<p>When simulating reactor physics experiments, uncertainties in nuclear data result in a bias between simulated and experimental values. For new reactor designs or for power reactor designs the bias can be estimated using a set of experiments. How- ever, the experiments used to estimate the bias must be applicable to the power reactor design of interest. Similarity studies can be performed to ensure this is the case. Here, potential experiments in the ZED-2 heavy water critical facility at Chalk River Laboratories were developed that would be applicable to the multiplication factor bias calculation of three thoria plutonia fuelled power reactor designs. The power reactor designs that were analyzed were the CANDU 6 with 37-element fuel bundles and 43-element fuel bundles, and a Canadian SCWR design with 78- element fuel assemblies. The power reactors were simulated using the code package SCALE 6.1 under burnup conditions that were determined using the lattice code DRAGON 3.06H and the diffusion code DONJON 3.02A. The intermediate results from DRAGON and DONJON were used to compare the benefits of various reactor designs. Various critical core configurations were then simulated in the ZED-2 re- actor using the SCALE 6.1 package. The similarities between the potential ZED-2 reactor experiments and the power reactors were analyzed. These results were used to design a set of experiments having sufficiently high completeness that they can be used as part of a bias calculation using the generalized linear least squares method. To do so a methodology was developed to guide the experiment set design process in which the fuel type, lattice arrangements, and coolant type are modified and the effects on the sensitivity coverage analyzed. A set of six experiments was designed for which all of the power reactor designs had a completeness of 0.7 or higher.</p> / Master of Applied Science (MASc)

<p> Reduced oxygen tension (i.e. hypoxia) regulates gene expression in various chromaffin cell types that synthesize catecholamines. In this study, the effect of chronic hypoxia on tyrosine hydroxylase (TH) mRNA and protein expression was investigated in the adrenomedullary chromaffin MAH cell line. RT-PCR results indicated that TH mRNA was expressed in MAH cells both during normoxia (20% 0 2) and hypoxia (5% 02). However, TH mRNA expression during chronic hypoxia was significantly higher than that during normoxia, increasing by approximately 2- fold after 16 hour exposure to chronic hypoxia. Western Blot analysis of the regulation of TH gene expression by chronic hypoxia indicated that TH protein initially decreased during 10 hr exposure to hypoxia and this was followed by a rapid increase in expression over the next 10 hr, and then by a slower increase (up to 1.3x initial control) after 72 hr exposure. Therefore, TH mRNA and protein levels were changed in MAH cells by hypoxia in a time-dependent manner. Surprisingly, cobalt treatment of MAH cells, expected to mimic the effects of chronic hypoxia, had little effect on TH gene expression. Interestingly, the decrease in TH expression protein after 10 hr exposure to hypoxia was prevented by nifedipine, an L-type calcium channel blocker. These results suggest that MAH cells represent a useful model system for examining hypoxia-induced gene regulation in an 02-sensitive cell line. Additionally, preliminary studies on HIF-1a expression in MAH cells showed that HIF-la mRNA was expressed and remained stable under both hypoxic and normoxic conditions. </p> / Thesis / Master of Science (MSc)

