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Synthesis and characterisation of peptide-based probes for quantitative multicolour STORM imagingTaylor, Edward John Robert January 2018 (has links)
Current single molecule localisation microscopy methods allow for multicolour imaging of macromolecules in cells, and for a degree quantification on molecule numbers in one colour. However, that has not yet been an attempt to develop tools capable of quantitative imaging with multiple colours in cells. This work addressed this challenge by designing linker peptides with chemospecific groups to allow attachment of activator and emitter dyes for STORM imaging, and a targeting module. The design ensured a stoichiometric ratio of targeting module to activator and emitter dyes. Peptides with HaloTag ligands attached were labelled with various activator and emitter pairs and used to label HaloTag fusions of S. pombe and mouse embryonic stem cells. These peptides were found to bind non-specifically to various areas of both cell types, and did not localise to HaloTag protein, whereas controls did. Another peptide was also labelled with activator-emitter pairs and attached to expressed anti-GFP and ant-mCherry nanobodies via native chemical ligation. The labelled anti-GFP nanobody was to demonstrate ensemble and single molecule imaging in S. pombe, as well as characterisation on single molecule surfaces in comparison to a conventional randomly labelled antibody. The stoichiometrically labelled nanobody had a more consistent number of photons detected per localisation, number of localisation per molecule and number of blinks per molecule, which implied that it could be more useful than randomly labelled nanobodies for counting experiments. It was also shown to be capable of specific laser activation for STORM imaging with both an Alexa405Cy5 and Cy3Cy5 pairs. These anti-GFP and anti-mCherry nanobodies and peptide linker are new tools for both counting and multicolour imaging in super-resolution, which could be widely applied to constructs that are already tagged with GFP or mCherry.
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Modelling greenhouse gas emissions in cattle: From rumen to the whole-farmAlemu, Aklilu W January 2011 (has links)
Mathematical modeling in animal agriculture can be applied at various levels including at the tissue, organ, animal, farm, regional and global levels. The purposes of this research were i) to evaluate models used to estimate volatile fatty acid (VFA) and methane (CH4) production and assess their impact on regional enteric CH4 inventory, and ii) to develop a process-based, whole-farm model to estimate net farm GHG emissions. In the first study, four VFA stoichiometric models were evaluated for their prediction accuracy of rumen VFA and enteric CH4 production. Comparison of measured and model predicted values demonstrated that predictive capacity of the VFA models varied with respect to the type of VFA in rumen fluid which impacted estimated enteric CH4 production. Moving to a larger scale assessment, we examined the enteric CH4 inventory from Manitoba beef cattle (from 1990 to 2008) using two mechanistic rumen models that incorporate VFA stoichiometric models: COWPOLL and MOLLY, and two empirical models: Intergovernmental Panel on Climate Change (IPCC) Tier 2 and a nonlinear equation (Ellis). The estimated absolute enteric CH4 production varied among models (7 to 63%) indicating that estimates of GHG inventory depend on model selection. This is an important consideration if the values are to be used for management and/or policy-related decisions. Development of models at the individual farm component level (animal, soil, crop) does not accurately reflect net GHG emissions generated from the whole production system. We developed a process-based, whole-farm model (Integrated Components Model, ICM), using the existing farm component models COWPOLL, manure-DNDC and some aspects of IPCC to integrate farm components and their associated GHG emissions. Estimates of total farm GHG emissions and their relative contribution using the ICM were comparable to estimates using two other whole-farm models (Integrated Farm System Model and Holos model). Variation was observed among models both in estimating whole-farm GHG emissions and the relative contribution of the different sources in the production system. Overall, whole-farm models are required to explore management options that will mitigate GHG emissions and promote best management practices. However, for full assessment of the production system, other benefits of the system (e.g., carbon sequestration, ecosystem services), which are not part of current whole-farm models, must be considered.
