Ce travail de cette thèse porte sur la dynamique des protéines, accompagnées de leur eau d'hydratation, une couche de solvant autour des protéines vitale pour leur fonction biologique. Chacune de ces deux composantes s'accompagne d'une dynamique qui lui est propre et dont la réunion reforme le paysage énergétique du système biologiquement actif. La mise en application conjointe de la deutération sélective, de la diffusion incohérente de neutrons ainsi que la spectroscopie terahertz a permis d'explorer de manière indépendante la dynamique des protéines et de celles des couches d'hydratation. L'influence de l'état de repliement de la protéine sur sa dynamique a été étudié par diffusion élastique de neutrons. Les protéines globulaires se sont montrées moins dynamiques que ses analogues intrinsèquement désordonnées. Eux même semblent être plus rigides que les protéines dépliées non physiologiques. L'état d'oligomérisation et les conséquences sur la dynamique de ces protéines ont été développés. Les agrégats d'une protéine globulaire se sont avérés être plus flexibles que la forme soluble. A l'inverse, les agrégats d'une protéine désordonnée voient leur dynamique moyenne baisser par rapport à la forme soluble. Ces observations témoignent de la grande diversité de dynamiques à travers le protéome. Les expériences de diffusion incohérente de neutrons sur les couches d'hydratation des protéines globulaires et désordonnées ont permis d'obtenir des informations sur la nature des mouvements de l'eau autour des protéines. Les mesures ont mis en évidence la présence de mouvements translationnels concomitants à l'apparition de la transition dynamique dans les couches d'hydratations, vers 220 K. Les mesures ont de même montré un couplage plus fort entre une protéine désordonnée et son eau d'hydratation que celui entre une protéine globulaire et son eau d'hydratation. La nature de la couche d'hydratation et son influence sur sa dynamique ont été explorés, avec l'utilisation de polymères qui miment le comportement de l'eau et agissent comme source de flexibilité pour la protéine. Pour terminer, la dynamique des groupements méthyles, impliqués dans les modifications dynamiques observées à 150 et 220 K, a été étudiée. / This thesis work focused on the dynamics of proteins, surrounded by their hydration layer, a water shell around the protein vital for its biological function. Each of these components is accompanied by a specific dynamics which union reforms the complex energy landscape of the system. The joint implementation of selective deuteration, incoherent neutron scattering and terahertz spectroscopy allowed to explore the dynamics of proteins and that of the hydration shell. The influence of the folding state of protein on its dynamics has been studied by elastic neutron scattering. Globular proteins were less dynamic than its intrinsically disordered analogues. Themselves appear to be stiffer than non physiological unfolded proteins. The oligomerization state and the consequences on the dynamics were investigated. Aggregates of a globular protein proved to be more flexible than the soluble form. In contrast, aggregates of a disordered protein showed lower average dynamics compared to the soluble form. These observations demonstrate the wide range of dynamics among the proteome. Incoherent neutron scattering experiences on the hydration layer of globular and disordered proteins have yielded information on the nature of water motion around these proteins. The measurements revealed the presence of translational motions concomitant with the onset of the transition dynamics of hydration layers, at 220 K. Measurements have also shown a stronger coupling between a disordered protein and its hydration water, compared to a globular protein and its hydration shell. The nature of the hydration layer and its influence on its dynamics has been explored with the use of polymers that mimic the water behavior and that act as a source of flexibility for the protein. Eventually, the dynamics of methyl groups involved in the dynamical changes observed at 150 and 220 K, was investigated.

The aim of this thesis is to explain the production of urban space at the southwestern periphery of Ankara between 1985 and 2007. It has been argued that urban development is not a self-regulatory process / on contrary it is a process produced by urban planning practice. In this respect this thesis asks how and what extent urban planning produces particular urban pattern at the peripheral areas. The southwestern periphery is taken into account as a field of case study due to the peculiar development dynamics. Historical development in this area reveals a contrast between planned development directed by master plans and problematic development that has been produced by fragmented and incoherent planning processes. The difficulties of urban plans and urban planning are intimately related with the legal and administrative structures of the planning system. A methodology offered in this thesis is devised to analyze the incremental and piecemeal nature of planning process with reference to these structures. The results of the research has shown that when confronted with legal and administrative conflicts and struggles, fragmented planning decisions manipulating the existing master plan intensify and become the root cause of dispersed, awkward and haphazard spatial patterns of urban expansion.