Le but de ma thèse est de conduire et d’utiliser les premières observations atmosphériquesde surface du CO2, de l’O2, du CH4 et de la composition isotopique de la vapeur d’eau et desprécipitations dans la région peu instrumentée du sud du Groenland. Quelles informations cesobservations locales peuvent-elles nous apporter à la fois concernant les processus atmosphériqueslocaux et concernant le transport atmosphérique à grande échelle ? Peut-on en extrairedes informations sur les échanges entre la surface et l’atmosphère, qui constituent une part crucialedes cycles biogéochimiques du carbone et de l’eau ? L’interprétation paléoclimatique desenregistrements de carottes de glace au Groenland peut-elle bénéficier de ces observations ?Après une validation des observations menées à Ivittuut, sur la côte sud-ouest du Groenland,en regard de normes internationales de qualité, confirmant leur représentativité des variationsatmosphériques, j’ai commencé par interpréter ces observations en analysant leur variabilité àdifférentes échelles de temps et découlant de processus spécifiques. Ceci m’a permis de montrerque le site de mesure était très peu influencé par des phénomènes locaux : peu de sources localesde gaz à effet de serre, et de processus locaux agissant sur la composition isotopique de la vapeurd’eau. Cette caractéristique facilite l’attribution des variations observées à des changements detransport atmosphérique de grande échelle en lien avec des sources distantes.Pour comprendre les variations observées, je les ai mises en relation avec des observationsissues d’autres sites ainsi qu’avec des sorties de modèles atmosphériques de grande échelle. D’unepart, j’ai constaté que de nombreuses variations de la composition atmosphérique à l’échelle synoptiquepouvaient être expliquées par des modifications du transport atmosphérique de grandeéchelle. J’ai aussi pu identifier la représentativité spatiale de nos observations, et contribuerà l’évaluation de modèles atmosphériques de grande échelle. Enfin, un cas d’étude durant lavague de chaleur ayant affecté la totalité du Groenland durant l’été 2012 m’a permis de suivrele transport atmosphérique de masses d’air et d’observer en plusieurs points ses impacts sur lacomposition isotopique de la vapeur d’eau, notamment sur la conservation du signal d’excès endeutérium, qui n’avait jamais été observée auparavant.Enfin, la combinaison des observations et de la modélisation atmosphérique m’a permis demettre en évidence les contributions de l’observation atmosphérique en terme de documentationdes échanges entre la surface et l’atmosphère : par une attribution des valeurs observées auxsources potentielles identifiées par modélisation des masses d’air affectant la station pour le CH4et la composition isotopique de la vapeur d’eau, et par la comparaison des observations à dessimulations de transport direct de sources connues issues d’inventaires pour le CH4 ou modéliséespour le CO2 et l’O2 océanique. / South Greenland is a key region placed under Arctic and Northern Atlantic influences, whichis poorly documented in terms of atmospheric monitoring. The aim of my thesis is to conductand use the first regional atmospheric observations of CO2, O2, CH4 and isotopic compositionof water vapour and precipitation performed in Ivittuut, a coastal site in south-west Greenland.Which information can we infer from these atmospheric observations, in terms of localatmospheric processes and large scale atmospheric transport variations? Can we use these observationsto document the surface-air exchanges of these compounds, which represent an importantpart of the water and carbon biogeochemical cycles?After validating the observations regarding international precision recommandations, I havebeen able to analyse the variabilities at different time scales, resulting from different specificprocesses. This highlighted the fact the atmospheric composition of our site is weakly influencedby local processes, either for local greenhouse gases sources or small scale atmosphericvariations affecting water vapour isotopic composition. This facilitates the interpretation of ourobservations in terms of large scale atmospheric transport signals.To better understand the observed variations, I related our data series with other observationsoriginating from different sites, and with outputs from different atmospheric models. Ihave first witnessed the links between variations of atmospheric composition and large synopticscale atmospheric transport changes. Then, I have identified the spatial representativity of ourobservations and contributed to the evaluation of atmospheric models. The case study of astrong heat wave covering Greenland during summer 2012 allowed me to study the transport ofwater vapour within an air mass between different stations. It allowed me to provide the firstexperimental observation of deuterium excess conservation during atmospheric transport.Finally, combining observations and atmospheric simulations, I have documented surfaceairexchanges of the observed compounds: first by the attribution of observed values of CH4and water vapour isotopic composition to their simulated potential origins, secondly by thecomparison of observed variations with the direct simulation of atmospheric transport of eitherCH4 sources estimated from inventories or simulated CO2 and O2 air-sea fluxes from an oceanmodel.

