of that , geographical investigations of theevolution of fluorescence signal in the Gapeau river till the sea were conducted. Furthermore, Temporal investigation of thefluorescence signal for four water points in the pathway of Gapeau river were done. The multilinear regression model developedwas applied to model the results of the geographical and temporal field experiments. Results have shown that Multilinearregression model for contribution of CP/PARAFAC components is excellent and could be done for the three endmembers. Inaddition the search for specific fluorescence signal or signature for river water, wastewater treatment plants and sea water couldn’tbe done in this work. In human impacted coastal zone, residual fluorescent organic matter come from wastewater treatment plant,and no specific signal from sea water could be detected near the coast.

In der vorliegenden Arbeit untersuchen wir verschiedene Aspekte von Herzrhythmen, von einzelnen Zellen bis zu den gesamten menschlichen Vorhöfen. Das Hauptprojekt ist die Entwicklung eines realistischen und effizienten Modells für die Erregungsausbreitung in den menschlichen Vorhöfen. Im ersten Kapitel untersuchen wir stimulierte Herzellen und den Verlust vom 1:1-Rhythmus für steigende Frequenzen. Weiter untersuchen wir Wellenausbreitung in Gewebe mit besonderen elektrophysiologischen Eigenschaften, die mit chronischen Erkrankungen der Vorhöfe in Verbindung stehen. Dann wenden wir uns Ionenmodellen zu, die ein zentraler Teil des Vorhofmodells sind. Wir untersuchen die Auswirkungen einer Verletzung der Ladungserhaltung, die in allen Ionenmodellen vorliegt, die die Konzentrationen der Ionen als Variablen enthalten, und erklären, warum diese Auswirkungen meist vernachlässigbar sind. Wir entwickeln weiter eine Methode, Ionenmodelle zu vereinfachen und dabei ihre für die Wellenausbreitung wichtigen Eigenschaften nur minimal zu verändern. Diese Methode wenden wir auf ein realistisches Ionenmodell für menschliches Vorhofgewebe an und kombinieren es mit anatomischen Daten, um das gewünschte realistische Vorhofmodell zu erhalten. Schließlich benutzen wir dieses Modell, um mögliche Mechanismen der Enstehung von Herzrhythmusstörungen zu untersuchen. / In this thesis, we study heart rhythms at different levels, from single cells to the entire human atria. The main project of this thesis is the development of a realistic and efficient model of wave propagation in the human atria. We start by studying paced single cells and their loss of 1:1 rhythmicity for increasing frequency. We go on to study wave propagation in tissue with special electrophysiologic properties, related to chronical disease of the atria. Then we treat ionic models, which are a central part of our atrial model. We discuss a recently discovered mathematical degeneracy present in all models of cardiac cells that include intracellular ion concentrations and we explain why this degeneracy has only a negligible effect on wave propagation. We develop a method to reduce the complexity of ionic models while closely retaining their wave propagation properties. Then we apply this method to a realistic ionic model of the human atria and combine it with anatomical data to get the desired model. We use this model to explore possible mechanisms for the genesis of arrhythmias.

