Macromolecular interactions play very important roles in regulation of all levels of biological processes. Aberrant macromolecular interactions often result in diseases. By applying a combination of spectroscopy, calorimetry, computation and other techniques, the protein-protein interactions in the system of the Shaw2 Kv channel and the protein-RNA interactions in West Nile virus RNA-cellular protein TIAR complex were explored. In the former system, the results shed light on the local structures of the key channel components and their potential interaction mediated by butanol, a general anesthetic. In the later studies, the binding modes of TIAR RRM2 to oligoU RNAs and West Nile virus RNAs were investigated. These findings provided insights into the basis of the specific cellular protein–viral RNA interaction and preliminary data for the development of strategies on how to interfere with virus replication

Deux thématiques sont développées dans la présente thèse. Tout d'abord, des surfaces de molybdène nues et carburées sont étudiées à l'aide de calculs basés sur la théorie de la fonctionnelle de la densité – DFT – appliquée aux systèmes périodiques. Les propriétés électroniques et structurales des surfaces 100, 110 et 111 du molybdène cristallin et p(1x1)-C, c(2x2)-C et c(3√2x√2)R45°-C Mo(100), p(4x4)-C Mo(110) et p(6x1)-C Mo(111) sont déterminées. L'activité de la surface p(4x4)-C Mo(110) vis-à-vis de l'adsorption de CO est abordée par la détermination des modes de vibration du monoxyde de carbone coordiné à divers sites de surface. Le modèle de surface proposé est validé par une comparaison des données expérimentales et théoriques.<br /> L'étude de la fonctionnalisation de surfaces carbonées - graphite et nanotube (8,0) - par un atome de métal de transition est réalisée par des calculs DFT. Il est déterminé que les atomes de Cr, Mn et Cu sont physisorbés alors que les autres atomes de la série 3d sont chimisorbés. L'occupation de l'orbitale 4s pour Cr, Mn et Cu conduit à une répulsion métal-surface, quelque soit la courbure du plan graphitique. Les surfaces d'énergie potentielle sont déterminées pour évaluer les barrières de diffusion. Sc, Ti, Fe et Co sont les métaux susceptibles d'être isolés en surface. Les autres diffusent (formation d'aggrégats). Le magnétisme, l'énergie d'adsorbtion et la structure géométrique sont analysés à l'aide de l'étude des densités d'états, des charges de Bader et de diagrammes orbitalaires de molécules organométalliques modèles. <br /> Finalement, l'activation du dihydrogène par un métal 3d de surface est étudiée. Des complexes dihydrures et d'hydrogène moléculaire sont localisés en surface. La faible élongation de la liaison s HH est observée préférentiellement pour Fe, Co et Ni tandis que la rupture de la liaison apparaît pour Sc, Ti et V. La saturation de certains métaux par adsorption de plusieurs molécules d'hydrogène est entreprise. Il est montré que ces matériaux hypothétiques pourraient stocker l'hydrogène.<br /> La création d'un cluster d'ordinateurs pour le calcul numérique est présentée. L'originalité consiste à utiliser des ordinateurs dédiés à l'enseignement et utilisables en dehors de ces périodes.

Ce travail permet de résoudre des problemes d'optimisation LMI dependant rationnellement d'un ou plusieurs parametres. Ce resultat est fondamental car il ouvre une solution efficace a la classe extremement large des problemes se formulant comme un probleme d'optimisation LMI dependant de parametres. En Automatique, une telle classe de problemes comprend celle de la conception de cor- recteurs dependant de parametres. Un cas particulier important est celui de la commande des systµemes non lineaires par sequencement de gains. Au depart, cette classe de problemes d'Automatique a ete motive par une nouvelle application possible : la conception de correcteurs dont les gains sont une fonction explicite du cahier des charges, baptises " correcteurs rereglables ". L'interet est de permettre un rereglage aise sur site d'exploitation par un utilisateur neophyte en Automatique, voire un rereglage automatique. Ce travail a permis de formaliser ce problµeme de rereglage, d'en proposer une solution complete et de la valider.

