L’oxydase de l’acide 1-AminoCyclopropane Carboxylique (ACC Oxydase, ACCO) catalyse la formation de l’éthylène, hormone essentielle à la vie des plantes. L’ACCO catalyse l’oxydation de l’ACC en éthylène en présence de dioxygène et de deux électrons (fournis in vitro par l’ascorbate). L'activité de l'enzyme requière également, pour des raisons encore incomprises, la présence de CO2 sous la forme d'ions bicarbonates. Il s’agit d’une enzyme qui contient un ion fer(II) dans un environnement non-hémique au site actif. Etant donné l’importance de l’éthylène chez les plantes, l’ACCO, ainsi que les autres enzymes impliquées dans sa biosynthèse, ont été très étudiées durant les vingt dernières années. Cependant, peu d’études ont porté sur le rôle de l’ion métallique et le mécanisme d’action ou sur les surprenants processus d’inactivation subis par l’enzyme. L’ACCO est en effet une enzyme connue pour son instabilité. Nous avons tout d’abord entrepris une caractérisation physicochimique et biochimique de l’enzyme. Le matériel protéique utilisé a tout d’abord été analysé une coupure entre les résidus Ala 290 et Gly 291 a été observée au cours de la purification de l'enzyme. Puis, grâce à l'utilisation de techniques spectroscopiques, nous avons cherché à obtenir plus d'informations sur la fixation des substrats/cofacteurs au site actif. Enfin l’étude des mutants et des complexes modèles de l’ACCO a été réalisée afin de mieux comprendre le mécanisme catalytique et de rechercher de nouvelles activités. Nous nous sommes aussi intéressés aux mécanismes d’inactivation de l’ACCO. En présence des effecteurs en excès, cette inactivation se traduit par une fragmentation et une modification de charge. Lorsque la concentration en fer est limitée, aucune modification physique de l’enzyme inactive n’est observée et l'enzyme garde un contenu global en aminoacide et une conformation tridimensionnelle intègres. Des processus oxydatifs se déroulant directement au site actif de l’enzyme sont susceptibles d’engendrer une telle perte d’activité par l'oxydation d'un nombre limité d'acides aminés. Des études en spectrométrie de masse ont été entreprises et sont toujours en cours afin d'identifier les modifications responsables de la perte d'activité de l'enzyme.Enfin nous avons recherché d’éventuelles partenaires protéiques qui pourraient conférer à l’ACCO une meilleure stabilité. Des études préliminaires ont été entreprises et des données de microscopie suggèrent que l'ACCO est localisée près des membranes de la vacuole. / The 1-AminoCyclopropane Carboxylic acid oxidase (ACC Oxidase, ACCO) catalyzes the last step of the biosynthesis of the plant hormone, ethylene. ACCO catalyzes the oxidation of ACC into ethylene in the presence of dioxygen and two electrons (provided in vitro by ascorbate). Carbon dioxide (or bicarbonate ions) are also required for optimum activity. ACCO is an non-heme iron(II) containing enzyme. Given the importance of ethylene in plants, studies on ACCO, as well as on the other enzymes involved in its biosynthesis, have attracted much attention in the past two decades. However, few studies focus on the role of the metal ion and on the catalytic mechanism or the intriguing inactivation processes. ACCO is indeed known for its instability. We first purified and characterised the enzyme. During the purification, a cleavage between residues Ala 290 and Gly 291 was observed. Then, using spectroscopic techniques, we intended to get more information on cofactor's binding in the active site. Finally studies of mutants and model complexes of ACCO were performed in order to get a better understanding of the catalytic mechanism and to look for new activities.We were also interested in the inactivation processes of ACCO. In the presence of an excess of effectors, this inactivation resulted in fragmentation and in pI modification. When the concentration of iron is limited, no modifications of the inactive enzyme were observed. The inactive enzyme maintained its amino acid content and three-dimensional conformation. The loss of activity is therefore likely to derive from oxidative processes directly at the active site. Mass spectrometry experiments were initiated and are still under progress. Finally we were interested in identifying possible protein partners of ACCO that could provide a better stability. Preliminary studies were thus initiated and from microscopy results, ACCO was found located close to the vacuole membrane.

