The general trends in the past decade of increasing solar cell efficiency, decreasing PV system costs, increasing government incentive programs, and several other factors have all combined synergistically to reduce the barriers of entry for PV systems to enter the market and expand their contribution to the global energy portfolio. The shortcomings of current inverter functions which link PV systems to the utility network are becoming transparent as PV penetration levels continue to increase. The solution this thesis proposes is an approach to control the inverters real and reactive power output to help eliminate the problems associated with PV systems at their origin and in addition provide the grid with ancillary support services. The design, modeling, and analysis of a grid-tied PV system was performed in the PSCAD software simulation environment. Results indicate that in the presence of grid disturbances the smart inverter can react dynamically to help restore the power system back to its normal state. A harmonic analysis was also performed indicating the inverter under study met the applicable power quality standards for distributed energy resources.

Réussir à contrôler la morphologie et la taille de particules solides obtenues par précipitation est un enjeu industriel majeur. C’est notamment le cas dans l’industrie nucléaire pour le recyclage du combustible usé. Les caractéristiques des précipités sont liées aux conditions de mélange des phases liquides dans les procédés. Les corrélations entre les paramètres physiques des particules obtenues et les conditions hydrodynamiques n’ont pas été examinées jusqu’à présent. Dans cette étude, des systèmes expérimentaux originaux, basés sur la coalescence de deux gouttes, sont utilisés afin de mieux comprendre les liens entre hydrodynamique et réaction de précipitation. Deux configurations de gouttes aqueuses ont été investiguées, la première consiste en deux gouttes posées à fort angle de contact (>90°) dans l’huile, il s’agit d’un système modèle pour les gouttes en émulsion, la second configuration correspond à deux gouttes posées à faible angle de contact (>25°) dans l’air. Dans chaque cas, une espèce réactive est dissoute dans chaque goutte, à savoir de l’acide oxalique ou du nitrate de cérium dans la seconde. Lorsque les deux gouttes se touchent, elles peuvent éventuellement coalescer, alors les espèces chimiques se mélangent et réagissent pour produire un précipité d’oxalate de cérium. Les caractéristiques de ce précipité et ses effets sur l’hydrodynamique sont examinés en fonction du solvant utilisé. De plus, dans le cas des gouttes posées sur une surface de silice dans l’air, une différence de tension de surface entre deux gouttes crée un gradient qui génère un flux de Marangoni dirigé de la goutte de faible tension de surface au-dessus de la goutte de forte tension de surface. En jouant sur la différence de tension de surface entre les deux gouttes, et ainsi sur le flux de Marangoni, il est possible de modifier les conditions hydrodynamiques lors de la coalescence des gouttes. Des mélanges eau/diols ont été utilisés comme solvant afin de pouvoir modifier la différence de tension de surface entre les liquides des deux gouttes indépendamment de leur concentration en réactif. Les diols utilisés, le 1,2-propanediol et le 1,3-propanediol sont des isomères, ils sont la même densité, des viscosités semblables mais des tensions de surface différentes. En fixant la fraction volumique d’eau dans le solvant, et en jouant sur les fractions volumiques de chaque diols, il est possible de contrôler la tension de surface des mélanges sur une gamme de 10 mN/m pour une concentration en réactifs donnée, et en conservant la densité et viscosité des solvants. Trois régimes de précipitation ont été identifiés dans le cas de la coalescence de gouttes d’eau/diols/réactifs en fonction de l’excès oxalique. Les motifs de précipitation en découlant ont été imagés par microscopie optique et les différents précipités ont été caractérisés à l’aide de microscopie confocale, MEB, DRX et SAXS. Le régime intermédiaire présente des motifs périodiques surprenants. Ces motifs correspondent à des domaines nettement délimités d’oxalate de cérium de différentes morphologies, à savoir des aiguilles et des « microflowers ». L’obtention de tels motifs peut s’expliquer par un mécanisme de rétroaction entre convection, réaction et diffusion. / The size and morphology control of precipitated solid particles is a major economic issue for numerous industries. For instance, it