Introduction The chemistry of transitional metal complexes bearing σ-bonded H−X (X = H, Si, C) species/fragments, the so called σ-complexes, are key intermediates in catalytic processes such as hydrogenation, hydrosilylation, alkane functionalization etc. Particularly, the σ-H2 complexes form the best-known group of σ-complexes in which H2 is bound to the metal center in η2-fashion. Several well characterized examples of η2-silane and η2-borane complexes have also been reported. Moreover, in recent years, the carbon analogues of these complexes in which alkanes are coordinated through η2-C-H bonds to the metal center have been attracting the attention of organometallic chemists. An approach towards direct functionalization of σ-bonds in simple alkanes is the heterolytic activation of the C−H bond using highly electrophilic complexes. After all, for fine catalyst design and the selective functionalization of H−H, silanes or simple alkanes, it is necessary to understand the bonding nature of these σ-complexes in depth. Objectives The objectives of this work are as follows a) An attempt to stabilize and gain insights into the bonding nature and reactivity behavior of various sigma ligands on ruthenium center [Ru(η2-HX)(Tpms)(PPh3)2][OTf], (X = H, SiR (R = Me3 or Me2Ph) and CH3). b) Synthesis, characterization and reactivity studies of electrophilic ruthenium(II) complexes bearing (C6F5)2PCH2CH2P(C6F5)2 (dfppe) ligand towards heterolysis of H2. c) An approach towards preparation of insoluble molecular clusters from [Ru(P(OH)3)(dppe)2][OTf]2 complex and Zn, Cd and Cu acetates to realize σ-bond activation under heterogeneous conditions. Significant results In our attempts to gain insights into the bonding nature and reactivity behavior of σ-H2, silane and methane complexes, we followed two strategies to generate these complexes in solution. First, we synthesized and well characterized two new Ru(II)-complexes [RuH(Tpms)(PPh3)2] and [Ru(OTf)(Tpms)(PPh3)2], (OTf = trifluoromethane sulfonate) where Ru-H and Ru-OTf are the key reactive centers, followed by their subsequent reactions with electrophilic reagents such as HOTf, Me3SiOTf and CH3OTf and with H2, PhMe2SiH and CH4 at low temperature, respectively. These reactions finally resulted in the characterization of σ-H2 and σ-silane complexes, however, no σ-methane complex was observed even at low temperature (Scheme 1). Scheme 1 In order to realize highly eletrophilic metal complexes, a chelating fluorinated phosphine ligand 1,2-bis-(pentafluorophenylphosphino)ethane, (C6F5)2PCH2CH2P(C6F5)2 (dfppe) was employed and the synthesis and structural characterization of a series of new, Ru(II) hydride complexes [RuH(P(OMe)3)(bpy)(dfppe)][OTf], cis-[RuH2(dfppe)(PPh3)2] and [RuH(CO)Cl(PPh3)(dfppe)] were accomplished. Protonation reaction of the hydride complexes [RuH(P(OMe)3)(bpy)(dfppe)][OTf] (Scheme 2) and [RuH(CO)Cl(PPh3)(dfppe)] (Scheme 3) with HOTf at low temperature gave free H2 and five-coordinate species [Ru(P(OMe)3)(bpy)(dfppe)][OTf]2 and [Ru(CO)Cl(PPh3)(dfppe)][OTf], respectively. Surprisingly, in all these reactions, dihydrogen complexes are formed which were unobservable in which the H2 ligand was found to be highly labile. Reaction of is-[Ru(bpy)(dfppe)(OH2)(P(OMe)3)][OTf]2 with H2 however, resulted in the heterolytic activation of the H–H bond and concomitant protonation of H2O to give the corresponding hydride complex cis-[Ru(H)(bpy)(dfppe)(P(OMe)3)][OTf] and H3O+ (Scheme 2) . Scheme 2 Scheme 3 In an attempt to prepare insoluble molecular clusters in order to realize σ-bond activation under heterogeneous conditions, we studied the reactivity of highly electrophilic [Ru(P(OH)3)(dppe)2]2+ (dppe = (C6H5)2PCH2CH2P(C6H5)2) complex with various metal acetates. Usage of Zn(OAc)2.2H2O afforded a novel [Ru2(dppe)4P2(OH)2O4Zn2(OAc)(DMP)(OTf)][OTf]2 (Ru-Zn ) soluble bimetallic complex (Scheme 4) which was characterized in detail by NMR and single crystal X-ray crystallography. To achieve the expected insoluble molecular cluster further studies are required to tune the electronics and the sterics around the phosphorous acid moiety. Scheme 4

