Le travail qui est présenté dans ce manuscrit est le résultat d'une série d'expériences qui ont été effectuées à la fois à l'Université du Maine (IMMM Le Mans) et aux lignes de lumière lD10 et lD02 de l'ESRF (Grenoble) où j'ai passé la moitié de mon temps. Le projet que j'ai travaillé pendant trois ans a été principalement orienté sur l'étude des nanomatériaux qui ont été exposés au CO2 supercritique en utilisant de diffusion des rayons X. Par conséquent une partie de ce travail a été consacrée à la description des propriétés de ce fluide supercritique et comment il interagit avec des matériaux tels que les polymères par exemple. Les matériaux analysés ont été le polystyrène sous forme de film et des ilots, ensuite des matériaux meso-structures avec des tensioactifs fluorés et finalement le carbonate de calcium. Due à la taille nanométrique de tous ces matériaux, les techniques de rayons X qui ont été largement utilisés dans ce travail étaient Small angle X-ray scattering (SAXS), Grazing Small angle X-ray scattering ( (GISAXS) et X-ray reflectivity (XRR). / The work that is presented in this manuscript is the result of a series of experiments that were performed both at the Université du Maine (IMMM Le Mans) and at the ID10 and ID02 beam lines of the ESRF (Grenoble) where I have equally spent half of my time. The project I have been working on for three years was mostly oriented on the study by means of X-ray scattering probes of nanomaterials that were exposed to supercritical CO2. As a result another part of this work will be also dedicated to describing the properties of this supercritical fluid and how it interacts with materials such as polymers for instance. The analyzed materials were thin film and small island of polystyrene, then materials mesostructures using fluoro-surfactants and finally calcium carbonate. Due to the nanoscale of these materials, the X-ray probes that were extensively used in this work were Small Angle X-ray scattering (SAXS), Grazing Incidence Small Angle X-ray Scattering (GISAXS) and X-ray Reflectivity (XRR).

The work in this PhD thesis covers two strands of x-ray experiments: firstly, the characterisation of large arrays of dense structures by means of x-ray scattering, and, secondly, the investigation of hybrid anisotropy square structures with x-ray microscopy. The ability to accurately characterise large arrays of nanoscale magnetic structures is a key requirement for both scientific understanding and technological advance such as bit patterned recording media (BPM). In this work small angle x-ray scattering (SAXS) was investigated as a characterisation technique for large arrays of patterned structures. Dense arrays of magnetic nanostructures were prepared on x-ray transparent membranes and measured. The SAXS data was then modelled to obtain structure parameters such as the mean structure diameter, the diameter distribution and the mean position variance with statistical significance. Arrays (500 x 500 μm2) of nominally uniform nanostructures with centre-to-centre distances between 250 nm-50 nm were structurally characterised and compared to structure diameters obtained by optical scanning electron microscopy measurements. The mean structure diameter was found to be between 39 nm-15nm and agree within the errors with the diameter obtained from SEM measurements. This work provides accurate data on the distribution (variance) of nanostructure sizes which is key for modelling these arrays for applicationin BPM. In the second part of the work, the static and dynamic properties of patterned hybrid anisotropy square structures ([Co/Pd]-Py) were investigated by using time-resolved scanning transmission X-ray microscopy (STXM). In these patterned structures the magnetisation in the layers change both in magnitude and direction and gives rise to interesting new domain configurations. The reciprocal interaction between magnetic vortices in the Py layer and locally circular stripe domains in the Co/Pd was investigated and a mutual domain imprint between the layer was observed. In dynamic excitation experiments the precession of the vortex core is studied and showed good agreement with micromagnetic simulations made by Hrkac and Bryan. As demonstrated patterned hybrid anisotropy square structures have promising magnetic properties with potential applications in data storage (vortex switching) or spintronics (vortex oscillators).