The aim of this thesis is to explain the production of urban space at the southwestern periphery of Ankara between 1985 and 2007. It has been argued that urban development is not a self-regulatory process / on contrary it is a process produced by urban planning practice. In this respect this thesis asks how and what extent urban planning produces particular urban pattern at the peripheral areas. The southwestern periphery is taken into account as a field of case study due to the peculiar development dynamics. Historical development in this area reveals a contrast between planned development directed by master plans and problematic development that has been produced by fragmented and incoherent planning processes. The difficulties of urban plans and urban planning are intimately related with the legal and administrative structures of the planning system. A methodology offered in this thesis is devised to analyze the incremental and piecemeal nature of planning process with reference to these structures. The results of the research has shown that when confronted with legal and administrative conflicts and struggles, fragmented planning decisions manipulating the existing master plan intensify and become the root cause of dispersed, awkward and haphazard spatial patterns of urban expansion.

No description available.

Helium-3 surface spin echo spectroscopy (HeSE) has been used to measure the diffusive dynamics of adsorbates on close-packed metal surfaces, namely hydrogen on Cu(111), Pd(111) and Ru(0001), carbon and oxygen on Ru(0001), and oxygen on Cu(111). Chapter 2 reviews the HeSE technique and describes the relevant dynamical models and statistical methods used to interpret data in later chapters. The performance of the ionizing detector is analysed, with a focus on the signal-to-noise ratio. In Chapter 3 expressions for the classical intermediate scattering function (ISF) are introduced for open and closed systems. The effects of corrugation and surface-perpendicular motion on the amplitude of different components in the ISF are modelled analytically and compared with simulation. The exact ISF for a particle on a flat surface, obeying the Generalized Langevin Equation with exponential memory friction, is calculated analytically. In Chapter 4 the analytical ISF is calculated for quantum Brownian motion and for coherent tunneling dynamics in a tight binding system. The bounce method for calculating quantum mechanical hopping rates in dissipative systems is applied to model diffusion of hydrogen on Ru(0001). Chapter 5 presents the first HeSE measurements of carbon and oxygen diffusion. C/Ru(0001) diffusion is assigned to a small carbon cluster. The jump rate has an activation energy $E_{A}=292\pm7\,$meV in the temperature range $550\,\textrm{K}\leq T \leq 1300\,$K. Oxygen diffusion is significantly slower. By comparison of literature data with the new HeSE results, the activation energy for oxygen diffusion at low coverage is estimated as $650\pm10$meV. Oxygen measurements at high coverage $\theta\approx0.22\,$ML are consistent with strong mutual O-O interactions. Surface diffusion is also observed after exposing Cu(111) to oxygen. Chapter 6 presents low-coverage measurements of protium (H) and deuterium (D) diffusion on Ru(0001), Pd(111) and Cu(111). In the quantum activated regime there is evidence for multiple jumps in all three systems, suggesting a low dynamical friction. The measurements on Ru(0001) indicate that the deep tunneling rate is much slower for D than for H.

Le sujet porte essentiellement sur la caractérisation du PolyEthylène Haute Densité (PEHD) à l'échelle de la microstructure au cours de sollicitations mécaniques. Une première partie présente une stratégie de modélisation du comportement du polymère qui se veut à la fois représentative des observations mécaniques macroscopiques et surtout adaptée à une métrologie fine de ses paramètres constitutifs. L'accent se porte ensuite sur des techniques d'investigation à la mésoéchelle (ordre du micromètre) par technique in-situ de transport de lumière incohérente polarisée (IPSLT) et par microtomographie X réalisée sous rayonnement synchrotron. L'objectif est de comprendre les phénomènes qui interviennent à toutes ces échelles pendant les phases successives de transformation de la matière, qui passe d'un état homogène quasi-isotrope constitué de deux phases, cristalline et amorphe, vers une mésostructure dite fibrillaire, fortement anisotrope. Entre autres constats majeurs, nous montrons que le polymère semi-cristallin étudié ne présente pas de phénomène de cavitation et que contrairement à la majorité des résultats publiés dans la littérature, le blanchiment observé ne peut donc pas lui être attribué. Ce résultat montre que les processus de déformation mécanique mis en jeu dans l'élasto-visco-plasticité avec durcissement hyperélastique, peuvent tout à fait se concevoir sans mécanismes prépondérants de création de porosité. Il ouvre donc la voie à de nouveaux scénarios pour expliquer les évolutions de microstructure observées en lien avec la déformation / This thesis mainly concerns the characterization of High Density Polyethylene (HDPE) at the microscopic scale when mechanically solicited. A first part presents a modeling strategy of the polymer behavior that is representative of the observations at the macroscopic scale and adapted to a good metrology of its constitutive parameters. Then, this work focus on investigation techniques that probe the mesoscopic scale (micrometer scale) through a technique (in-situ) based on the transport of incoherent and polarized light (IPSLT) ; and synchrotron X-ray microtomography. The aim is to understand the phenomena that take place at this scale during the successive phases of matter transformation (which switch from a homogeneous biphasic quasi-isotropic state to a very anisotropic fibrillar mesostructure). We show that this polymer does not exhibit any cavitation phenomena and that contrary to most of the results published in the literature, whitening which can be observed macroscopically is not due to the presence of cavities. This result suggests that the mechanical deformation processes put at stake in elastoviscoplasticity with hyperelastic hardening can take place without paramount porosity mechanisms and paves the way for new scenarios that could explain the microstructure evolution as function of strain