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Modelling greenhouse gas emissions in cattle: From rumen to the whole-farmAlemu, Aklilu W January 2011 (has links)
Mathematical modeling in animal agriculture can be applied at various levels including at the tissue, organ, animal, farm, regional and global levels. The purposes of this research were i) to evaluate models used to estimate volatile fatty acid (VFA) and methane (CH4) production and assess their impact on regional enteric CH4 inventory, and ii) to develop a process-based, whole-farm model to estimate net farm GHG emissions. In the first study, four VFA stoichiometric models were evaluated for their prediction accuracy of rumen VFA and enteric CH4 production. Comparison of measured and model predicted values demonstrated that predictive capacity of the VFA models varied with respect to the type of VFA in rumen fluid which impacted estimated enteric CH4 production. Moving to a larger scale assessment, we examined the enteric CH4 inventory from Manitoba beef cattle (from 1990 to 2008) using two mechanistic rumen models that incorporate VFA stoichiometric models: COWPOLL and MOLLY, and two empirical models: Intergovernmental Panel on Climate Change (IPCC) Tier 2 and a nonlinear equation (Ellis). The estimated absolute enteric CH4 production varied among models (7 to 63%) indicating that estimates of GHG inventory depend on model selection. This is an important consideration if the values are to be used for management and/or policy-related decisions. Development of models at the individual farm component level (animal, soil, crop) does not accurately reflect net GHG emissions generated from the whole production system. We developed a process-based, whole-farm model (Integrated Components Model, ICM), using the existing farm component models COWPOLL, manure-DNDC and some aspects of IPCC to integrate farm components and their associated GHG emissions. Estimates of total farm GHG emissions and their relative contribution using the ICM were comparable to estimates using two other whole-farm models (Integrated Farm System Model and Holos model). Variation was observed among models both in estimating whole-farm GHG emissions and the relative contribution of the different sources in the production system. Overall, whole-farm models are required to explore management options that will mitigate GHG emissions and promote best management practices. However, for full assessment of the production system, other benefits of the system (e.g., carbon sequestration, ecosystem services), which are not part of current whole-farm models, must be considered.
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Modeling photosynthesis and related metabolic processes : from detailed examination to consideration of the metabolic contextArnold, Anne January 2014 (has links)
Mathematical modeling of biological systems is a powerful tool to systematically investigate the functions of biological processes and their relationship with the environment. To obtain accurate and biologically interpretable predictions, a modeling framework has to be devised whose assumptions best approximate the examined scenario and which copes with the trade-off of complexity of the underlying mathematical description: with attention to detail or high coverage. Correspondingly, the system can be examined in detail on a smaller scale or in a simplified manner on a larger scale. In this thesis, the role of photosynthesis and its related biochemical processes in the context of plant metabolism was dissected by employing modeling approaches ranging from kinetic to stoichiometric models.
The Calvin-Benson cycle, as primary pathway of carbon fixation in C3 plants, is the initial step for producing starch and sucrose, necessary for plant growth. Based on an integrative analysis for model ranking applied on the largest compendium of (kinetic) models for the Calvin-Benson cycle, those suitable for development of metabolic engineering strategies were identified.
Driven by the question why starch rather than sucrose is the predominant transitory carbon storage in higher plants, the metabolic costs for their synthesis were examined. The incorporation of the maintenance costs for the involved enzymes provided a model-based support for the preference of starch as transitory carbon storage, by only exploiting the stoichiometry of synthesis pathways.
Many photosynthetic organisms have to cope with processes which compete with carbon fixation, such as photorespiration whose impact on plant metabolism is still controversial. A systematic model-oriented review provided a detailed assessment for the role of this pathway in inhibiting the rate of carbon fixation, bridging carbon and nitrogen metabolism, shaping the C1 metabolism, and influencing redox signal transduction.
The demand of understanding photosynthesis in its metabolic context calls for the examination of the related processes of the primary carbon metabolism. To this end, the Arabidopsis core model was assembled via a bottom-up approach. This large-scale model can be used to simulate photoautotrophic biomass production, as an indicator for plant growth, under so-called optimal, carbon-limiting and nitrogen-limiting growth conditions.
Finally, the introduced model was employed to investigate the effects of the environment, in particular, nitrogen, carbon and energy sources, on the metabolic behavior. This resulted in a purely stoichiometry-based explanation for the experimental evidence for preferred simultaneous acquisition of nitrogen in both forms, as nitrate and ammonium, for optimal growth in various plant species.
The findings presented in this thesis provide new insights into plant system's behavior, further support existing opinions for which mounting experimental evidences arise, and posit novel hypotheses for further directed large-scale experiments. / Mathematische Modellierung biologischer Systeme eröffnet die Möglichkeit systematisch die Funktionsweise biologischer Prozesse und ihrer Wechselwirkungen mit der Umgebung zu untersuchen. Um präzise und biologisch relevante Vorhersagen treffen zu können, muss eine Modellierungsstrategie konzipiert werden, deren Annahmen das untersuchte Szenario bestmöglichst widerspiegelt und die dem Trade-off der Komplexität der zugrunde liegenden mathematischen Beschreibung gerecht wird: Detailtreue gegenüber Größe. Dementsprechend kann das System detailliert, in kleinerem Umfang oder in vereinfachter Darstellung im größeren Maßstab untersucht werden. In dieser Arbeit wird mittels verschiedener Modellierungsansätze, wie kinetischen und stöchiometrischen Modellen, die Rolle der Photosynthese und damit zusammenhängender biochemischer Prozesse im Rahmen des Pflanzenstoffwechsels analysiert.