Content: Pre-treatments are widely used during tanning processes as to improve the performance of the main tannage. Synchrotron small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) were used to study four common types of pre-treatments, viz. monodentate complexing agent (sodium formate, SF), chelating agent (disodium phthalate, DSP), covalent cross-linker (glutaraldehyde, GA) and nanoclay (sodium montmorillonite, MMT) about their effects on chromium-collagen cross-linking reaction during tanning. Based on the results, the performance of chromium-collagen cross-linking with and without pre-treatments was presented considering five aspects: cross-linking, the level of hydration, hydrothermal stability, uniformity through leather cross-section and the uptake of chrome. Comparing to the original ThruBlu chrome tanning, at the same chrome offers, leather pre-treated using SF, DSP and MMT showed improved hydrothermal stability, uniformity and the level of hydration, while GA showed decreased hydration. All of the pre-treatments reduce surface fixation by decreasing the reactivity of chromium with collagen. Changes in the reaction performance can influence the properties of the leather products as well as the efficiency of the leather manufacturing processes. Insights into the structural changes of collagen during tanning with varied reaction conditions can guide the design of novel, benign tanning processes to reduce environmental impact. Take-Away: 1. Uniformity of the hydrothermal stability through leather cross-section were improved by all of the studied pre-treatments. 2. Reactivity of chromium to cross-link with collagen was reduced as a result of the complexing, covalent cross-linking, or preferential adsorption. 3. Complexing agents and nanoclay pre-treatments tend to retain collagen bound water, while covalent cross-linker causing decrease in the level of hydration of collagen.

Apoptosis signal-regulating kinase 1 (ASK1) is an apical kinase of the mitogen-activated protein kinase cascade. Its activity is triggered by various stress stimuli such as reactive oxygen species (ROS), cytokines, endoplasmic reticulum (ER) stress or osmotic stress resulting in the activation of p38 and c-Jun N-terminal kinase metabolic pathways and leading to inflammation or cell death. Dysregulation of ASK1 is linked to several pathologies such as neurodegenerative and cardiovascular diseases and cancer, which makes this protein a potential target of therapeutic intervention. The activity of ASK1 is regulated through protein-protein interactions with 14-3-3 proteins and thioredoxin1 being among the most important negative regulators and tumour necrosis factor receptor-associated factors being an example of positive regulators. Apart from that, ASK1 is also tightly regulated via oligomerization. Despite continual progress being made, the precise molecular mechanism of ASK1 regulation and the role of ASK1 oligomerization in this process still remains unclear to this day owing to the lack of structural data. Interaction of the N-terminal parts of two protomers of ASK1 dimer is one of the key steps in ASK1 activation. It was shown, that the isolated ASK1 catalytic domain (ASK1-CD) forms stable...

Indiana University-Purdue University Indianapolis (IUPUI) / There are three parts in this work centered on the catalyst layer of Polymer Electrolyte Fuel Cell (PEFC) in this thesis. The first part is for making best MEA structure. One of the major aims of this investigation is to understand the micro-structural organization of ionomer particles and Pt/C aggregates dispersed in a catalyst ink. The dispersion of Nafion® ionomer particles and Pt/C catalyst aggregates in liquid media was studied using ultra small angle x-ray scattering (USAXS) and cryogenic TEM technologies. A systematic approach was taken to study the dispersion of each component (i.e. ionomer particles and Pt/C aggregates) first, then the combination, last the catalyst ink. A multiple curve fitting was used to extract the particle size, size distribution and geometry from scattering data. The results suggests that the particle size, size distribution and geometry of each system are not uniform, rather, vary significantly. The results also indicate that interaction among components (i.e. ionomer particles and Pt/C aggregates) exists. The cryogenic TEM, by which the size and geometry of particles in a liquid can be directly observed, was used to validate the scattering results, which shows the excellent agreement. Based on this study, a methodology of analyzing dispersion of Pt/C