Fluorescent nucleic acid base analogues (FBAs) are an important class of molecule used to study the structure and dynamics of DNA and RNA. These base analogues are molecules with structures that resemble one of the natural bases but which, unlike the natural bases, have high fluorescence quantum yields. 2-Aminopurine (2AP) has long been the most widely used fluorescent base analogue and is one of the few base analogues commercially available. One problem with 2AP is that it undergoes significant quenching when incorporated into DNA: the quantum yield decreases 100 fold from that of the free base, thus becoming too low for use in, for example, single molecule studies. A secondary problem is that the 305 nm absorption peak requires excitation in the UV. A variety of new fluorescent base analogues are being produced, with a view to remedying the deficiencies of 2AP and expanding the current range of use. The first part of this thesis explores the one-photon photophysical properties of several of these novel FBAs. The first of these novel FBAs is the 6-aza-uridine family. These compounds, analogues of uridine, have large Stokes shifts and their absorption and emission spectra are red-shifted in comparison to 2AP; their quantum yields as free bases have been shown to exceed that of 2AP and their environmental sensitivity has been demonstrated. Time-resolved measurements reported in this thesis indicate the presence of multiple emitting species. A density functional theory (DFT) study has been carried out to rationalise these emitting species as rotational isomers. Similar fluorescence lifetime measurements were made on a second class of FBAs, the quadracyclic adenine analogues, qANs; these results also indicated the presence of multiple emitting species. Experimental results show that these FBAs undergo excited-state proton transfer. The final FBA studied in this thesis is pentacyclic adenine, pA. This FBA showed some of the most promising characteristics of all the analogues investigated, such as a high quantum yield in both polar and non-polar solvents. A time-resolved investigation into pA-containing oligonucleotides indicated that in an oligonucleotide pA adopts multiple stacked conformations and its behaviour is highly sequence dependent. Several of these aforementioned fluorescent base analogues have absorption spectra in a region that makes them accessible to two-photon (2P) excitation with a Ti:Sapphire laser. In biological systems, multiphoton excitation has several advantages over one-photon excitation. By avoiding the use of ultraviolet light there is reduced phototoxicity. Out of focus photobleaching and autofluorescence are also minimised which leads to a higher signal-to-background ratio and allows deeper tissue penetration to be achieved. Fluorescent base analogues tend to have small Stokes shifts; this is another problem that can be overcome by using two-photon excitation. To be of potential use in multiphoton microscopy, a FBA must have a high two-photon absorption cross-section and a high two-photon brightness. Previously, the highest two- photon brightness measured for a fluorescent base analogue was less than 2 GM. Amongst the base analogues investigated here, are several that have higher two-photon brightness than ever reported for FBAs; these include pA which is shown to have the highest 2P brightness of a FBA in an oligonucleotide, 1.3 GM, and a member of the 6-azauridine family which as a free base has a 2P brightness of 18 GM. Detection of individual molecules represents the ultimate level of sensitivity and enables details about a molecular system that would otherwise be concealed using conventional ensemble techniques to be revealed. With the improved 2P brightness of the molecules measured in this thesis, it has become feasible to detect single FBA molecules using 2P excitation. To maximise the chance of detection, ultrafast, shaped laser pulses have been used as the excitation source. For the first time, the signal has been high enough and the molecule of interest sufficiently photostable such that 2P fluorescence correlation spectroscopy of a fluorescent base analogue in an oligonucleotide could be measured. In summary, this thesis reports the fluorescence lifetimes and two-photon cross-sections of a series of novel fluorescent base analogues, as well as fluorescence correlation spectroscopy measurements of the most promising candidates.

Neste trabalho, uma análise quantitativa e qualitativa para a estabilização dinâmica de um pêndulo invertido com uma força externa senoidal aplicada no ponto de suspensão é feita. Inicialmente, a perturbação externa é composta de um único cosseno, então uma generalização é feita, usando uma soma de N cossenos com diferentes amplitudes e frequências. Aproximações são testadas e o tempo durante o qual o pêndulo invertido permanece estável é explorado quando N é grande, a fim de recuperar o padrão do caso onde N = 1. O caso específico de oscilações periódicas e quase periódicas, quando N = 2, é analisado e diagramas de estabilidade considerando diferentes frequências e amplitudes são estudados. Depois, um ruído Gaussiano additivo é adicionado ao sistema para que a degradação dos diagramas de estabilidade gerados por variâncias diferentes possam ser estudados. Todos os pontos deste trabalho são corroborados por simulações, as quais integram numericamente as equações de movimento do sistema através do método de Runge-Kutta de quarta ordem. Os algoritmos e detalhes extras dos métodos de integração usados são explorados numa publicação deste trabalho, a qual está apresentada, nesta dissertação, como um apêndice. / In this work a quantitative and qualitative analysis of the dynamical stabilization of an inverted pendulum with a sinusoidal external perturbation applied at the suspension point is made. Initially, the external perturbation is composed of a single cosine, then a generalization is made using a sum of N cosines with different amplitudes and frequencies. Approximations are tested, and the time for which the inverted pendulum remains stable is explored when N is large, in order to recover the pattern of the case when N = 1. The specific case of periodic and almost periodic oscillations, when N = 2, is analysed and stability diagrams considering different frequencies and amplitudes are studied. Later, an additive Gaussian noise is added to the system so the degradation of the stability diagrams generated by different variances can be studied. All points of this work are corroborated by simulations, which numerically integrate the system’s equation of motion through a fourth order Runge-Kutta method. Algorithms and extra details on the integration methods used are explored in a publication of this work, which is presented in this thesis as an appendix.