Der Calvin-Benson-Zyklus, als primärer Stoffwechselweg der Kohlenstofffixierung in C3-Pflanzen, ist der erste Schritt der Stärke- und Saccharoseproduktion, welche maßgeblich für das Wachstum von Pflanzen sind. Basierend auf einer integrativen Analyse zur Modellklassifizierung wurden aus der größten bekannten Sammlung von (kinetischen) Modellen des Calvin-Benson-Zyklus diejenigen ermittelt, die für die Entwicklung von Metabolic-Engineering-Strategien geeignet sind.
Angeregt von der Fragestellung warum Kohlenstoff transitorisch vorwiegend in Form von Stärke anstatt Saccharose gespeichert wird, wurden die metabolischen Kosten beider Syntheseprozesse genauer betrachtet. Die Einbeziehung der Bereitstellungskosten der beteiligten Enzyme stützt die Tatsache, dass bevorzugt Stärke als temporärer Kohlenstoffspeicher dient. Die entprechende Untersuchung erfolgte einzig auf Grundlage der Stöchiometrie der Synthesewege.
In vielen photosynthetisch-aktiven Organismen findet zudem Photorespiration statt, die der Kohlenstofffixierung entgegenwirkt. Die genaue Bedeutung der Photorespiration für den Pflanzenmetabolismus ist noch umstritten. Eine detaillierte Einschätzung der Rolle dieses Stoffwechselweges bezüglich der Inhibierung der Kohlenstofffixierungsrate, der Verknüpfung von Kohlenstoff- und Stickstoffmetabolismus, der Ausprägung des C1-Stoffwechsels sowie die Einflussnahme auf die Signaltransduktion wurde in einer modell-basierten, kritischen Analyse vorgenommen.
Um die Photosynthese in ihrem metabolischen Kontext verstehen zu können, ist die Betrachtung der angrenzenden Prozesse des primären Kohlenstoffmetabolismus unverzichtbar. Hierzu wurde in einem Bottom-up Ansatz das Arabidopsis core Modell entworfen, mittels dessen die Biomasseproduktion, als Indikator für Pflanzenwachtum, unter photoautotrophen Bedingungen simuliert werden kann. Neben sogenannten optimalen Wachstumsbedingungen kann dieses großangelegte Modell auch kohlenstoff- und stickstofflimitierende Umweltbedingungen simulieren.
Abschließend wurde das vorgestellte Modell zur Untersuchung von Umwelteinflüssen auf das Stoffwechselverhalten herangezogen, im speziellen verschiedene Stickstoff-, Kohlenstoff- und Energiequellen. Diese auschließlich auf der Stöchiometrie basierende Analyse bietet eine Erklärung für die bevorzugte, gleichzeitige Aufnahme von Nitrat und Ammonium, wie sie in verschiedenen Spezies für optimales Wachstum experimentell beobachtet wurde.
Die Resultate dieser Arbeit liefern neue Einsichten in das Verhalten von pflanzlichen Systemen, stützen existierende Ansichten, für die zunehmend experimentelle Hinweise vorhanden sind, und postulieren neue Hypothesen für weiterführende großangelegte Experimente.