particles, Nafion® particles in a catalyst ink has been developed and can serve as a powerful tool for making a desired catalyst ink which is a critical step for making rational designed MEA. The carbon corrosion process is the second part of the thesis. The carbon corrosion process of low–surface-area Pt/XC72 and high-surface-area Pt/BP2000 was investigated xi using an developed accelerated durability testing (ADT) method under simulated fuel cell conditions (a Rotating Disk Electrode (RDE) approach). Compared with the complex MEA system, this innovated approach using RDE can simply focus on carbon corrosion process and avoid the use of MEA in which many degradation/corrosion processes simultaneously occur. It was observed that different carbon corrosion processes resulted in different performance (electrochemical active surface area, mass activity and double layer capacity) decay of catalysts. The corrosion process was studied using TEM. It was found that in the case of Pt/XC72, major corrosion occurred at the center of the Pt/XC72 particle, with some minor corrosion on the surface of the carbon particle removing some amorphous carbon black filaments, while in the case of Pt/BP2000, the corrosion started on the surface. The understanding of carbon corrosion process provides the guidance for making high corrosion resistance catalysts to increase the durability performance of PEFC. Based on the second work, XC72 carbon blacks were etched using steam under different time and used as a new high corrosion resistance catalysts support for the oxygen reduction reaction. TEM results show that the center part of the XC72 particle was more easily etched away. XRD results show that the 002 and 10 peaks of the XC72 based samples are initially sharp, but then broaden during the corrosion process. TEM results of Pt particles show that the steam etching can improve dispersion uniformity of Pt nanoparticles on the surface of carbon support and reduce the Pt particles size. Electrochemical characterization results show that the mass activity of etched carbon black for 1 hour was 1.3 and 34 times greater than that of the carbon blacks etched for 3h and that of carbon blacks non-ecthed. ECSA of the carbon blacks was also significantly increased after etching. MEA test showed after 45 hours testing, the performance MEA with steam etching 1 hour XC72 based catalyst decreases much less than the MEA with commercial catalyst. Clearly, steam etching is a simple and efficient method to increase the performance and durability of the fuel cells catalysts.

Protein-protein interactions (PPIs) play a crucial role in almost all biological processes. Many proteins require a number of dynamic interactions with other proteins and/or biomolecules to function. Proteomic studies have suggested that human protein-protein interactome consists of several hundred thousands of protein complexes. A detailed insight into these PPIs is essential for a complete understanding of the processes mediated by these protein complexes. Because many PPIs are involved in disease-related signaling pathways, such PPIs are important targets for pharmaceutical interventions, especially in situations where a more conventional target (e.g. the active site of an enzyme, the binding site of a receptor) cannot be used. This doctoral thesis focuses on 14-3-3 proteins, a family of eukaryotic adaptor and scaffolding proteins involved in the regulation of many signaling pathways. The 14-3-3 proteins function as interaction hubs and critical regulators of many enzymes, receptors and structural proteins. The main aim was to structurally characterize selected 14-3-3 protein complexes and investigate their stabilization by small molecule compounds. Using combination of protein crystallography, differential scanning fluorimetry, fluorescence polarization and analytical ultracentrifugation, the...

Laser-Plasma-Beschleunigung mittels ultraintensiver Laserstrahlung ist eine vielversprechende Technologie für die Entwicklung kompakter Strahlungsquellen. Diese werden in einem breiten Spektrum technischer Anwendungsfälle genutzt, zum Beispiel zur Krebstherapie, in der Laborastrophysik und für die Trägheitsfusion, weshalb viele interdisziplinären Forschungsfelder ein großes Interesse an ihrer Entwicklung haben. Die ersten Machbarkeitsstudien zur Nutzung gepulster Protonenstrahlung zur Tumorbehandlung haben bereits erfreuliche Ergebnisse geliefert. Dennoch lagen die erzielten Parameter des Protonenstrahls weit unter den erwarteten Werten. Die bekannten Faktoren, die diese Performance einschränken, wurden fast ausschließlich