This thesis describes an experimental study of superelastic electron scattering from the 6^2P_3/2 state of caesium. The present status of electron-atom collision studies is initially reviewed and the motivation behind the current work is then presented. A description of the theoretical framework is subsequently provided in the context of the present experimental study, followed by an overview of the several theoretical approaches for describing electron-atom interactions which are currently available. The apparatus and experimental setup used throughout the project are also described in detail. Technical specifications and data are provided, including diagrams (where appropriate) for a laser frequency locking system, electron gun and spectrometer, atomic beam source and data acquisition system. The experimental procedures are explained and discussed, including a detailed analysis of the optical pumping process required to excite the atomic target. A substantial component of this project was to address several potential sources of systematic error and to reduce these wherever possible. All of the errors and uncertainties relevant to the experiment are discussed in chapter 5. In chapter 6 the results of the present superelastic electron scattering experiments are reported for incident electron energies of 5.5eV, 8.5eV and 13.5eV, corresponding to superelastic electron energies of 7eV, 10eV and 15eV. These results are presented as three reduced Stokes parameters, P1, P2, P3 and a coherence parameter, P+ . For comparison, predictions from a number of currently available theories are presented alongside the experimental results. Finally, conclusions are drawn on this work in the context of the current status of electron-atom scattering from alkali-metals.

The present study was largely concerned with measuring accurate absolute values for the electronic state excitation cross sections in H2O, in the incident electron energy range 15eV to 50eV. It is hoped that these data will eventually help to improve the current state of electron - molecule scattering theory, as well as being useful in various fields of modelling. As an illustration of this latter point, the cross sections determined here were used to calculate quantities of importance in atmospheric modelling, namely, electron energy transfer rates and rates for the excitation of water molecules by auroral secondary electrons.

L'étude des propriétés optiques des matériaux semiconducteurs et, notamment, des composés émettant dans l'ultra-violet (UV) constitue depuis quelques années une thématique de recherche de plus en plus importante du fait des applications potentielles de ces matériaux en optoélectronique. Dans cette perspective, étudier les propriétés optiques du nitrure de bore hexagonal (hBN) et des nanotubes de nitrure de bore (BN) est particulièrement intéressant, étant donné leur caractère semiconducteur à grand gap (autour de 6 eV). <br /> L'objectif de cette étude est d'analyser les propriétés optiques de ces matériaux et, plus particulièrement, leurs effets excitoniques, en développant des méthodes de caractérisation optique adaptées pour observer des émissions UV.<br />Les techniques expérimentales de photoluminescence et de cathodoluminescence développées au cours de cette thèse ont tout d'abord permis de comprendre les propriétés de luminescence du hBN. Ainsi, nous avons pu confirmer la présence d'excitons libres émettant à 5.77 eV. Ensuite, en corrélant ces mesures optiques avec des analyses structurales en microscopie électronique en transmission de cristaux individuels, nous avons mis en évidence l'existence d'excitons liés à des défauts structuraux bien déterminés et émettant autour de 5.5 eV. Une fois les propriétés de luminescence du matériau massif connues, nous avons analysé de la même manière différents types de nanotubes de BN multifeuillets. Ces mesures ont pour la première fois montré que ces nano-objets émettent également dans l'UV. En se basant sur notre étude de la luminescence de hBN, nous proposons une interprétation pour l'origine de leurs émissions lumineuses UV.

Cette thèse s'appuie sur la spectroscopie de NiH établie à la fin des années 1980 et au début des années 1990, principalement par le groupe du Pr. R. W. Field au MIT. Les mesures expérimentales ont amélioré de manière significative les travaux antérieurs, tant en spectroscopie en champ nul qu'en spectroscopie Zeeman. Le radical NiH est obtenu avec une source à décharge à température ambiante (310 K). Les radicaux formés dans la décharge sont excités par un laser continu à colorant et étudiés soit en spectroscopie d'excitation laser soit en fluorescence dispersée. Un circuit magnétique à aimants permanents (NdFeB) fournit un champ magnétique statique (0.4 - 0.9 T). En champ nul, les spectres de fluorescence par transformée de Fourier ont élargi les observations de l'état électronique fondamental jusqu'à 6000 cm-1, pour 58NiH et 60NiH. Les énergies sont modélisées avec un Hamiltonien effectif obtenu à partir du formalisme du modèle du 3d9 supermultiplet développé par le groupe de Field. Les mesures Zeeman se sont principalement concentrées sur l'étude des états Ω=3/2. Les facteurs de Landé effectifs ont été déterminés pour chaque niveau ro-vibrationnel pour les états de basse énergie et les états excités de 58NiH. L'inhabituelle dépendance en J des facteurs de Landé obtenus pour les états de basse énergie est expliquée par le modèle du supermultiplet, quantifiant alors l'ampleur des mélanges spin-orbite présents dans les états inférieurs. Les transitions étudiées ont un intérêt astrophysique depuis que plusieurs transitions d'hydrure métallique ont été observées dans les spectres d'étoiles froides et les taches solaires.