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Exploring the limits of hydrogen assisted jet ignitionHamori, Ferenc Unknown Date (has links) (PDF)
Homogeneously charged spark ignition (SI) engines are unable to stabilise the combustion in ultra lean mixtures, therefore they operate with a near stoichiometric air-fuel ratio (AFR) at all load points. This produces high engine out NOx and CO emissions with a compromise on fuel consumption. Moreover, stoichiometric operation is needed for effective operation of a three way catalyst, which is not adequate to meet future fuel consumption targets. (For complete abstract open document)
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Electrochemical Advanced Oxidation Processes for removal of Pharmaceuticals from water : Performance studies for sub-stoichiometric titanium oxide anode and hierarchical layered double hydroxide modified carbon felt cathode / Procédés électrochimiques d'oxydation avancée pour l'élimination des composés pharmaceutiques de l'eau : Etude des performances d'une anode d'oxyde de titane sous-stoechiométrique et feutre de carbone modifie par double couche d'hydroxideGaniyu, Soliu 02 December 2016 (has links)
AbstractLes polluants émergents que sont les résidus de produits pharmaceutiques sont devenus une problématique majeure de par leur persistance et leur accumulation continue dans les différents compartiments de l’environnement. Leur élimination est un des challenges majeurs de ce siècle. Les procédés électrochimiques d’oxydation avancée (PEOA) tel que l’oxydation anodique (AO) et l’électro-Fenton (EF) ont démontré leur efficacité pour la dégradation et la minéralisation complète de cette classe de polluant. Un oxyde de titane sous-stœchiométrique déposé par plasma sur un alliage de titane a été étudié comme anode alternative peu coûteuse, stable et efficace au cours des procédés d’OA et d’EF pour la dégradation et la minéralisation de deux pharmaceutiques, l’amoxicilline (AMX) et le propanolol (PPN). Une excellente minéralisation de ces deux composés a été atteinte avec l’anode Ti4O7 comparé à l’utilisation d’une anode dimensionnellement stable (ADS) et d’une anode de platine (Pt) avec des conditions expérimentales similaires, mais une plus faible efficacité a été observé par comparaison à une anode de diamant dopé au bore (DDB) au cours du procédé d’OA. Une quasi-total minéralisation (96%) du PPN a été atteinte avec l’anode Ti4O7 au cours du procédé EF après 8 h d’électrolyse à 120 mA. Plusieurs intermédiaires aromatiques, bicycliques et autres ont été identifiés et quantifiés au cours du traitement électrochimique des deux composés pharmaceutiques, ainsi que des acides carboxyliques à chaîne courte et des ions inorganique comme produits finaux de dégradation. Des voies plausibles de dégradation ont été proposées à partir des intermédiaires identifiés, des ions inorganiques libérés ainsi que des données obtenues sur les acides carboxyliques et le COT. La solution initiale d’AMX a mené à une relativement forte inhibition de la bactérie V. fisheri, qui a ensuite augmenté au cours des premiers stades de l’électro-oxydation de par la formation d’intermédiaires cycliques plus toxiques que la molécule mère, avant de diminuer nettement au cours des étapes suivantes de l’électrolyse. Puisque le Ti4O7 est produit principalement à partir du TiO2, un matériau bon marché et abondant, ce matériau d’anode pourrait être une alternative intéressante pour le traitement des eaux usées industrielles par oxydation électrochimique. Par ailleurs, une cathode de feutre de carbone modifiée par des composés hydroxydes à double couche CoFe (CoFe-LDH/CF) et synthétisée par un procédé solvothermique a été étudiée come catalyseur/électrode pour la dégradation du polluant organique Acide Orange II (AO7) par le procédé EF sur une gamme large de pH. Une excellente minéralisation de ce colorant a été atteinte pour des pH allant de 2 à 7.1, avec une élimination du COT largement supérieure à celle atteinte en utilisant le procédé EF avec une cathode de feutre de carbone brut, quel que soit le pH étudié. La cathode préparée a montré une bonne capacité de réutilisation et peut constituer une alternative pour le traitement des eaux usées à des valeurs de pH naturel / Pharmaceuticals residues as emerging pollutants have become a major concern due to their persistence and continuous accumulation in various environmental compartments and their removal is one the major challenges of this century. Electrochemical advanced oxidation processes (EAOPs) such as anodic oxidation (AO) and electro-Fenton (EF) have shown to be efficient techniques for complete degradation and mineralization of this class of pollutants. A substoichiometric titanium oxide (Ti4O7) deposited on titanium alloy by plasma elaboration was investigated as an alternative stable and efficient low cost anode materials for application in AO and EF for degradation of pharmaceuticals amoxicillin (AMX) and propranolol (PPN) and mineralization of their aqueous solutions. Excellent mineralization of both pharmaceuticals was achieved with Ti4O7 anode compared to dimensional stable anode (DSA) and platinum (Pt) anodes at similar experimental conditions, but less efficient when compared with boron doped diamond (BDD) anode during AO treatment. Almost complete mineralization (96%) was attained with Ti4O7 anode in EF degradation of PPN at 120 mA after 8 h of electrolysis. Several aromatic, bicyclic and other intermediate byproducts were identified and quantified during the electrochemical treatment of both pharmaceuticals, with the final end products in the treated solutions being short-chain carboxylic acids and inorganic ions. Plausible mineralization pathways for both pharmaceuticals were proposed based on the identified intermediates, released inorganic ions and carboxylic acids as well as TOC data. Initial AMX solution shows