durch Simulationen identifiziert. Der experimentelle Zugang zur Laser-Plasma-Wechselwirkung ist bisher auf die Auswertung der resultierenden Strahlung und auf makroskopische Oberflächeneffekte beschränkt, die mit optischen Messtechniken untersucht werden können. Diese Diagnostiken liefern allerdings keinerlei Informationen über die Vorgänge im Inneren des Plasmas, die letztlich die Parameter der beschleunigten Protonen bestimmen. Diese Prozesse werden in ihrer Größe und Zeitskala durch die Plasmaoszillation bzw. deren Frequenz und Wellenlänge bestimmt. Das Ziel dieses Forschungsprojekts war es, diese Lücke in der Auflösung bestehender Messmethoden zu schließen und eine Diagnostik zu entwickeln, die in der Lage ist, nanoskopische Plasma-Phänomene im Inneren der lasergetriebenen Probe zu untersuchen. Dieses Ziel konnten wir durch die Einführung von Röntgenkleinwinkelstreuung (SAXS) in Laserexperimenten an Röntgen-Freie-Elektronen-Lasern (XFELs) erreichen. In dieser Arbeit erläutere ich das technische Design und die methodische Auswertung des ersten dedizierten SAXS Experiments, das an der Matter in Extreme Conditions Messstation (auch MEC, Materie unter extremen Bedingungen) der Linac Coherent Light Source (auch LCLS, Linearbeschleuniger als kohärente Lichtquelle) durchgeführt wurde. Dieses Experiment war vorrangig eine Machbarkeitsstudie, die als Basis für die weitere Verwendung von SAXS in Laserexperimenten dienen soll. Meine Arbeit wird ausführlich die dafür nötigen experimentellen Techniken, den Aufbau, die Reinigung des gemessenen Beugungsbilds, das Probendesign und den Auswerteprozess erläutern. Um die experimentelle Durchführbarkeit dieser Methode zu testen, nutzten wir SAXS, um die Ausbreitung einer nanostrukturierten Probe in der Zeit kurz vor und während des Beginns des Laserpulses zu messen. Der Ausbreitungsparameter, den wir so aus den experimentellen Daten gewinnen konnten, liegt im einstelligen Nanometer- und teilweise im Subnanometer-Bereich und stimmte gut mit den Ergebnissen einer Particle In Cell (PIC) Simulation zur frühen Ausbreitungsphase überein. Dies zeigt, dass SAXS in der Lage ist, Plasma Prozesse zu messen, die für andere Diagnostiken bisher nicht zugänglich waren. Außerdem beobachteten wir eine Abweichung der experimentellen Daten von dem von uns entwickelten Modell zur Beschreibung der ungehinderten Ausbreitung des Plasmas ins Vakuum. Dies veranlasste uns zu einer genaueren Untersuchung der Ausbreitung mittels PIC Simulation und tatsächlich sahen wir darin die Bildung von Plasma-Strömen, die auch in der SAXS-Auswertung qualitativ bestätigt werden konnten. Die Komplexität des Ausbreitungsprozesses, die wir in diesem Forschungsprojekt aufdecken konnten, zeigt, dass weitere Studien dazu durchgeführt werden sollten. Wenn wir die Ergebnisse der hier präsentierten SAXS Modelle nutzen, um unser Verständnis des Effekts von Vorpulsen und Intensitäts-Plateaus auf die Protonenbeschleunigung mit nanostrukturierten Proben zu verbessern, werden wir zukünftig in der Lage sein, die damit erzielten Strahlparameter zu verbessern. Der entwickelte SAXS Aufbau wurde auch an die Gegebenheiten von Experimenten zur Schockwellenverdichtung mittels Hochenergielasern angepasst und angewendet. Es gibt großes wissenschaftliches Interesse an der Entmischung von Kohlenwasserstoffen im Zustand warmer dichter Materie (WDM). Viele Laborastrophysikexperimente untersuchen das Innere von Eisriesen wie Uranus und Neptun, insbesondere den Verlauf der Phasentrennung von leichten Elementen wie Kohlenstoff und Wasserstoff, die zu Diamantregen führt. Bisher war es bei diesen Messungen nicht möglich, nanoskopische Dichteänderungen im Inneren einer dichten Probe unter extremen Bedingungen zu untersuchen. Im Rahmen dieser Forschungsarbeit wurde SAXS als ergänzende Diagnostik in Hochenergiedichte-Experimenten mit Lasern an Einrichtungen wie an der MEC Messstation und an anderen XFELs etabliert. Ich wendete bekannte SAXS Auswerteroutinen auf den besonderen Fall eines sich von Schuss zu Schuss ändernden Dichtekontrasts an. Die verschiedenen Komponenten der SAXS Daten wurden mit den Informationen korreliert, die aus anderen Diagnostiken wie Beugung und VISAR gewonnen wurden. So konnte ich durch die Auswertung der Nanodiamant-Komponente eine Schätzung der Diamantgröße und des Diamant-Volumenanteils ableiten, indem ich spezifische Modelle fittete, die auf hydrodynamischen Simulationen basieren. Zukünftig möchten wir diese experimentellen Grundlagen auch auf die Untersuchung von Flüssig-Flüssig-Entmischung leichter Elemente im WDM Zustand anwenden. In