Forests represent one of the biggest terrestrial ecosystems of Earth, that can produce important raw renewable materials such as wood with the help of sun, air and water. To efficiently extract these raw materials, the tree harvesting process is highly mechanized in developed countries, meaning that advanced forestry machines are continuously used to fell, to process and to transport the logs and biomass obtained from the forests. However, working with these machines is demanding both mentally and physically, which are known factors to negatively affect operator productivity. Mental fatigue is mostly due to the manual operation of the on-board knuckleboom crane, which requires advanced cognitive work with two joystick levers, while the most serious physical strains arise from cabin vibrations. These vibrations are generated from knuckleboom crane vibrations as a result of aggressive manual operation. To enhance operator workload, well-being, and to increase productivity of the logging process, semi-automation functions are suggested, which are supervised automatic executions of specific work elements. Some of the related issues are addressed in the current thesis. Therefore, the content is divided into: (1) the design and development of a semi-automation function focused only on the base joint actuator (slewing actuator) of a knuckleboom crane, and (2) active vibration damping solutions to treat crane structure vibrations induced by the main lift cylinder (inner boom actuator). The considered reference machine is a downsized knuckleboom crane of a forwarder machine, which is used to pick up log assortments from a harvesting site. The proposed semi-automation function presented in the first part could be beneficial for operators to use during log loading/unloading scenarios. It consists from a closed-loop position control architecture, to which smooth reference slewing trajectories are provided by a trajectory planner that is automated via operator commands. The used trajectory generation algorithms are taken from conventional robotics and adapted to semi-automation context with proposed modifications that can be customizable by operators. Further, the proposed active vibration damping solutions are aimed to reduce vibrations of the knuckleboom crane excited by the inner boom actuator due to aggressive manual commands. First, a popular input shaping control technique combined with a practical switching logic was investigated to deal with the excited payload oscillations. This technique proved to be useful with a fixed crane pose, however it did not provide much robustness in terms of different link configurations. To tackle this problem an H2-optimal controller is developed, which is active in the pressure feedback-loop and its solely purpose is to damp the same payload oscillations. During the design process, operator commands are treated and explained from input disturbance viewpoint. All of the hypothesis throughout this thesis were verified with extensive experimental studies using the reference machine.

For performance optimisation of modern liquid cryogenic bipropellant rocket combustion chambers, one component which plays an important role in reducing the wall side heat flux, is the behaviour of the cooling film. At the Institute of Space Propulsion of the German Aerospace Center (DLR) in Lampoldshausen, hot test runs have been performed using the experimental combustion chamber BKM, to investigate the wall side heat flux which is -- among other factors -- dependent on cooling film properties. To gain more insight into the film behaviour under real rocket-like conditions, optical diagnostics have been applied. The chosen methods were shadowgraphy and OH* imaging producing optical data sets which are analysed in this study. In this context, a description of the necessary background information is given, concerning rocket combustion chambers, film cooling and optical diagnostics of O2/H2 combustion. The applied methodology for optical analysis is described, followed by a presentation of the results. During the test campaign, it became clear that the optical setup was not optimised for creating meaningful shadowgraphy recordings which is why the shadowgraphy data has to be treated as flame emission imaging. The behaviour of the gas layer adjacent to the chamber wall could be characterised based on qualitative (luminosity, LOx shadow, reflection, recirculation zone and flame shape) and quantitative (layer thickness, layer length, pressure conditions) analysis. The thickness could be identified for each load step and an average length of the layer was found as well. OH* imaging has been used supplementary to support the observations from the flame emission images. An in depth frame by frame analysis was not possible due to time constraints. However, the time averaged images yielded results in accordance to the flame emission and could give a relative figure for the temperature distribution in the combustion volume. An artefact in the data was found, stemming presumably from the image intensifier. This artefact needs to be researched for a future error reduction in the data of this and other campaigns. Additionally, the thickness of the layer suggested a correlation to the models for film cooling efficiency. Such a correlation could not be established. Nevertheless, the film cooling models show the same behaviour as the data obtained from the flame emission imaging. Finally, suggestions are given how the data analysis and the optical setup could be improved for future, similar campaigns.

H2 Green Steel AB was founded in 2020 to build a large-scale green steel factory in Boden, Norrbotten, Sweden. The factory consists of green hydrogen production, iron production and steel production. In 2030, the factory’s annual steel production will be 5 million tonnes annually. The objective of the thesis was to build a concept to improve a recommendation for a Hydrogenproduction site in an early stage of engineering. It included improving the understanding and basis for three criteria. The first criteria consisted of technical and customer requirements, seeing the requirements for the specific application of hydrogen as the critical factor. The second criteria consisted of further investigating how existing interfaces and utilities can be used in hydrogen production and building the basis for qualification. The third criteria consisted of adapting the concept to existing internal design tools by building it forward compatible. The thesis was initiated by bench-marking possible activities related to the recommendation acting as technical support and extensions to existing solutions. The research approach used was Design Research Methodology (DRM), held as the framework for execution. The result from the thesis delivers a database model built upon three linked packages providing a methodology of increased technical information, forward compatibility and a modular approach for design.