relatively high inhibition to V. fischeri bacteria, which further increased at the early stage of electrooxidation due to formation of cyclic intermediates more toxic than mother molecules but sharply decreased at the later stage of electrolysis. Since the Ti4O7 is produced mainly from TiO2 which is very cheap and highly abundant material, this anode material could be an interesting alternative electrode in industrial wastewater treatment by electrochemical oxidation. On the other hand, CoFe-layer double hydroxide modified carbon-felt (CoFe-LDH/CF) cathode synthesized by solvothermal process was studied as a heterogeneous catalyst/electrode for degradation of organic pollutant Acid Orange II (AO7) over a wide pH range. Excellent mineralization of this azo dye solution was achieved in pH range 2 – 7.1, with TOC removal much higher than corresponding homogeneous EF with raw carbon-felt (CF) at all pH studied. The prepared cathode exhibited good reusability and can constitute an alternative for the treatment wastewater effluents at neutral pH values
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Study of the evolution of symbiosis at the metabolic level using models from game theory and economics / L’étude de l’évolution de la symbiose au niveau métabolique en utilisant des modèles de la théorie des jeux et de l’économieWannagat, Martin 04 July 2016 (has links)
Le terme symbiose recouvre tous types d'interactions entre espèces et peut être défini comme une association étroite d'espèces différentes vivant ensemble. De telles interactions impliquant des micro-organismes présentent un intérêt particulier pour l'agriculture, la santé, et les questions environnementales. Tous les types d'interactions entre espèces tels que le mutualisme, le commensalisme, et la compétition, sont omniprésents dans la nature et impliquent souvent le métabolisme. La libération de métabolites par des organismes dans l'environnement permet à d'autres individus de la même espèce ou de différentes espèces de les récupérer pour leur usage propre. Dans cette thèse, nous étudions comment les interactions entre espèces façonnentl'environnement. Nous examinons les questions de (i) quels sont les besoins minimaux en éléments nutritifs pour établir la croissance, et (ii) quels métabolites peuvent être échangés entre un organisme et son environnement. L'énumération de tous les ensembles minimaux stoechiométriques de précurseurs et de tous les ensembles minimaux de métabolites échangés,en utilisant des modèles complets de réseaux métaboliques, fournit un meilleur aperçu des interactions entre les espèces. Dans un environnement spatialement homogène, les métabolites qui sont libérés dans un tel environnement sont partagés par tous les individus. Le problème qui se pose alors est de savoir comment les tricheurs, les individus qui profitent des métabolites libérés sans contribuer au bien public, peuvent être exclus de la population. Ceci et d'autres configurations ont déjà été modélisées avec des approches de la théorie des jeux et de l'économie. Nous examinons comment les concepts d'ensembles minimaux de précurseurs stoechiométriques et d'ensembles minimaux de composés échangés peuvent être introduits dans ces modèles / Symbiosis, a term that brings all types of species interaction under one banner, is defined as a close association of different species living together. Species interactions that comprise microorganisms are of particular interest for agriculture, health, and environmental issues. All kinds of species interactions such as mutualism, commensalism, and competition, are omnipresent in nature and occur often at the metabolic level. Organisms release metabolites to the environment which are then taken up by other individuals of the same or of different species. In this thesis, we study how species interactions shape the environment. We examine the questions of (i) what are the minimal nutrient requirements to sustain growth, and (ii) which metabolites can be exchanged between an organism and its environment. Enumerating all minimal stoichiometric precursor sets, and all minimal sets of exchanged metabolites, using metabolic network models, provide a better insight into species interactions. In a spatially homogeneous environment, the metabolites that are released to such an environment are shared by all individuals. The problem that then arises is how cheaters, individuals that profit from the released metabolites without contributing to the public good, can be prevented from the population. This and other configurations were already modeled with approaches from game theory and economics. We examine how the concepts of minimal stoichiometric precursor sets and minimal sets of exchanged compounds can be introduced into such models
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Study of SATP Gas Parameter on CCPP Performance Optimum Empirical Proof and Analysis (For NAN-PU CC¡1~4 Unit)Huang, Sung-liang 21 July 2004 (has links)
Combined cycle power plants haven becoming one of the mainstream power plants in the twenty-one century. The emergence of high 600¢J exhaust temperature of the gas turbine, due to the recent rapid enhancement of aerospace material and blade cooling methods, upgrades the gas turbine from low efficiency dual pressure non-reheat unit to high efficiency triple pressure reheat combined cycle power plants. In addition, the increase of turbine inlet temperature by 10~15¢J every year leads to the renewal of the advanced models gas turbine less than ten years. There are three-turbine inlet temperature (TIT) definitions in the gas turbine:
(1) TA defines firing temperature as the mass flow mean total temperature before the first-stage stationary diagram edge plane.( Westinghouse or MHI product)
(2) TB defines fire temperature as the mass flow mean total temperature at the first-stage nozzle trailing edge plane, ( GE product).