dieser Arbeit erläutere ich die von mir entwickelten Auswerteprozesse, die auf weitere Messungen angewendet werden können, sobald deren Messbereich und Sensitivität so verbessert wurde, dass die Parameter von Interesse bestimmbar sind. Dieses Projekt half dabei, SAXS als Standarddiagnostik in Forschungseinrichtungen zu etablieren, die XFELs mit Hochleistungslaserexperimenten verbinden. Es bereitet sowohl die technische als auch die methodische Grundlage für weitere Experimente. / Laser plasma acceleration with ultra-high intensity (UHI) lasers is a promising technology for building compact radiation sources. These hold immense potential for a wide array of applications including cancer therapy, laboratory astrophysics and inertial confinement fusion and there is great interest in their development in many interdisciplinary fields of research. But while proof of concept experiments using proton pulses for tumor irradiation have delivered encouraging results, the achieved proton beam parameters fell short of the originally expected values. The limiting factors to this performance have mostly been identified in simulation only. Experimental access to the interaction between the drive laser and the dense plasma is so far limited to the analysis of the emitted radiation and the macroscopic surface effects that can be probed by visible light. These diagnostics cannot provide information about the processes in the bulk of the plasma that eventually determine the properties of the accelerated particles. Their spatial and temporal domain is dominated by the plasma oscillation frequency and wavelength. The aim of this project was to bridge this resolution gap with a diagnostic that is capable of investigating nanoscopic plasma features in the bulk of a laser-driven sample on a femtosecond scale. This was achieved by establishing the use of Small Angle X-Ray Scattering (SAXS) at UHI laser experiments at X-Ray Free Electron Lasers. My thesis will outline the technical design and scientific analysis of the first dedicated SAXS experiment at the Matter in Extreme Conditions (MEC) instrument of the Linac Coherent Light Source. The primary goal of the experiment was proof of concept as a foundation for regular use of SAXS in UHI experiments in the future. I will discuss the experimental procedures, the setup, the cleaning of the diffraction pattern, the target design and the analysis process that were developed for this new diagnostic in detail. To test the feasibility of this method, we used SAXS to measure the expansion of a nanostructured target in the femtosecond time span before and around the onset of a low intensity drive laser pulse. The expansion parameter that was extracted from the experimental data is in the in the sub- to single nanometer range and was in good agreement with the results of a particle-in-cell (PIC) simulation describing the early expansion phase. This demonstrates that SAXS is capable of measuring plasma processes on scales that were previously unobtainable by other diagnostics. We also identified a deviation of the experimental data from the simple model that we developed to describe an unobstructed expansion of plasma into vacuum. This lead us to examine the expansion in more detail via PIC simulation and indeed we discovered the formation of plasma jets at a later phase of the plasma expansion in simulation for a grating target. This additional effect was confirmed qualitatively by the SAXS analysis. The complexity of the plasma expansion process for a structured target we found in this project demonstrates the need for further studies. If we use the SAXS models presented here to improve our understanding of the effect of prepulses and pedestals on proton acceleration using nanostructured targets, we can apply this knowledge to the improvement of the proton beam parameters in future developments. %Additionally the technical implementation of SAXS for UHI laser experiments was developed in the framework of this thesis and established as a useful tool for the investigation of other nanoscopic plasma features. The developed experimental setup for SAXS was also adapted and applied to laser shock compression experiments using high energy drive lasers. There is great research interest in the demixing of hydrocarbons in the Warm Dense Matter (WDM) state. Many laboratory astrophysics experiments investigate the internal structure of ice giants like Uranus and Neptune, specifically the dynamics of the phase separation of light elements like carbon and hydrogen which can result in diamond rain. So far these measurements lacked