La molécule de méthane possède la liaison C-H la plus forte parmi les hydrocarbures (BDE = 104 kcal mol-1) : son oxydation en conditions douces représente un challenge d'importance. La Méthane Monoxygénase particulaire (pMMO) est une enzyme à cuivre qui catalyse l'oxydation du méthane (CH4) en méthanol (CH3OH). Le site actif de l'enzyme est composé d'atomes de cuivre séparés par 2.6 Å. Des recherches récentes suggèrent qu'un cluster Cu2 III,II/O2 à valence mixte soit un intermédiaire-clé du cycle catalytique. L'objectif de ce travail vise à la synthèse et caractérisation de nouveaux complexes dinucléaires à valence mixte de type bis(µ-oxo)Cu2 III,II ou (µ-OH, µ-O)Cu2 III,II. Deux familles de motifs coordinants ont été mises en oeuvre, polypyridyle ou polyamide ; les deux sites sont assemblés par des ponts courts et rigides, phenoxo, naphthyridine ou alkoxo. De nouveaux complexes ont été caractérisés par électrochimie, spectroscopies UV-visible et RPE, et par des calculs théoriques. Un dispositif original de cryo-spectroélectrochimie UV-vis-NIR a été développé en parallèle de cette étude : il permet l'identification spectroscopique d'intermédiaires transitoires, réputés très instables à température ambiante. De nouveaux composés à valence mixte, Cu2 III,II(μ-OH, μ-O) et Cu2 III,IIbis(μ-OH) ont été identifiés. Ces résultats élargissent le champ des données de cette famille d'intermédiaires instables limitée jusqu'ici à un seul exemple. / Methane has the strongest C-H bond of any hydrocarbon (BDE = 104 kcal mol-1); its oxidation under mild conditions remains a great challenge. The particulate Methane Monooxygenase (pMMO) is a copper enzyme that oxides methane (CH4) to methanol (CH3OH). In the active site of the enzyme, two copper ions are located at a short distance (2.6 Å). Recent researches have suggested a mixed-valent Cu2III,II/O2 cluster as a key intermediate in the catalytic cycle. The main objective of this work was the synthesis and characterization of new mixed-valent CuIIICuII bis(μ-oxo) and (μ-OH, μ-O) dinuclear complexes. For this purpose we designed promising symmetrical and unsymmetrical complexes based on specific and distinct scaffolds for each side of the structure. Two families of coordination pattern have been used, polypyridyle or polyamide; the two sites are shortly and rigidly bridged by phenoxo, alkoxo or naphthyridine linkers. New complexes have been characterized by electrochemistry, UV-vis and EPR spectroscopies, and by theoretical calculations. A new cryo-UV-Vis-NIR spectroelectrochemical set up, developed in parallel during this work, has allowed the spectroscopic identification of these transient intermediate species, known to be unstable at room temperature. New mixed-valence Cu2 III,II(μ-OH, μ-O) and Cu2 III,IIbis(μ-OH) complexes have been characterized. These results expand the recent knowledge on the only mixed valent CuIII(μ-OH)CuII species described so far.

L’objectif de cette thèse est de développer des outils et des procédures pour l’approche par lamicro-cinétique expérimentale, de la réaction CO/O2 appliquée aux catalyseurs à base d’iridium et departicules bimétalliques Pt-Pd supportées sur alumine. La caractérisation de la première étape cléd’adsorption du réactif CO sur différents métaux (type d’adsorption, chaleurs d’adsorption de chaqueespèce) a nécessité le développement d’une méthode initialement adaptée à l’analyse IR en modetransmission dite méthode AEIR (Adsorption Equilibrium InfraRed spectroscopy). Les conditionsexpérimentales permettant une exploitation quantitative des spectres IR en mode réflexion diffuse ontété déterminées pour l’utilisation de la méthode AEIR. Cette méthode a ensuite été développée enétendant son domaine d’application à des catalyseurs reconnus comme dissociant fortement le COd’une part en mode réflexion diffuse pour des catalyseurs ne pouvant être étudiés en modetransmission (Fe/Al2O3) et d’autre part en mode transmission (Co/Al2O3). L’impact des paramètres liésà la préparation du catalyseur (nature du support, dispersion de la phase métallique et formation departicules bimétalliques) sur les chaleurs d’adsorption a ensuite été évalué sur des catalyseurs à based’iridium et des catalyseurs tels que Pt-Pd, Pt-Cu respectivement. Enfin l’approche micro-cinétique dela réaction CO/O2 appliquée aux catalyseurs à base d’iridium et de particules bimétalliques Pt-Pd, viaune étude par oxydation isotherme des espèces CO adsorbées à basses températures, a montré que lesétapes superficielles impliquées étaient similaires à celles sur platine et palladium. Les impacts dedivers paramètres expérimentaux sur l’oxydation des espèces CO adsorbées caractérisée par unepériode d’induction sont qualitativement identiques, seuls les paramètres cinétiques tels que l’énergied’activation apparente de la réaction sont modifiés. / The aim of this thesis is to develop tools and procedures to study by the experimentalmicrokinetic approach, in particular for the CO/O2 reaction applied to metal supported catalystcontaining iridium particles and bimetallic Pt-Pd particles. The characterization of the first elementarystep of CO adsorption on different metals (nature of adsorption, heat of adsorption of each species) hasrequired the development of a method initially adapted for the IR analysis in transmission mode:AEIR method (Adsorption Equilibrium InfraRed spectroscopy). The experimental conditions allowinga quantitative exploitation of IR spectra in diffuse reflectance mode has been established allowing theuse of the AEIR method. This method has been developed extending the range of application oncatalysts that dissociate strongly CO firstly using diffuse reflectance mode for catalyst which can notbe study in transmission mode (Fe/Al2O3) and then in transmission mode (Co/Al2O3). The impact ofparameters linked to the preparation of catalyst (nature of the support, dispersion of metallic phase,and formation of bimetallic particles) on the heat of adsorption has been evaluated on Ir catalysts andbimetallic particles like Pt-Pd, Pt-Cu respectively. Then, the microkinetic approach of the CO/O2reaction dedicated to Ir and Pt-Pd catalysts, considering the isothermal oxidation of CO adsorbedspecies at low temperature, has shown that the superficial steps involved were similar to those for Ptand Pd catalysts. The impacts of several experimental parameters on the oxidation of CO adsorbedspecies characterized by an induction period are qualitatively identical, only the kinetic parameterslike the apparent activation energy are modified.