(3) TC defines ISO firing temperature; it is a stoichiometric combustion temperature. It is not a physical temperature. ( Siemens ¡® Alstom ABB product).
This study shows how to calculate compressor inlet mass flow balance, turbine power balance and heat balance on the combustion chamber system.
In order to prove correctness of the balance equation, the data are taken from the heat balance diagram and acceptance test of Nan-pu power station combined cycle. The result shows that the study is sultable for application of the optimum analysis for CCPP operation performance. This type of combined cycle power plant suits not only for the base-load but also for the cycling-load operation.
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Etude des mécanismes de diffusion de l’oxygène dans SrFeO3-x et Pr2NiO4+d, réalisée par diffraction du rayonnement synchrotron in situ sur monocristal / Exploring oxygen diffusion mechanisms in SrFeO3-x and Pr2NiO4+d, followed up on single crystals by in situ synchrotron diffractionMaity, Avishek 26 September 2016 (has links)
La compréhension des aspects fondamentaux de la diffusion de l'oxygène dans les oxydes solides à des températures modérées, jusqu'à température ambiante, est un enjeu majeur pour le développement d'une variété de dispositifs technologiques dans un avenir proche. Cela concerne, par exemple, le développement de la prochaine génération des électrolytes et membranes solides d'oxygène pour les piles à combustible de type SOFC. Autrement, les réactions d'intercalation de l'oxygène réalisées à basse température présentent un outil puissant pour contrôler le dopage en oxygène ainsi que des propriétés physiques. Dans ce contexte, les oxydes ayant une structure type brownmillérite (A2BB'O5) ou type K2NiF4, ont attiré beaucoup d'attention, car ils montrent une mobilité de l'oxygène déjà à température ambiante.Dans cette thèse, nous avons étudié les mécanismes d'intercalation d'oxygène dans SrFeO2.5+x, ainsi que Pr2NiO4+x par des méthodes de diffraction in situ, réalisées sur des monocristaux dans une cellule électrochimique spécifiquement conçue, explorant principalement le rayonnement synchrotron. Ceci a permis d’explorer en 3D tout le réseau réciproque, et d'obtenir des informations précieuses sur la diffusion diffuse, sur les faibles intensités des raies de surstructure, ainsi que des informations sur la fraction volumique des différents domaines de maclage au cours de la réaction, impossibles à accéder par diffraction de poudre.Les deux systèmes montrent des changements structuraux complexes, accompagnés par une mise en ordre de l'oxygène à longue portée. Au cours de l'intercalation d'oxygène nous avons mis en évidence deux phases intermédiaires, SrFeO2.75 et SrFeO2.875, possédant des lacunes en oxygène ordonnées à longue échelle. En raison du maclage, avec jusqu'à douze possibles individus, nous avons suivi directement la formation et l'évolution des domaines de maclage ainsi que leur micro-structure apparentée. Nous avons ainsi observé un mécanisme de réaction topotactique pour SrFeO2.5 vers SrFeO2.75, tandis que l'oxydation de SrFeO2.75 conduit à des importants réarrangements de l’oxygène, associés à un changement de nombre de domaines de maclage. La réduction électrochimique de la phase orthorhombique Pr2NiO4.25 donne Pr2NiO4.0 comme produit final, ayant la même symétrie, tandis que la phase tétragonale Pr2NiO~4.12 apparaît comme phase intermédiaire. Utilisant un monocristal avec un diamètre de 50 microns, la réaction se déroule dans des conditions d'équilibre dans moins que 24 heures, ce qui implique un coefficient de diffusion de l’oxygène anormalement élevé, supérieur à 10-^11cm2*s-1 à température ambiante. Nous avons également étudié le diagramme de phase de Pr2NiO4.25 sur monocristal jusqu’à 1100°C en chauffant sous air. Une série complexe de transition de phases a été mise en évidence, la vraie symétrie de Pr2NiO4.25 s’avérée en fait monoclinique.Outre l'exploration des diagrammes de phases complexes de SrFeO2.5+x et Pr2NiO4+d, nous avons pu étudier les changements détaillés concernant la micro-structure à l'aide de diffraction sur monocristaux in situ, impossible à accéder par des méthodes de diffraction de poudre classique. Les changements de la micro-structure des domaines va bien au-delà des composés étudiés ici et porte une grande importance pour extrapoler sur la performance, la stabilité et la durée de vie par exemple des matériaux utilisés pour le stockage de l’énergie. / Understanding fundamental aspects of oxygen diffusion in solid oxides at moderate temperatures, down to ambient, is an important issue for the development of a variety