Le sujet de cette thèse porte sur les phénomènes d’auto-organisations d’ondes optiques non-linéaires. Ce travail principalement théorique et numérique repose sur différents formalismes de turbulenced’ondes, les singularités Hamiltoniennes et diverses expériences.Une première partie de la thèse porte sur les processus irréversibles de thermalisation et de conden-sation d’ondes. Le phénomène de condensation se caractérise par la formation d’une structure cohérenteà grande échelle (condensat) qui reste immergée dans une mer de fluctuations aux petites échelles (parti-cules non condensées). En dépit des longueurs de propagation rédhibitoires pour atteindre l’état d’équilibrecondensé, nous avons mis en évidence expérimentalement et théoriquement un phénomène de pré-condensation qui a lieu loin de l’équilibre etqui joue un rôle précurseur pour l’état d’équilibre asymptotique. Par ailleurs, sur la base d’observations ex-périmentales récentes du phénomène de nettoyage de faisceau dans une fibre optique multimode, nousavons développé une approche cinétique de turbulence d’ondes prenant en compte le désordre structu-rel du matériau. La théorie révèle que le désordre entraîne une accélération significative du processus decondensation permettant d’expliquer l’effet de nettoyage de faisceau. Les expériences effectuées reportentl’observation d’une transition de la distribution thermique vers la condensation, avec une fraction macro-scopique de puissance condensée dans le mode fondamental. Nous avons aussi étudié l’impact d’une ré-ponse fortement non-locale (ou non-instantanée) sur la propagation d’un speckle, ce qui a permis d’iden-tifier un mécanisme d’émergence spontanée de cohérence de phase à longue portée.Une seconde partie des travaux est centrée sur le phénomène d’attraction de polarisation lors de l’in-jection d’ondes incohérentes aux deux extrémités d’une fibre optique. La dynamique spatio-temporelle desondes partiellement polarisées contra-propagatives relaxe vers un état stationnaire où se produit un phé-nomène d’auto-polarisation survenant au point milieu de la fibre. Ce phénomène est lié à la présence desingularités dans le système Hamiltonien associé à l’état stationnaire. / The subject of this thesis concerns the study of phenomena of self-organization of incoherentoptical waves. This work is essentially theoretical and numerical and relies on different formalisms of waveturbulence theory, the Hamiltonian singularities, and different experiments.The first part of the thesis deals with the irreversible processes of thermalization and condensation ofincoherent waves. The phenomenon of condensation is characterized by the formation of a large scale co-herent structure (condensate) that remains immersed in a sea of small scale fluctuations (uncondensedparticules). In spite of the large propagation lengths required to reach the condensed equilibrium state, wehave identified theoretically and experimentally in atomic vapors a phenomenon of pre-condensation thatoccurs far from thermal equilibrium and that plays the role of a precursor for the asymptotic equilibriumstate. On the other hand, on the basis of recent experimental observations of the effect of beam self-cleaningin multimode optical fibers, we have developed a kinetic wave turbulence approach that accounts for theimpact of a structural disorder of the material. The theory reveals that disorder leads to a significant ac-celeration of the condensation process, which can explain the beam self-cleaning effect. Our experimentsreport the observation of the transition from the thermal distribution toward condensation with a macro-scopic fraction of condensed power into the fundamental mode. We have studied the impact of a highlynonlocal (or non-instantaneous) response on the nonlinear propagation of a speckle beam, which allowedus to identify a mechanism of spontaneous emergence of long-range phase coherence.The second part of the manuscript is based on a phenomenon of polarization attraction when two in-coherent waves are injected at both ends of an optical fiber. The spatio-temporal dynamics of the counter-propagating partially polarized waves relax toward a quasi-stationary state characterized by a phenomenonof self-polarization that occurs just in the middle point of the optical fiber. This effect is related to the pre-sence of singularities in the Hamiltonian system associated to the stationary state.