a diagnostic that is capable of probing nanoscopic density modulations in the bulk of a dense target in an extreme state of matter. SAXS allowed us to gain access to the parameters of the demixing process. In the framework of this project SAXS was established as a complementary diagnostic to the standard setup for high energy density laser experiments at the MEC instrument and at other XFELs. I applied existing SAXS analysis procedures to the special case of a density contrast that changes on every shot. The different components of the SAXS data were correlated to information from other standard diagnostics including diffraction and VISAR. I was able to quantitatively analyze the component caused by nanodiamonds and retrieved an estimate of the diamond size and volume fraction from fits to custom models that are based on hydrodynamic simulations. In the future, we would like to extend this experimental basis to the investigation of liquid-liquid demixing of light elements in the WDM state. In this thesis I will discuss the SAXS analysis procedures that I dweveloped so that they can be applied to future measurements, once the experimental range and sensitivity has been improved to retrieve the parameters of interest. This project helped to establish SAXS as a standard diagnostic at facilities combining XFELs with high power laser experiments. It is supposed to lay both the technical and methodical groundwork for further experiments.

No / An experimental configuration that combines the powerful capabilities of a short-term shearing apparatus with simultaneous optical and X-ray scattering techniques is demonstrated, connecting the earliest events that occur during shear-induced crystallization of a polymer melt with the subsequent kinetics and morphology development. Oriented precursors are at the heart of the great effects that flow can produce on polymer crystallization (strongly enhanced kinetics and formation of highly oriented crystallites), and their creation is highly dependent on material properties and the level of stress applied. The sensitivity of rheo-optics enables the detection of these dilute shear-induced precursors as they form during flow, before X-ray techniques are able to reveal them. Then, as crystallization occurs from these precursors, X-ray scattering allows detailed quantification of the characteristics and kinetics of growth of the crystallites nucleated by the flow-induced precursors. This simultaneous combination of techniques allows unambiguous correlation between the early events that occur during shear and the evolution of crystallization after flow has stopped, eliminating uncertainties that result from the extreme sensitivity of flow-induced crystallization to small changes in the imposed stress and the material. Experimental data on a bimodal blend of isotactic polypropylenes are presented.

This study seeks to develop smart hydrogel formulations for injectable controlled drug delivery from Pluronics to enhance patients compliance, decrease side effects, reduce dose and frequency. A biocompatible copolymer, Pluronic F127 was probed as the main ingredient for the injectable systems owing its low gelation concentration and ease of modification the system properties through excipients addition. The matrix properties were studied through a series of thermal, rheological and structural (SAXS/SANS) experiments as a function of concentration and shear rate, covering both static and dynamic environments. It has shown that gelled viscosity (and structure) can be critically controlled by shear rate and the structures recorded do not match those predicted for sheared colloids. Two further Pluronics F68 and F108, were studied showing similar but shifted gelation properties to F127. Effects of additives were studied by introducing different Mw PEGs and a model hydrophobic drug ‘ibuprofen’ to a F127 20% formulation. PEGs addition effects on the system properties and gelation transition were largely dependent on the Mw used in the blend, which became more prominent with increasing chain length. Ibuprofen’s addition has resulted in reduced gelation temperature and smaller hard spheres without having a great effect on the system rheological properties compared to neat gels. Blends containing both additives PEG and ibuprofen exhibited a synergistic effect, where comparisons show that Ibuprofen had the largest effect on the blends lowering gelation boundaries and slightly increasing the size of the hard spheres indicating the necessity of full characterisation of the formulation with any API.

No description available.