of technological devices in the near future. This concerns e.g. the progress and invention of next generation solid oxygen ion electrolytes and oxygen electrodes for solid oxide fuel cells (SOFC) as well as membrane based air separators, oxygen sensors and catalytic converters to transform e.g. NOx or CO from exhaust emissions into N2 and CO2. On the other hand oxygen intercalation reactions carried out at low temperatures present a powerful tool to control hole doping, i.e. the oxygen stoichiometry, in electronically correlated transition metal oxides. In this aspect oxides with Brownmillerite (A2BB’O5) and K2NiF4-type frameworks, have attracted much attention, as they surprisingly show oxygen mobility down to ambient temperature. In this thesis we investigated oxygen intercalation mechanisms in SrFeO2.5+x as well as Pr2NiO4+x by in situ diffraction methods, carried out on single crystals in especially designed electrochemical cell, mainly exploring synchrotron radiation. Following up oxygen intercalation reactions on single crystals is challenging, as it allows to scan the whole reciprocal lattice, enabling to obtain valuable information as diffuse scattering, weak superstructure reflections, as well as information of the volume fraction of different domains during the reaction, to highlight a few examples, difficult or impossible to access by powder diffraction. Both title systems are able to take up an important amount of oxygen on regular and interstitial lattice sites, inducing structural changes accompanied by long range oxygen ordering. For SrFeO2.5+x the uptake of oxygen carried out by electrochemical oxidation yields SrFeO3 as the final reaction product. The as grown SrFeO2.5 single crystals we found to show a complex defect structure, related to the stacking disorder of the octahedral and tetrahedral layers. During the oxygen intercalation we evidenced the formation of two reaction intermediates, SrFeO2.75 and SrFeO2.875, showing complex and instantly formed long range oxygen vacancies. Due to the specific twinning with up to totally twelve possible twin individuals, we directly follow up the formation and changes of the specific domain and related micro-structure. We thus observed a topotactic reaction mechanism from SrFeO2.5 to SrFeO2.75, while further oxidation lead to important rearrangements in the dimensionality of the oxygen defects in SrFeO2.75, implying the formation of an additional twin domain in course of the reaction. The electrochemical reduction of orthorhombic Pr2NiO4.25 yields stoichiometric Pr2NiO4.0 as the final reaction product with the same symmetry, while tetragonal Pr2NiO~4.12 appears as a non-stoichiometric intermediate phase. Using a single crystal with 50µm diameter, the reaction proceeded under equilibrium conditions in slightly less than 24h, implying an unusually high oxygen ion diffusion coefficient of > 10^-11cm2*s-1 at already ambient temperature. From the changes of the associated twin domain structure during the reduction reaction, the formation of macro twin domains was evidenced. Heating up Pr2NiO4.25 single crystals in air revealed a complex series of phase transition, evidencing the true symmetry of the starting phase to be in fact monoclinic. Beside exploring the complex phase diagrams of SrFeO2.5+x and Pr2NiO4+d we were able to investigate detailed changes in the micro-structure using in situ single crystal diffraction techniques, impossible to access by classical powder diffraction methods. The importance of changes in the domain structure goes far beyond the investigated title compounds and has utmost importance of the performance, stability and lifetime of e.g. battery materials.
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Efeitos ocasionados pela deficiência e excesso de lítio nas propriedades estruturais e ópticas do composto LiAl5O8 dopado com cério, európio ou térbioSilva, Ariosvaldo Junior Sousa 19 July 2017 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The study describes the preparation, structural and optical characterization of
Lithium Aluminate (LiAl5O8) pristine and doped with trivalent lanthanide ions (Ln3+
=Ce3+, Eu3+ or Tb3+). In this study, Lithium Aluminate pure and doped were produced
via sol-gel route, using glucose anhydrous as polymer agent. Structural analysis was performed
using X-rays di raction (XRD) and optical properties through photoluminescence
spectroscopy. The X-ray di raction (XRD) patterns showed signi cant evidence of formation
of the desired crystalline phase. Based on XRD patterns and using the Scherrer
equation, it is estimated that all of the samples produced have a nanosize dimensions.