This thesis deals with the silicon etching technology. It Examines using of water solution of potassium hydroxide. It focuses on plasma etching of silicon using mixture of CF4 and O2 as the dry way of etching. Important parameters of etching like etching rate of silicon and masking materials, etching selectivity, surface roughness and underetching of mask are determined for both ways. Some additional processes has been examined as well, namely creating of mask of resist and silicon dioxide, lithography process and etching of resist using oxygen plasma.

(U,Pu)O2 (aussi appelé MOX) est actuellement utilisé comme combustible dans les réacteurs nucléaires à eau pressurisée (REP) avec une teneur massique en Pu d’environ 10 %. Il est également envisagé comme combustible de référence pour les réacteurs à neutrons rapides à caloporteur sodium, avec une teneur massique en Pu d’environ 25 %. En conditions opérationnelles, (U,Pu)O2 est soumis à des réactions de fission qui génèrent une grande quantité de défauts et de produits de fission. Par migration, ces défauts et produits de fission gazeux peuvent s'agréger en nano-cavités, dislocations et bulles de gaz, conduisant à une modification de la microstructure. Une meilleure description du comportement du combustible à l’échelle atomique, notamment des mécanismes élémentaires impliqués dans la diffusion des défauts et des produits de fission, est donc nécessaire pour affiner les modèles utilisés dans les codes de performance des combustibles. Pour l’étude des propriétés de (U,Pu)O2, nous avons effectué des calculs de structure électronique basés sur la méthode DFT+U combinée au contrôle des matrices d’occupation des orbitales corrélées. Des minimisations d’énergie ainsi que la dynamique moléculaire ab initio ont été utilisées. Nous avons étudié dans un premier temps les propriétés du cristal de (U,Pu)O2 pour différentes teneurs en Pu. Nous avons ensuite étudié la stabilité des défauts ponctuels ainsi que les modifications structurales et électroniques induites par ces défauts ponctuels dans (U,Pu)O2 et (U,Ce)O2, matériau utilisé comme simulant de (U,Pu)O2. Enfin, nous avons étudié le piégeage et la solubilité des gaz de fission (Kr, Xe) et de l’hélium dans la matrice de (U,Pu)O2 / (U,Pu)O2 (commonly called MOX) is currently used as nuclear fuel in pressurized water reactors with a Pu content of around 10 wt.%, and is envisaged as the reference fuel in Generation IV sodium fast reactors (SFR) with a Pu content of around 25 wt.%. Under operation, (U,Pu)O2 is submitted to fission reactions which generate a large quantity and variety of point defects, as well as fission products. By migrating, point defects and gaseous fission products can aggregate into nano-voids, dislocations and fission gas bubbles, which lead to the modification of the fuel microstructure. Therefore, a better description of the fuel behaviour at the atomic scale, and especially of the elementary mechanisms involved in the diffusion of point defects and fission products, is necessary to refine the models used in the fuel performance codes used to simulate the behaviour of fuels at the macroscopic scale. We use electronic structure calculations based on the DFT+U method combined with the occupation matrix control scheme (OMC) to investigate (U,Pu)O2 properties for various Pu contents. Static energy minimizations and ab initio molecular dynamics were used. We have first determined bulk structural, electronic and thermodynamics properties of (U,Pu)O2. We then studied the stability of point defects in (U,Pu)O2 and (U,Ce)O2, as well as the structural and electronic modifications induced by these point defects, in (U,Pu)O2 and the common experimental surrogate (U,Ce)O2. Finally, the fission gas (Kr and Xe) and helium (He) trapping and solubility in (U,Pu)O2 matrix are investigated