Afin de répondre aux besoins en management efficace de l’énergie électrique dans les bâtiments intelligents, le laboratoire GREMAN a proposé une nouvelle topologie d’interrupteur bidirectionnel de 600 V nommé TBBS. Les études antérieures ont validé la bidirectionnalité en courant et en tension de cette nouvelle topologie. Les travaux de recherche menées dans cette thèse avaient pour l’objectif d’approfondir, de compléter nos connaissances sur ce nouvel interrupteur bidirectionnel ainsi que sur le transistor bipolaire à fort gain. Le premier chapitre introduit le fonctionnement principal du TBBS et sa modélisation physique sous un environnement de simulation à éléments finis. Le deuxième chapitre présente le travail concernant la caractérisation expérimentale du TBBS et du transistor bipolaire à fort gain sous température contrôlée. Enfin la modélisation électrique du TBBS et du transistor bipolaire à fort gain est présentée dans le troisième et dernier chapitre. / In order to meet the requirement of more efficient electrical energy management for intelligent buildings, a new 600V bidirectional switch, named as TBBS, has been proposed by the GREMAN laboratory. Previous studies have validated the current and voltage bidirectionality of this newly proposed topology. The research work carried out in this thesis deals with a deeper and more comprehensive study of this bidirectional switch and its elementary component - the High-gain bipolar juncion transistor. The first chapter introduces the operation of the TBBS and its physical modeling in a finite element simulation environment. The second chapter presentes the research work related to the experimental caracterisation of the TBBS and the High-gain bipolar junction transistor. At last the third chapter deals with the electrical modeling of these two bipolar components.

Cette thèse de doctorat introduit un modèle et un algorithme six-dimensions pour la reconstruction des orientations cristallines locales dans les matériaux polycristallins. Le modèle s’applique actuellement aux données obtenues avec un rayonnement synchrotron (faisceau parallèle et monochromatique), mais il est également possible d’envisager des extensions aux instruments et sources de laboratoire (polychromatique et divergent). Le travail présenté est principalement une extension de la technique connue sous le nom de “Diffraction Contrast Tomography” (DCT) qui permet la reconstruction de la forme et de l’orientation cristalline des grains dans des matériaux polycristallins (avec certaines restrictions concernant la taille et le nombre total de grains ainsi que la mosaicité intragranulaire). / This Ph.D. thesis is about the development and formalization of a six-dimensional tomography method, for the reconstruction of local orientation in poly-crystalline materials. This method is based on a technique known as diffraction contract tomography (DCT), mainly used in synchrotrons, with a monochromatic and parallel high energy X-ray beam. DCT exists since over a decade now, but it was always employed to analyze undeformed or nearly undeformed materials, described by “grains” with a certain average orientation. Because an orientation can be parametrized by the used of only three num- bers, the local orientation in the grains is modelled by a six-dimensional space X6 = R3 ⊗ O3, that is the outer product between a three-dimensional real- space and another three-dimensional orientation-space. This means that for each point of the real-space, there could be a full three-dimensional orientation- space, which however in practice is restricted to a smaller region of interest called “local orientation-space”. The reconstruction problem is then formulated as a global minimisation prob- lem, where the reconstruction of a single grain is the solution that minimizes a functional. There can be different choices for the functionals to use, and they depend on the type of reconstructions one is looking for, and on the type of a priori knowledge is available. All the functionals used include a data fidelity term which ensures that the reconstruction is consistent with the measured diffraction data, and then an additional regularization term is added, like the l1-norm minimization of the solution vector, that tries to limit the number of orientations per real-space voxel, or a Total Variation operator over the sum of the orientation part of the six-dimensional voxels, in order to enforce the homogeneity of the grain volume. When first published, the results on synthetic data from the third chapter high- lighted some key features of the proposed framework, and showed that it was in principle possible to extend DCT to the reconstruction of moderately de- formed materials, but it was unclear whether it could work in practice. The following chapters instead confirm that the proposed framework is viable for reconstructing moderately deformed materials, and that in conjunction with other techniques, it could also overcome the limitations imposed by the grain indexing, and be applied to more challenging textured materials.