The results revels stoichiometric variation of lithium and the incorporation of the dopant
ion did not cause signi cant changes in the LiAl5O8. Photoluminescence measurement of
(LiAl5O8) pristine and doped with Ce3+, Eu3+ or Tb3+, for samples with and without
variation of lithium stoichiometry were performed. The Excitation and emission spectra
of the LiAl5O8 pristine showed with wide and high intensity bands, all attributed to the
Fe3+ ion. The presence of iron ions are attributed to its existence in precursor reagents.
Excitation spectra of Ce3+, Eu3+ or Tb3+, have high intensity wide band and wavelengths
of higher excitation intensity in the ultraviolet region (240-290 nm), all attributed the speci
c intercon guration transitions of each dopant ion. Being for the ions Ce3+ and Tb3+
due to the transition 4f!5d, and for the ion Eu3+ due to the charge transfer between
Oxygen and Europium. The emission spectra, exhibited high emission intensity in the
blue colors when doped with Ce3+ ions, red when doped with Eu3+ ions and green with
Tb3+ ions. Based on the emission spectra and chromaticity diagrams, it was possible to
verify that the accomplishment of the stoichiometric variation of Lithium in uences quantitatively
in the spectral emission, motivating a variation in the chromaticity coordinates.
Therefore, it can conclude that the variation of the Lithium stoichiometry signi cantly
changes the optical properties of the LiAl5O8 when doped Ce3+, Eu3+ or Tb3+. This
is capable to emitting di erent color bands in the region of blue, red and green when
exposed to ultraviolet radiation. / O presente estudo apresenta à sintetização, caracterização estrutural e óptica do
Aluminato de Lítio (LiAl5O8) puro e dopado com íons lantanídeos trivalentes (Ln3+ =
Ce3+, Eu3+ ou Tb3+). Os aluminatos de lítio puro e dopados foram produzidos através da
rota de síntese via sol-gel, utilizando glicose anidra como agente polimerizador. A análise
estrutural foi realizada por meio da difração de raios X (DRX), re namento Rietveld e
óptica através da espectroscopia fotoluminescente. Os padrões de DRX evidenciaram de
maneira signi cativa a formação da fase cristalina desejada, estando em conformidade
com o padrão teórico mais aceito na literatura. Com base nos DRX e através da equação
de Scherrer, estima-se que todas as amostras produzidas neste estudo apresentam-se com
dimensões nanométricas. Mediante o re namento Rietveld, veri cou-se que o desvio estequiom
étrico de lítio assim como à introdução do íon dopante não ocasionaram mudanças
de grande relevância na formação estrutural do LiAl5O8. O estudo fotoluminescente do
LiAl5O8 puro e dopado com Ce3+, Eu3+ ou Tb3+ para as amostras com e sem desvio de
estequiometria de lítio foram realizados através dos espectros de excitação e emissão. Os
espectros de excitação e emissão do LiAl5O8 puro apresentaram-se com bandas largas e
de grande intensidade, todas atribuídas ao íon Fe3+. A presença do ferro é atribuída a
sua existência nos reagentes precursores. Os espectros de excitação do Ce3+, Eu3+ ou
Tb3+ se apresentam na forma de uma banda larga com alta intensidade e comprimentos
de onda de maior intensidade de excitação na região do ultravioleta (240-290 nm),
todas devidamente atribuídas as transições intercon guracionais especí cas de cada íon
dopante, sendo para os íons Ce3+ e Tb3+ oriunda da transição 4f!5d, e para o íon Eu3+
devido à transferência de carga entre o oxigênio e o európio. Já os espectros de emissão,
exibiram alta intensidade de emissão nas cores azul proveniente do Ce3+, vermelho devido
a utilização do íon Eu3+ e verde oriundo do dopante Tb3+. Com base, nos espectros
de emissão e pelos diagramas de cromaticidade, constatou-se que a realização do desvio
estequiométrico de lítio in uência quantitativamente na formação espectral, motivando
uma variação nas coordenadas de cromaticidade. Isto determina a mudança na cor de
emissão do material, ou seja, a variação da estequiometria de lítio proporciona de maneira
signi cativa mudanças nas propriedades ópticas do LiAl5O8 quando dopado. Portanto,
obteve-se como resultado materiais com o mesmo padrão estrutural, capazes de emitir em
diferentes faixas de cores na região do azul, vermelho e verde, quando expostos a radiação
ultravioleta. / São Cristóvão, SE
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