is interesting for the nuclear industry, concerning the recovery of radioactive species from used nuclear fuel. The precipitates features, which are a key parameter from the post-precipitate processing, depend on the process local mixing conditions. So far, the relationship between precipitation features and hydrodynamic conditions have not been investigated. In this study, a new experimental configuration consisting of coalescing drops is set to investigate the link between reactive crystallization and hydrodynamics. Two configurations of aqueous drops are examined. The first one corresponds to high contact angle drops (>90°) in oil, as a model system for flowing drops, the second one correspond to sessile drops in air with low contact angle (<25°). In both cases, one reactive is dissolved in each drop, namely oxalic acid and cerium nitrate. When both drops get into contact, they may coalesce; the dissolved species mix and react to produce insoluble cerium oxalate. The precipitates features and effect on hydrodynamics are investigated depending on the solvent. In the case of sessile drops in air, the surface tension difference between the drops generates a gradient which induces a Marangoni flow from the low surface tension drop over the high surface tension drop. By setting the surface tension difference between the two drops and thus the Marangoni flow, the hydrodynamics conditions during the drop coalescence could be modified. Diols/water mixtures are used as solvent, in order to fix the surface tension difference between the liquids of both drops regardless from the reactant concentration. More precisely, the used diols, 1,2-propanediol and 1,3-propanediol, are isomer with identical density and close viscosity. By keeping the water volume fraction constant and playing with the 1,2-propanediol and 1,3-propanediol volume fractions of the solvents, the mixtures surface tensions differ up to 10 mN/m for identical/constant reactant concentration, density and viscosity.Three precipitation behaviors were identified for the coalescence of water/diols/recatants drops depending on the oxalic excess. The corresponding precipitates patterns are visualized by optical microscopy and the precipitates are characterized by confocal microscopy SEM, XRD and SAXS measurements. In the intermediate oxalic excess regime, formation of periodic patterns can be observed. These patterns consist in alternating cerium oxalate precipitates with distinct morphologies, namely needles and “microflowers”. Such periodic fringes can be explained by a feedback mechanism between convection, reaction and the diffusion.

Axon initial segment (AIS) disruption has been described in a number of pathological environments where neuroinflammation is a contributing factor; however, whether this disruption is reversible in unknown. To address the principle of AIS structural recovery, we employed an acute neuroinflammatory model. Acute neuroinflammation induced disruption of AIS structural and functional domains and, importantly, upon resolution of neuroinflammatory conditions, was reversed. Consistent with other studies, we observed a close interaction of microglia with AISs, and utilized this acute neuroinflammatory model to investigate the relationship between reactive microglia and AIS integrity. Gene expression analysis of microglial transcription profiles identified reactive oxygen species (ROS)-producing enzymes as candidates in AIS pathogenesis. Experiments employing mice lacking the major ROS-producing enzyme NOX2, identified ROS as mediators of AIS disruption. Furthermore, we established calcium-dependent protease calpain as a disruptor of AIS protein clustering in inflammation-induced disruption. Since we observed an intimate interaction between microglia and the AIS, we conducted studies designed to identify a candidate in microglia that regulates microglial-AIS contact. During chronic inflammatory conditions, microglia enhance contact with AISs often completely surrounding the domain. Concomitant with this morphological change, neurofascin (Nfasc) expression increased in microglia. Nfasc is a cell adhesion molecule with cell-specific isoforms known to mediate glial-neuronal interactions, but until now, was not reported to be expressed by microglia. Here, I characterize the unique Nfasc isoform expressed by microglia and present evidence that suggests that microglial Nfasc may mediate microglial-AIS contact, a potentially pivotal interaction in the induction of AIS disruption by pro-inflammatory factors.