Lithium-ion batteries are a possible choice for the energy storage system onboard hybrid electric vehicles and low-earth-orbit satellites, but lifetime performance remains an issue. The challenge is to diagnose the effects of ageing and then investigate the dependence of the magnitude of the deterioration on different accelerating factors (e.g. state-of-charge (SOC), depth-of-discharge (DOD) and temperature). Lifetime studies were undertaken incorporating different accelerating factors for two different applications: (1) coin cells with a LixNi0.8Co0.15Al0.05O2-based positive electrode were studied with a EUCAR power-assist HEV cycle, and (2) laminated commercial cells with a LixMn2O4-based positive electrode were studied with a low-earth-orbit (LEO) satellite cycle. Cells were disassembled and the electrochemical performance of harvested electrodes measured with two- and three-electrode cells. The LixNi0.8Co0.15Al0.05O2-based electrode impedance results were interpreted with a physically-based three-electrode model incorporating justifiable effects of ageing. The performance degradation of the cells with nickelate chemistry was independent of the cycling condition or target SOC, but strongly dependent on the temperature. The positive electrode was identified as the main source of impedance increase, with surface films having a composition that was independent of the target SOC, but with more of the same species present at higher temperatures. Furthermore, impedance results were shown to be highly dependent on both the electrode SOC during the measurement and the pressure applied to the electrode surface. An ageing hypothesis incorporating a resistive layer on the current collector and a local contact resistance (dependent on SOC) between the carbon and active material, both possibly leading to particle isolation, was found to be adequate in fitting the harvested aged electrode impedance data. The performance degradation of the cells with manganese chemistry was accelerated by both higher temperatures and larger DODs. The impedance increase was small, manifested in a SOC-dependent increase of the high-frequency semicircle and a noticeable increase of the high-frequency real axis intercept. The positive electrode had a larger decrease in capacity and increase in the magnitude of the high-frequency semi-circle (particularly at high intercalated lithium-ion concentrations) in comparison with the negative electrode. This SOC-dependent change was associated with cells cycled for either extended periods of time or at higher temperatures with a large DOD. An observed change of the cycling behaviour in the second potential plateau for the LixMn2O4-based electrode provided a possible kinetic-based explanation for the change of the high-frequency semi-circle. / Litiumjonbatteriet är en möjlig kandidat för energilagring i hybridfordon och i satelliter i låg omloppsbana, men än så länge är livslängden på batterierna ett problem. Utmaningen ligger i att kunna förstå hur batteriet åldras genom att utforska hur åldringsprocessen accelereras av faktorer som laddningstillstånd, urladdningsdjup och temperatur. Livslängdsstudier för två olika typer av batterier tänkta för olika applikationer utfördes: (1) knappceller med positiva LixNi0,8Co0,15Al0,05O2-baserade elektroder studerades med en effektstödd (power-assist) hybridcykel från EUCAR, och (2) laminerade kommersiella celler med positiva LixMn2O4-baserade elektroder studerades med en satellitcykel, avsedd för en satellit med låg omloppsbana. Cellerna öppnades och de uttagna elektrodernas elektrokemiska egenskaper utvärderades i två- och tre-elektroduppställningar. Resultaten från elektrokemiska impedansmätningar för den positiva LixNi0,8Co0,15Al0,05O2-baserade elektroden tolkades med hjälp av en fysikalisk tre-elektrod modell som tog hänsyn till de i litteraturen främst föreslagna effekterna av åldring. Prestandadegraderingen av celler med nickelkemi var oberoende av cykel och laddningstillståndet där åldringen skedde, men starkt beroende av temperaturen. Den positiva elektroden visade sig vara den största orsaken till impedansökningen i batteriet. Ytfilmerna på den positiva elektroden hade en sammansättning som var oberoende av laddningstillståndet men beroende av temperaturen. Impedansresultaten från de uttagna elektroderna