Ce travail vise à approfondir la connaissance du comportement mécanique de polymères structurés sur de multiples échelles. Il repose sur l'acquisition simultanée d'informations couplées relatives à la mécanique, à la thermique et à la microstructure. Nous avons à cet effet étudié le comportement du Polyéthylène Haute Densité (PEHD) sous sollicitations de traction à déformation contrôlée à l'aide de trois techniques optiques utilisées in situ simultanément : (i) Le système Vidéotraction® pour l'accès aux contraintes et aux déformations vraies. (ii) La thermographie infrarouge pour l'accès aux sources thermiques. (iii) Une technique de rétrodiffusion de lumière (ISLT) pour l'accès à une forme d'endommagement. Le corps du travail porte sur la reconstruction des sources thermiques 2D à partir de cartographies des champs de température mesurés au cours d'essais. Le problème inverse de reconstruction des champs de sources ther-miques est résolu par deux méthodes différentes : minimisation sous contrainte avec formulation adjointe et décomposition modale. Des techniques de régularisation du problème sont décrites en détail pour chaque méthode. D'autre part, la technique ISLT nous permet de suivre l'endommagement : l'apparition progressive de "mi-crocavités" isotropes puis un développement d'une forte anisotropie pendant la phase de durcissement hyperélastique. Nous montrons que ces informations sur la microstructure viennent corroborer les phénomènes observés sur la source thermique. Nous replaçons alors l'ensemble des informations obtenues dans le contexte d'une modélisation thermodynamique des lois de comportement. Une étude de sensibilité aux paramètres du modèle est développée, ce qui conduit à une réduction du modèle adaptée à leur bonne estimation / This research aims at looking further into current knowledge of the mechanical behavior of semi-crystalline polymers at multiple scales. It relies on the simultaneous acquisition of coupled information relating to me-chanical, thermal and microstructural behaviors. For this purpose, we have studied the response of High Density Polyethylene (HDPE) under tensile tests with controlled strain rates, using three optical techniques : (i) Vidéotraction®, a videoextensemeter to access the true stress and strain. (ii) Infrared thermography to access the thermal sources evolution. (iii) Backscattering of Incoherent Light (ISLT technique) to access information on damage mechanisms. The core of the research concerns the reconstruction of the 2D thermal sources starting from temperature fields maps measured during the test. This ill-posed problem has been solved with two different methods : A constrained optimization based on the adjoint formulation and a minimization based on a reduced spectral model. The regularization tools used in the problem are detailed for each method. The ISLT technique allows to monitor damaging processes due to crazing : the creation of isotropic micro-cavities followed by the development of a strong anisotropy during the hardening phase. We show that these information at microstructural level confirm the evolutions of the heat source thermal. All these experimental information are finally considered within a thermodynamical framework used for deri-ving constitutive laws. A sensitivity analysis applied to the parameters of our law led to a reduced model that is more appropriate for their proper estimation

Advances in digital signal processing (DSP) and computing technology have resulted in the emergence of increasingly adaptive radar systems. It is clear that the Electronic Attack (EA), or jamming, of such radar systems is expected to become a more difficult task. The reason for this research was to address the issue of jamming adaptive radar systems. This required consideration of adaptive jamming systems and the development of a methodology for outlining the features of such a system is proposed as the key contribution of this thesis. For the first time, game-based optimization methods have been applied to a maritime counter-surveillance/counter-targeting scenario involving conventional, as well as so-called ‘smart’ noise jamming.Conventional noise jamming methods feature prominently in the origins of radar electronic warfare, and are still widely implemented. They have been well studied, and are important for comparisons with coherent jamming techniques.Moreover, noise jamming is more readily applied with limited information support and is therefore germane to the problem of jamming adaptive radars; during theearly stages when the jammer tries to learn about the radar’s parameters and its own optimal actions.A radar and a jammer were considered as informed opponents ‘playing’ in a non-cooperative two-player, zero-sum game. The effects of jamming on the target detection performance of a radar using Constant False Alarm Rate (CFAR)processing were analyzed using a game theoretic approach for three cases: (1) Ungated Range Noise (URN), (2) Range-Gated Noise (RGN) and (3) False-Target (FT) jamming.Assuming a Swerling type II target in the presence of Rayleigh-distributed clutter, utility functions were described for Cell-Averaging (CA) and Order Statistic (OS) CFAR processors and the three cases of jamming. The analyses included optimizations of these utility functions, subject to certain constraints, with respectto control variables (strategies) in the jammer, such as jammer power and spatial extent of jamming, and control variables in the radar, such as threshold parameter and reference window size. The utility functions were evaluated over the players’ strategy sets and the resulting matrix-form games were solved for the optimal or ‘best response’ strategies of both the jammer and the radar.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.