L’objectif de ce travail est la réalisation de nouveaux microactionneurs à base depolymère conducteur électronique pouvant être envisagés pour une application denanodrone à ailes battantes.Deux réseaux interpénétrés de polymères (RIPs) POE/PTHF (poly(oxyded’éthylène)/polytétrahydrofurane) et POE/NBR (poly(oxyde d’éthylène/Nitrile Butadiene Rubber) ont été synthétisés et caractérisés. Par le contrôle de la synthèse de ces RIPs,une co-continuité de phase des deux réseaux partenaires a pu être obtenue. Ce travail a ainsi permis l’obtention de matériaux combinant les propriétés propres de chaque réseau, une bonne conductivité ionique (POE) et de bonnes propriétés mécaniques (PTHF et NBR). Les propriétés mécaniques du matériau ont permis de réaliser des matériaux polymères support d’électrolyte manipulables avec des épaisseurs inférieures à 10 μm.Des RIPs conducteurs ont pu être élaborés à partir de ces matériaux en incorporant le polymère conducteur électronique (poly(3,4-éthylènedioxythiophène) - PEDOT), par une dispersion non homogène à partir de la surface vers l’intérieur du film. Après incorporation d’un liquide ionique (le 1-éthyl-3-méthylimidazolium bis-(trifluorométhylsulfonyl)imide ou EMImTFSI), ces matériaux électroactifs ont été caractérisés et ont montré qu’ils pouvaient actionner à des fréquences élevées (100Hz) par rapport aux autres dispositifs de ce type.La mise en forme micrométrique de ces matériaux a ensuite été réalisée par un procédé propre aux microsystèmes. Les techniques de photolithographie et de gravure ionique réactive ont été adaptées et étudiées pour l’élaboration de ces microactionneurs. Un mécanisme de dégradation chimique du matériau a été proposé afin d’expliquer l’étape de gravure. Enfin, la caractérisation des microactionneurs a ensuite aussi été réalisée.La force développée par ces microactionneurs est de l’ordre du μN et le pourcentage de déformation est de 1,8 %. / The aim of this work is the realization of new microactuators based on electronicconducting polymer (ECP) for a flapping wing nano-aerial vehicle.Two Interpenetrating Polymer Networks (IPNs) PEO/PTHF(polyethyleneoxide/polytetrahydrofurane) and PEO/NBR (polyethyleneoxide/NitrileButadiene Rubber) were synthesized and characterized. By controlling the synthesis of these IPNs, a phase co-continuity of the two networks could be obtained. This work has enabled the production of materials combining the specific properties of each network, good ionic conductivity (PEO) and good mechanical properties (PTHF and NBR). The mechanical properties of the material allowed the synthesis of solid polymer electrolyte materials that can be elaborated and manipulated with thicknesses below 10 microns.The conducting IPNs are synthesized from previous IPNs in which the conductingpolymer (poly(3,4-ethylenedioxythiophene)), PEDOT, is non homogeneously dispersed i.e. the content decreases from the outside towards the center of the film.After incorporation of an ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide or EMImTFSI), these electroactive materials werecharacterized and showed their capacity to operate at frequency high frequency (100 Hz) compared to others systems in literature.The micrometer shaping of these materials was then carried out by processes specific to microsystems. Photolithography techniques and Reactive Ion Etching (RIE) have been adapted and designed for the development of microactuators. A chemical degradation mechanism of the material has been proposed to explain the etching step. Finally, the characterization of microactuators have been carried out. The force developed by these microactuators is in the range of N and the bending strain has reached 1.8%.

Ce travail est une contribution à la compréhension des capacités adaptatives des personnes âgées déprimées et non déprimées. Pour répondre à cet objectif nous avons utilisé une méthode expérimentale et une observation clinique : une étude de cas suivie longitudinalement pendant 6 ans. La relation dépression - flexibilité cognitive est évaluée au moyen d'épreuves de shifting et de fluence auprès de deux groupes de personnes âgées non démentes, déprimées et non déprimées, résidant en maisons de retraite.L'analyse quantitative et qualitative met en évidence un affaiblissement de la flexibilité cognitive qui se traduit par une corrélation négative entre les scores de dépression et ceux obtenus aux épreuves de flexibilité réactive et spontanée. Nous établissons une analogie entre les comportements adaptatifs au quotidien et les données quantitatives, et nous proposons un schéma théorique expliquant le comportement adaptatif des personnes âgées. Notre étude de cas permet une meilleure compréhension de la relation dépression-flexibilité cognitive notamment l'amélioration des capacités adaptatives suite à la baisse du niveau de dépression. / This thesis is a contribution to the understanding of adaptive capacity of depressed and non-depressed aging adults. To achieve this goal we have used an experimental method and a clinical observation: a six-year longitudinal case study. The relationship between depression and cognitive flexibility is assessed by means of shifting and fluency tasks applied to two groups of non-dement depressed and non-depressed elderly who reside in nursing institutions.The quantitative and qualitative analysis shows a decrease in cognitive flexibility which highlights a negative correlation between depression and flexibility scores. We establish an analogy between daily adaptive behaviours and quantitative data, and we propose a theoretical mechanism that explains the adaptive behaviour of the elderly. Our case study offers a deeper understanding of the relationship between depression and cognitive flexibility, particularly the improvements of adaptive capacities due to a decrease of depression.