var starkt beroende av både laddningstillstånd och yttre tryck på elektrodytan. Det visade sig att det var tillräckligt att ta hänsyn till ett resistivt skikt på strömtilledaren och en lokal kontaktresistans mellan kolet och det aktiva materialet (som är beroende av laddningstillståndet) för att anpassa modellen till impedansdata mätt på de uttagna elektroderna. Prestandadegraderingen av celler med mangankemi påskyndades av både högre temperaturer och högre urladdningsdjup. Impedansen ökade något, då både högfrekvenshalvcirkeln och högfrekvensintercepten ändrades. Positiva elektroden hade en större degradering i kapaciteten och en större ökning i magnituden av högfrekvenshalvcirkeln (speciellt vid högre litiumjon koncentrationer i elektroden) jämfört med den negativa elektroden. Denna laddningstillståndsberoende impedans-ökning var kopplad till celler som hade cyklats under en längre tid eller vid en högre temperatur och med ett högt urladdningsdjup. Ökningen i magnituden av högfrekvenshalvcirkeln skulle kunna vara relaterad till kinetiska begränsningar eftersom cyklingsbeteendet vid andra spänningsplatån ändrades samtidigt för de LixMn2O4-baserade elektroderna. / QC 20100621

The effect of solidification conditions on microstructural and mechanical properties of eutectic TiFe alloy cast under different conditions was examined. Samples exhibit different ultrafine eutectic structures (β-Ti(Fe) solid solution + TiFe). Different cooling conditions lead to the evolution of ultrafine eutectic oval-shaped colonies or elongated lamellar colonies with preferred orientation. Isotropic as well as anisotropic mechanical properties were obtained. Alloys exhibit compressive strengths between 2200 and 2700 MPa and plastic strains between 7 and 19 pct. in compression.

Diese Arbeit befasst sich mit der Nanostrukturierung von magnetischen Schichtsystemen mit Tunnelmagnetowiderstandseffekt (TMR-Effekt), welche in der Form von Nanosäulen in magnetoresistiven Speichern (MRAM) eingesetzt werden. Solche Nanosäulen können zukünftig ebenfalls als Nanoemitter von Mikrowellensignalen eine Rolle spielen. Dabei wird von der Auswahl eines geeigneten TMR-Schichtsystems mit einer MgO-Tunnelbarriere über die Präparation der Nanosäulen mit Seitenisolierung bis hin zum Aufbringen der elektrischen Zuleitungen eine komplette Prozesskette entwickelt und optimiert. Die Strukturen werden mittels optischer Lithographie und Elektronenstrahllithographie definiert, die anschließende Strukturübertragung erfolgt durch Ionenstrahlätzen (teilweise reaktiv) sowie durch Lift-off. Rückmeldung über Erfolg oder Probleme bei der Strukturierung geben Transmissionselektronenmikroskopie (teilweise mit Zielpräparation per Ionenfeinstrahl, FIB), Rasterelektronenmikroskopie sowie die Lichtmikroskopie. Es können so TMR-Nanosäulen mit minimalen Abmessungen von bis zu 69 nm x 71 nm hergestellt werden, von denen Nanosäulen mit Abmessungen von 65 nm x 87 nm grundlegend magneto-elektrisch charakterisiert worden sind. Dies umfasst die Bestimmung des TMR-Effektes und des Widerstandes der Tunnelbarriere (RA-Produkt). Weiterhin wurde das Verhalten der magnetischen Schichten bei größeren Magnetfeldern bis +-200mT sowie das Umschaltverhalten der magnetisch freien Schicht bei verändertem Winkel zwischen magnetischer Vorzugsachse des TMR-Elementes und dem äußeren Magnetfeld untersucht. Der Nachweis des Spin-Transfer-Torque Effektes an den präparierten TMR-Nanosäulen ist im Rahmen dieser Arbeit nicht gelungen, was mit dem zu hohen elektrischen Widerstand der verwendeten Tunnelbarriere erklärt werden kann. Mit dünneren Barrieren konnte der Widerstand gesenkt werden, allerdings führt ein Stromfluss durch diese Barrieren schnell zur Degradation der Barrieren. Weiterführende Arbeiten sollten das Ziel haben, niederohmige und gleichzeitig elektrisch belastbare Tunnelbarrieren in einem entsprechenden TMR-Schichtsystem abzuscheiden. Eine erste Auswahl an Ansatzpunkten dafür aus der Literatur wird im Ausblick gegeben. / This thesis deals with the fabrication of nanopillars with tunnel magnetoresistance effect (TMR-effect), which are used in magnetoresistive memory (MRAM) and may be used as nanooscillators for future near field communication devices. Starting with the selection of a suitable TMR-layer stack with MgO-tunnel barrier, the whole