La photocatalyse est une voie de synthèse prometteuse de l’hydrogène comme carburant solaire. La production photocatalytique est un moyen, à la fois de stocker l’énergie solaire sous forme d’énergie chimique et de produire des carburants de manière renouvelables en utilisant l’eau ou des alcools biosourcés comme matière première. L’objectif de cette thèse est d’étudier la déshydrogénation photocatalytique d’alcools à l’aide de sulfures de métaux de transitions, supportés sur TiO2 (MSx/TiO2). Ces sulfures de métaux de transitions ont des propriétés d’activation de l’hydrogène, des propriétés électrochimiques et des propriétés optiques intéressantes. Une série de sept MSx/TiO2 (M = Co, Ni, Cu, Mo, Ru, Ag, Hg) ont été étudiés. La réaction de déshydrogénation photocatalytique du propan-2-ol est utilisée comme réaction modèle. Des corrélations sont établies entre les propriétés intrinsèques de ces MSx/TiO2 et leur activité photocatalytique. De plus, la mesure d’énergie d’activation d’apparente apporte une compréhension supplémentaire sur les mécanismes photocatalytiques. Cette dernière montre que la production photocatalytique d’hydrogène est principalement limitée par les phénomènes de séparation et de transfert de charges dans les photocatalyseurs. Ainsi, une méthodologie combinant la spectroscopie de photoélectrons UV et la spectroscopie d’absorption UV-Visbile a été mis en place pour déterminer la structure électronique des poudre photocatalytiques. Ce travail conclue sur le caractère central de la structure électronique en photocatalyse. Dans le cas du photocatalyseur RuS2/TiO2, le transfert électronique est l’étape cinétiquement déterminante pour la déshydrogénation photocatalytique du propan-2-ol / Photocatalysis is a promising way to synthesize H2 as a solar fuel. On one hand, the photocatalytic H2 production stores solar energy under chemical energy. On the other hand, it produces H2 with a renewable process using water and bio-based alcohols as a feedstock. This Ph.D thesis aims to study the photocatalytic dehydrogenation of alcohols with transition metal sulfides supported on TiO2 (MSx/TiO2). Those transition metal sulfides have versatile and highly tunable properties. They can activate H2, they have promising electrochemical behavior and optical properties. Seven MSx/TiO2 (M = Co, Ni, Cu, Mo, Ru, Ag, Hg) are therefore studied. The photocatalytic dehydrogenation of propan-2-ol is used as a model reaction. Structure-activity relationships are found between the intrinsic properties of the MSx/TiO2 and their photocatalytic activity. Measuring an apparent activation energy provides additional mechanistic insights. It shows that the photocatalytic production of hydrogen is mostly limited by the charge carrier separation and by the electronic transfer. Therefore a method combining the UPS and the UV-Visbile absorption spectroscopies has been develop to establish the electronic structure of photocatalytic powders. This work concludes that the electronic structure plays a crucial role in photocatalysis. With RuS2/TiO2 photocatalyst, the electron transfer is evidenced as the rate-determining step of the photocatalytic dehydrogenation of propan-2-ol

We address the question of performance of large-scale networks with distributed feedback control. We consider networked dynamical systems with single and double integrator dynamics, subject to distributed disturbances. We focus on two types of problems. First, we consider problems modeled over regular lattice structures. Here, we treat consensus and vehicular formation problems and evaluate performance in terms of measures of “global order”, which capture the notion of network coherence. Second, we consider electric power networks, which we treat as dynamical systems modeled over general graphs. Here, we evaluate performance in terms of the resistive power losses that are incurred in maintaining network synchrony. These losses are associated with transient power flows that are a consequence of “local disorder” caused by lack of synchrony. In both cases, we characterize fundamental limitations to performance as networks become large. Previous studies have shown that such limitations hold for coherence in networks with regular lattice structures. These imply that connections in 3 spatial dimensions are necessary to achieve full coherence, when the controller uses static feedback from relative measurements in a local neighborhood. We show that these limitations remain valid also with dynamic feedback, where each controller has an internal memory state. However, if the controller can access certain absolute state information, dynamic feedback can improve performance compared to static feedback, allowing also 1-dimensional formations to be fully coherent. For electric power networks, we show that the transient power losses grow unboundedly with network size. However, in contrast to previous results, performance does not improve with increased network connectivity. We also show that a certain type of distributed dynamic feedback controller can improve performance by reducing losses, but that their scaling with network size remains an important limitation. / <p>QC 20160504</p>

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