The brain renin-angiotensin system (RAS), of which angiotensin II (AngII) is the primary effector peptide, plays a critical role in the neurohumoral regulation of cardiovascular and body fluid homeostasis by modulating blood pressure, secretion of hypothalamic and pituitary hormones, and water intake. AngII produced locally in the brain or in the systemic circulation can act on brain regions called circumventricular organs (CVO), which lack the blood-brain-barrier. Dysregulation of central AngII signaling is implicated in the pathogenesis of hypertension; therefore, understanding the mechanisms of AngII in the CNS is an important area of investigation. Recently, a novel signaling mechanism for AngII in the periphery has been shown to involve NAD(P)H oxidase-derived reactive oxygen species (ROS). Although ROS are now known to be involved in numerous AngII-regulated processes in peripheral tissues, and are increasingly implicated in CNS neurodegenerative diseases, the role of ROS in central regulation of AngII-induced cardiovascular function remains unexplored. The hypothesis that ROS are critically involved in central AngII signaling and in AngII-dependent blood pressure and drinking behavior was tested by harnessing the power of an array of selective genetic tools, in combination with novel technologies for analysis of cardiovascular function in conscious mice. More specifically, central injections of adenoviruses encoding ROS-modulating molecules were used to examine the redox mechanisms in central AngII-mediated cardiovascular responses in vivo. Neuronal cell cultures were also used to investigate the involvement of NAD(P)H oxidase-derived ROS in AngII signaling, as well as to examine a link between calcium and ROS in intra-neuronal AngII signaling. Finally, in order to better understand the potential role of ROS in the brain in the pathogenesis of AngII-dependent hypertension, a mouse model that recapitulates the characteristics of human hypertension was employed in conjunction with genetic modulation of the redox state of the brain. These studies provide new evidence that ROS are involved in the intracellular signaling mechanism of AngII in the brain under normal and pathological conditions and offer new insight to how dysregulation of redox mechanisms in the brain may lead to the pathogenesis of AngII-dependent hypertension.

Polychlorinated biphenyls (PCBs) are the persistent environmental pollutants with the continuous concerns over adverse human health effects. As semi-volatile compounds, PCBs were found in indoor and outdoor air. The observation of high levels of airborne PCBs in old school buildings raised the concerns of inhalation exposure and toxicity of PCBs. Lower chlorinated PCBs (LC-PCBs), major components of airborne PCBs, are subject to biotranformation. In vitro and in vivo studies revealed that reactive metabolites of LC-PCBs formed covalent adducts on DNA and proteins. The hypothesis of the project is that the reactive metabolites of LC-PCBs are able to form adducts on proteins or even protein crosslinks, and the formation of protein adducts and crosslinks causes the dysfunction of the target proteins. In addition, the objectives of the project are also to identify protein targets by PCB metabolites, which may be related to the mechanism of toxicity of LC-PCBs. The alkaline permethylation (AP) was established and optimized to identify and measure the protein adducts from LC-PCB metabolites. The AP method evidenced PCB metabolites formed protein adducts through the sulfhydryl groups and also one molecule of PCB quinoid metabolites was able to bind to more than one protein. Application of cytochrome c as the model protein revealed PCB quinoid metabolites also formed adducts on lysine and glutamic acid. The adduct formation and crosslinks caused the dysfunction of cytochrome c. In addition, the quinone protein adducts still kept the ability for redox reactions, which may lead to unexpected toxicity. The SILAC method was applied to identify the target proteins in the samples of in vitro proteome incubation. The instability of PCB quinone protein adducts was found by further reaction of quinone protein adducts. This may be the reason why cysteine-PCB quinone adducts were not frequently identified by proteomics method. The further understanding of protein adducts by reactive PCB metabolites helps to identify the target proteins, and ultimately reveal the role of protein adducts impacting on human health.