process chain covering the fabrication of the nanopillars, sidewall isolation and preparation of the supply lines on top is developed and optimised. The structures are defined by optical and electron beam lithography, the subsequent patterning is done by ion beam etching (partially reactive) and lift-off. Techniques providing feedback on the nanofabrication are transmission electron microscopy (partially with target preparation by focused ion beam, FIB), scanning electron microscopy and optical microscopy. In this way nanopillars with minimal dimensions reaching 69 nm x 71 nm could be fabricated, of which nanopillars with a size of 65 nm x 87 nm were characterized fundamentally with respect to their magnetic and electric properties. This covers the determination of the TMR-effect and the resistance of the tunnel barrier (RA-product). In addition, the behaviour of the magnetic layers under higher magnetic fields (up to +-200mT) and the switching behaviour of the free layer at different angles between the easy axis of the TMR-element and the external magnetic field were investigated. The spin transfer torque effect could not be detected in the fabricated nanopillars due to the high electrical resistance of the tunnel barriers which were used. The resistance could be lowered by using thinner barriers, but this led to a quick degradation of the barrier when a current was applied. Continuative work should focus on the preparation of tunnel barriers in an appropriate TMR-stack being low resistive and electrically robust at the same time. A first selection of concepts and ideas from the literature for this task is given in the outlook.

Developmental biology adresses how cells are organised into functional structures and eventually into a whole organism. It is crucial to understand the molecular basis for processes in development, by studying the expression and function of relevant genes and their relationship to each other. A gene function can be studied be creating loss-of-function situations, in which the change in developmental processes is examined in the absense of a functional gene product, or in gain-of-function studies, where a gene product is either intrinsically overproduced or ectopically upregulated. One approach for a loss-of-function situation is the creation of specific mutants in single genes, and the zebrafish (Danio rerio) has proven to be an excellent model organism for this purpose. In this thesis, I report on two forward genetic screens performed to find new mutants affecting brain development, in particular mutants defective in development and function of the midbrain-hindbrain boundary (MHB), an organiser region that patterns the adjacent brain regions of the midbrain and the hindbrain. In the first screen, I could identify 10 specific mutants based on morphology and the analysis of the expression patterns of lim1 and fgf8, genes functioning as early neuronal markers and as a patterning gene, respectively. Three of these mutants lacked an MHB, and by complementation studies, I identified these mutants as being defective in the spg locus. The second screen produced 35 new mutants by screening morphologically and with antibodies against acetylated Tubulin, which marks all axonal scaffolds, and anti-Opsin, which is a marker for photoreceptors in the pineal gland. According to their phenotype, I distributed the mutant lines into 4 phenotypic subgroups, of which the brain morphology group with 18 mutant lines was studied most intensively. In the last part of my thesis, I characterise one of these brain morphology mutants, broken heart. This mutant is defective in axonal outgrowth and locomotion, and shows a striking reduction of serotonergic neurons in the epiphysis and in the raphe nuclei in the hindbrain, structures involved in serotonin and melatonin production. Studies in other model organisms suggested a role of factors from the floor plate and the MHB in induction of the serotonergic neurons in the hindbrain, and using broken heart, I show that Fgf molecules such as Fgf4 and Fgf8 can restore partially the loss of serotonergic neurons in the mutant. I conclude that forward genetic screens are an invaluable tool to generate a pool of mutations in specific genes, which can be used to dissect complex processes in development such as brain development.