The primary objective of the research was to study the physiological and biochemical changes in Hass avocado fruit stored in different combination of oxygen and carbon dioxide concentrations at both 0 degrees and 5 degrees Centigrade (C), and to determine whether storage in controlled atmosphere (CA) can decrease the incidence of chilling injury (CI). A secondary objective was to identify possible correlations between CA, the incidence of CI, the activity of some ripening related enzymes and changes in proteins during ripening at 20 degrees C following storage at low temperatures. Fruit suffered no CI and ripened normally following CA storage for 3 weeks at both 0 degrees and 5 degrees C, then transferred to air for 6 days at 20 degrees C. CI symptoms did develop after CA storage for 6 and 9 weeks at 0 degrees C. Changes in proteins during ripening were analysed by 2D-PAGE. Some polypeptides were detected in unripe fruit but decreased with ripening. Polypeptides of 16.5, 25, 36 and 56 kD (kilo Dalton) were present early in ripening and their levels further increased during ripening. The appearance of three ripening related polypeptides with estimated molecular weights 80 kD (pI 3.6), 36 kD (pI 5.8) and 16.5 kD (pI 5.7) was observed in fruit at the climacteric stage. Three polypeptides with estimated molecular weights of 41 kD (pI7.8), 36 kD (pI 5.8) and 33 kD (pI 5.1) were found in air stored fruit but were not detected in fruit stored in CA. This research showed that CA did not ameliorate CI at 0 degrees C, instead storage at 0 degrees C caused a premature increase in ethylene production when the fruit were returned to air at 20 degrees C. In contrast, CA storage at 5 degrees C retarded ethylene production and ripening in fruit after it was returned to air at 20 degrees C. / Doctor of Philosophy (PhD)

Cyclotides are plant proteins with a unique topology, defined as the cyclic cystine knot motif. The motif endows cyclotides with exceptional chemical and biological stability. They also exhibit a wide range of biological activities including insecticidal, cytotoxic, anti-HIV and antimicrobial effects. Hence, cyclotides have become potential candidates in the development of peptide-based drugs; either as scaffolds to stabilize susceptible peptide sequences or as drugs by their own right. In this thesis, important parameters that could be inputs toward this development have been tuned. An extraction protocol that can be extended to industrial scale production of the cyclotides from natural sources was developed; accordingly, a single maceration with hydroalcoholic solutions of medium polarity represented an optimum extraction method. Moreover, it was shown that investigating the cyclotide content of cyclotide-bearing plants from diverse environments is a promising approach for extending the knowledge of both structural and biological diversity of these proteins. Five novel cyclotides with new sequence diversity were isolated and characterized from a violet that grows on Ethiopian highlands at an altitude of 3400 m. One of the areas where the cyclotide framework has attracted interest is the development of stable antimicrobial peptides. A stability study was carried out to determine the stability of the cyclotide framework in a cocktail of bacterial proteases and serum where the native forms of tested cyclotides exhibited high stability profile. Understanding the modes of cyclotide-cell interaction is certainly an important factor for the potential development of cyclotide-based drugs. Cellular studies were carried out using the comet assay and microautoradiography. A bell-shaped dose response curve was obtained for the DNA damaging effect of the cyclotides in the comet assay, which was the first toxicological assay of its kind on this class of proteins. The microautoradiography study revealed that the cyclotides penetrate into the cells even at cytotoxic concentrations. From previous reports, it was known that the cyclotides interact with membranes; the cellular studies in this thesis added to this knowledge by clearly demonstrating that these proteins have multiple modes of action.

The theme of this thesis is the development of mononuclear Ru-based complexes that are capable of catalyzing the water oxidation (or O2-evolving) reaction, e.g. 2 H2O → O2 + 4 H+ + 4 e−. Several families of mononuclear Ru water oxidation catalysts were designed and prepared. They feature with anionic ancillary ligands that contain carboxylate or phenolate donors. The properties of the catalysts were investigated in various aspects including coordination geometry, electrochemical behavior, and ligand exchange. All catalysts showed outstanding catalytic activity towards water oxidation in the presence of cerium(IV) ammonium nitrate as a sacrificial oxidant. High-valent Ru intermediates involved in the reactions were characterized both experimentally and theoretically. The kinetics of catalytic water oxidation was examined based on one catalyst and a prevailing catalytic pathway was proposed. The catalytic cycle involved a sequence of oxidation steps from RuII−OH2 to RuV=O species and O−O bond formation via water-nucleophilic-attack to the RuV=O intermediate. By comparing properties and catalytic performance of Ru catalysts herein with that of previously reported examples, the effect of anionic ancillary ligands was clearly elucidated in the context of catalytic water oxidation. Aiming to further application in an envisaged artificial photosynthesis device, visible light-driven water oxidation was conducted and achieved primarily in a homogeneous three-component system containing catalyst, photosensitizer, and sacrificial electron acceptor. Moreover, one model Ru catalyst was successfully immobilized on ordinary glass carbon surface through a facile and widely applicable method. / <p>QC 20121112</p>