Particulate air pollution is known to exacerbate respiratory diseases, such as asthma and chronic obstructive pulmonary disease, in humans. It has been proposed that transition meta ls from inhaled particles may play a role in this exacerbation by generating radical species leading to damage in the lungs. The aim of this research was to determine the role that iron from particulate air pollution played in the generation of reactive oxygen species and subsequently the induction of inflammatory mediators in cells in culture. The production of reactive oxygen species by particulate air pollution was found to be dependent on the mobilization of iron from the particles by chelators, such as the physiologically relevant citrate. The amount of iron mobilized from the combustion particulate, coal fly ash, was dependent on the type of coal used to generate the fly ash and was greatest in the smallest size fraction collected for three different coal types. In addition, the amount of iron mobilized from coal fly ash by citrate correlated closely with the amount mobilized in human lung epithelial (A549) cells, as indicated by induction of the iron storage protein, ferritin. The amount of the proinflammatory cytokine, interleukin-8, secreted in response to coal fly ash treatment varied with the amount of iron mobilized intracellularly from the particles, with the greatest response to the smaller size fractions which released the largest amounts of iron. There was a direct relationship, above a threshold level of bioavailable iron, between the level of interleukin-8 and bioavailable iron in cells treated with coal fly ash. Tetramethyl thiourea and dimethyl sulfoxide prevented the increased production of interleukin-8 by human lung epithelial cells treated with coal fly ash, suggesting the role of a radical species in the induction of this inflammatory mediator. The mobilization of iron from coal fly ash by citrate or in human lung epihelial cells, as well as the induction of interleukin-8, did not correlate with the total amount of iron in the particles. Instead, preliminary results suggest that these measured values vary directly with the amount of iron contained in the aluminosilicate fraction of the fly ash.

Although transition metals are essential for life, misregulation of redox-active metal uptake, delivery, storage, and excretion has been linked with a series of neurodegenerative disorders. Alzheimer's disease (AD) is considered an epidemic and is the most widespread of all forms of dementia. Copper ions found in large concentrations localized in amyloid-ß plaques in the brain of AD patients have been linked with the generation of reactive oxygen species which are suspected to be the culprits leading to neuronal cell death. Herein a series of mechanistic and spectroscopic studies elucidate the chemistry about the metal-centered oxidation of biomolecules, including catecholamine neurotransmitters and some analogues by copper-complexes of amyloid-ß peptide. Transition metals can also be useful tools for characterization of metalloproteins due to their unique chemical and spectroscopic features. Herein a series of studies of the native Zn²+ and Cu²+-derivative of recombinant Blastula Protease 10 (BP10) from the sea urchin Paracentrotus lividus are presented in order to elucidate its catalytic mechanism, with the use of enzymology, metal substitution, and electronic absorption spectroscopy.

Este estudo objetivou avaliar os efeitos da melatonina sobre a qualidade e as taxas de blastocistos bovinos PIV. A melatonina é um poderoso eliminador de radicais livres e tem efeitos benéficos na PIV de algumas espécies. Foram feitas sessões de PIV (n=12), sendo aspirados os folículos (2 a 7 mm) de ovários obtidos de abatedouro. Complexos cumulus oócito (COCs) que apresentavam cumulus compacto e oócito com citoplasma homogêneo foram selecionados e randomicamente distribuídos ente os grupos controle (GC) e tratado com Melatonina (GM). Submetidos a MIV por 22h em 400&micro;l de TCM199(Dia-1). Para a FIV COCs foram transferidos para 400&micro;l de meio de fertilização, inseminado com sêmen descongelado previamente submetido ao gradiente descontínuo de Percoll&reg;, e incubados por 18h (dia0). As células do cumulus dos presumíveis zigotos foram removidas com hialuronidase e pipetagem sucessiva, sendo então cultivados (CIV) em 400&micro;l de KSOM- BSA (Dia 1). No Dia 3, foi avaliada a taxa de clivagem em estereomicroscópio e adicionados 400&micro;l