In the present work a Metal / organic / inorganic semiconductor hybrid heterostructure (Ag / DiMe−PTCDI / GaAs) was built under UHV conditions and characterised in situ. The aim was to investigate the influence of the organic layer in the surface properties of GaAs(100) and in the electrical response of organic−modified Ag / GaAs Schottky diodes. The device was tested by combining surface−sensitive techniques (Photoemission spectroscopy and NEXAFS) with electrical measurements (current−voltage, capacitance−voltage, impedance and charge transient spectroscopies). Core level examination by PES confirms removal of native oxide layers on sulphur passivated (S−GaAs) and hydrogen plasma treated GaAs(100) (H+GaAs) surfaces. Additional deposition of ultrathin layers of DiMe−PTCDI may lead to a reduction of the surface defects density and thereby to an improvement of the electronic properties of GaAs. The energy level alignment through the heterostructure was deduced by combining UPS and I−V measurements. This allows fitting of the I−V characteristics with electron as majority carriers injected over a barrier by thermionic emission as a primary event. For thin organic layers (below 8 nm thickness) several techniques (UPS, I−V, C−V, QTS and AFM) show non homogeneous layer growth, leading to formation of voids. The coverage of the H+GaAs substrate as a function of the nominal thickness of DiMe−PTCDI was assessed via C−V measurements assuming a voltage independent capacitance of the organic layer. The frequency response of the device was evaluated through C−V and impedance measurements in the range 1 kHz−1 MHz. The almost independent behaviour of the capacitance in the measured frequency range confirmed the assumption of a near geometrical capacitor, which was used for modelling the impedance with an equivalent circuit of seven components. From there it was found a predominance of the space charge region impedance, so that A.C. conduction can only takes place through the parallel conductance, with a significant contribution of the back contact. Additionally a non linear behaviour of the organic layer resistance probably due to the presence of traps was deduced. ( ) ω ' R QTS measurements performed on the heterostructure showed the presence of two relaxations induced by deposition of the organic layer. The first one is attributed to the presence of a deep trap probably located at the metal / organic interface, while the second one has very small activation energy ( ~ 20 meV) which are probably due to disorder at the organic film. Those processes with small activation energies proved to be determinant for fitting the I−V characteristics of DiMe−PTCDI organic modified diodes using the expressions of a trapped charge limited current regime TCLC. Such a model was the best analytical approach found for fitting the I−V response. Further improving probably will involve implementation of numerical calculations or additional considerations in the physics of the device.

No description available.

In the Master’s Thesis “Pre-investigation of Stormwater Quality at Metals Scrap Processing Plant” the literature review of 136 sources was performed with the focus on storm water pollution, physical and chemical properties of specific pollutants, origins of the pollution and pathways of the pollutants transport to the environment. Types of industrial storm water samples and sampling methodologies are described as well. Raprinfall data calculation are performed for the design of industrial storm water collection and treatment systems. The comprehensive analyses of storm water treatment are done. The experimental part of the work was carried out at the metal scrap processing industry with paved and unpaved aeries of the surfaces. During the research the industrial storm water screening characterisation was done at different locations of the whole territory. The treatment technology, including the sedimentation tank, retention tank and filtration trench was selected and calculated for the treatment of storm water of the investigated industry. The generalized conclusions and results of the work can be useful for state institutions, research institutions and the enterprises engaged in storm water management.