KSOM-20% SFB. No Dia 5, 200&micro;l de meio foram removidos e 400&micro;l KSOM-10% SFB adicionado. No dia 7 foi avaliado o estágio de desenvolvimento dos embriões, e as porcentagens calculadas em relação ao total de presumíveis zigotos. Todos os procedimentos foram realizados em placa de 4 poços (Nunc Multidishes&reg;) sem cobertura de óleo mineral Na MIV e no CIV, os grupos receberam ou 0ng/ml ou 50ng/ml de melatonina, GC e GM, respectivamente. No Dia 7, de 4 sessões de PIV, todos os blastocistos expandidos foram corados com Iodeto de Propídeo e Hoechst 33342. Os demais blastocistos expandidos, das outras sessões, foram vitrificados, assim como todos os presentes no Dia 8. Uma amostra deste meio foi retirada para avaliação da concentração de espécies reativas ao ácido tiobarbitúrico (TBARS). Posteriormente os embriões foram descongelados e cultivados para a avaliação do efeito da melatonina sobre os embriões no cultivo pós-descongelação. A análise estatística foi feita usando SAS system for Windows 9.2&reg;. Dados paramétricos foram submetidos ao teste T de Student e os não paramétricos ao Wilcoxon, diferenças foram consideradas significativas quando p<0,05. Blastocistos expandidos do GM apresentaram maior número de células, sendo que estas apresentaram porcentagem menor de ruptura de membrana que os do GC. A melatonina não influenciou as taxas de clivagem, de blastocistos no Dia 7 nem a taxa de blastocistos passíveis de vitrificação. Não foi observado efeito da melatonina sobre a tolerância dos embriões à vitrificação nem no período de cultivo após o descongelamento. Inesperadamente, a melatonina aumentou a concentração de TBARS no meio. A melatonina melhorou a qualidade embrionária, contudo suas propriedades antioxidantes não foram evidenciadas. / This aimed to evaluate melatonin effect over bovine embryo quality and rates on in vitro embryo production procedures (IVP). Melatonin is an effective free radical scavenger and beneficial effects of melatonin have been demonstrated in IVP for some species. Embryo production sessions (12) were performed; follicles (2 to 7 mm) were aspirated from slaughterhouse-derived ovaries. Cumulusoocyte complexes (COCs) who had a compact cumulus and oocyte with homogeneous cytoplasm were selected and randomly allocated (35 to 55 per group) on either control Group (CG) or Melatonin Treatment Group (MG). COCs underwent in vitro maturation (IVM) for 22 hours in 400&micro;l of TCM199 (Day -1). For in vitro fertilization (IVF) COCs were moved to fertilization medium 400&micro;l and were inseminated with previously submitted to discontinuous PercollTM gradient, frozenthawed semen, incubated for 18 hours (Day 0). After IVF presumptive zygotes were striped from remaining cumulus cells by incubation with hyaluronidase and gentile pipetting, then moved to 400&micro;l of KSOM- BSA (Day 1). On Day 3 embryos were inspected under a stereomicroscope to evaluate cleavage rate, and 400&micro;l KSOM-20% FCS was added. On Day 5 200&micro;l of medium were removed and 400&micro;l KSOM-10% FCS was added. On Day 7 embryos were evaluated regarding their developmental stage, percentages (%) were calculated over the total of presumptive zygotes, expanded blastocysts were vitrified. All procedures were performed on a Nunc MultidishesTM 4 well dish without mineral oil overlay. During IVM and IVC groups received either 0ng/ml or 50 ng/ml of melatonin, CG and MG respectively. On Day 7 out of 4 replicates all expanded blastocysts were dyed with Propidium Iodide and Hoechst. Remaining expanded blastocysts ass well as all the expanded blastocysts on Day 8 were vitrified. A medium sample was withdrawn for thiobarbituric acid assay (TBARS). Latter embryos were thawed and cultured aiming to evaluate melatonin effect over cryotolerance and post thaw culture system. Statistical analysis was performed using SAS system for Windows 9.2TM parametric data was submitted to student T-test and non parametric to Wilcoxon. Differences were considered meaningful when p<0,05. Expanded blastocysts from MG presented more cells and less cells with ruptured membrane than the ones from CG. But melatonin treatment neither influenced cleavage nor Blastocyst rates on Day 7, nor the rate of blastocysts that can be vitrified. Neither over embryos cryotolerance nor over post thaw culture system. Unexpectedly melatonin increased TBARS levels on medium. Melatonin improves bovine embryo quality however its antioxidant properties were not demonstrated.