Dissertationen zum Thema „Oxygen (O2)“

L’efficacité énergétique d’un électrolyseur alcalin est liée aux surtensions de réactions aux électrodes. Dans le but d’améliorer cette efficacité, nous avons développé de nouvelles électrodes composites polymère/particules maximisant la surface active des meilleurs catalyseurs, les propriétés de conductivité électrique et de transport des espèces en choisissant le polymère-liant le plus avantageux pour la cinétique réactionnelle. Les notions théoriques et l’état de l’art des principaux matériaux d’anodes et de cathodes et des différents paramètres régissant le fonctionnement d’un électrolyseur alcalin sont présentés afin de faire une synthèse des nombreux travaux réalisés. Des méthodes de fabrication d’électrodes au laboratoire ou lors d’essais préindustriels ont été explorées et comparées. Les performances électrochimiques des cathodes et anodes composites développées pour les réactions de l’évolution d’hydrogène et d’oxygène en milieu alcalin concentré sont étudiées par voltammétrie cyclique, polarisation linéaire et spectroscopie d’impédance électrochimique. Ce travail donne lieu à la description des différents paramètres clés du fonctionnement des électrodes composites polymère/particules. Différentes formulations de cathodes et d’anodes ont donc été étudiées afin d’établir des corrélations entre les propriétés physico-chimiques des polymères liants et des particules sur le comportement électrochimique des électrodes réalisées. Ces résultats sont discutés en termes de surtension de réactions, de cinétique électrochimique et de densités de sites actifs. Enfin, les résultats de la mise à l’échelle des cathodes composites et de leur procédé de fabrication pour une application industrielle sont rapportés avec l’objectif d’intégrer celles qui ont démontré des performances supérieures à celles de l’état de l’art dans un dispositif prototype industriel d’électrolyse. La démarche de la mise à l’échelle, les moyens expérimentaux développés, et une partie des résultats des essais y sont présentés
The electrolyzer efficiency is directly related to the electrode reaction overpotentials. To improve this efficiency, new composite electrodes with selected binders and electrocatalysts showing large active area have been formulated to enhance the electrochemical kinetics. First, a state of the art of electrode materials and electrolysis parameters have been reported in a relevant literature survey about different topics developed in the thesis manuscript. Then, a few laboratory and preindustrial electrode fabrication processes were explored and compared on both technical and economical aspects. Moreover, the electrochemical performances of composite cathodes and anodes for hydrogen and oxygen evolution reactions have been studied by cyclic voltammetry, linear polarization and electrochemical impedance spectroscopy. This comprehensive study leads to a precise description of the interfacial phenomena at the microscopic scale during gas production and the evaluation of key parameters for the formulation of advanced electrodes. Many electrode formulations were studied for the correlation of physicochemical properties of components and corresponding electrochemical behaviors. These results are discussed in terms of overpotentials, electrochemical kinetics and active site density. Finally, scale-up of composite cathode is reported. The aim of this work is to integrate the best formulated composite electrodes in a real scale prototype. The scale-up process, experimental devices developed and some electrochemical results are presented

Li-O2 batteries have been attracting increasing attention and R&D efforts as promising power sources for electric vehicles (EVs) due to their significantly higher theoretical energy densities compared to conventional Li-ion batteries. The research presented in this thesis covers the investigation of factors influencing the decomposition of Li2O2, the development of highly active electrocatalysts, and the design of low-cost and easy-operation binder-free O2 electrodes for Li-O2 batteries. Being the main technique, SR-PXD was used both as a continuous light source to advance the electrochemical decomposition of Li2O2 under the X-ray illumination and an operando tool that allowed us to probe the degradation of Li2O2. Since XRD was intensively used in my thesis work, the effect of X-ray irradiation on the stability of Li2O2 was studied. The accelerating effect of X-rays on the electrochemical decomposition of Li2O2 was, for the first time, explored. The electrochemical decomposition rate of Li2O2 was proportional to the X-ray intensity used. It is proposed that the decomposition might involve a three-step reaction with [Li2O2]x+ and Li2-xO2* as intermediates, which followed pseudo-zero-order kinetics. Then, three electrocatalysts (Pt/MNT, Ru/MNT and Li2C8H2O6) were developed, which exhibited good electrocatalytic performances during the OER. Their activities were evaluated by following the Li2O2 decomposition in electrodes during the charging processes. In addition, the time-resolved OER kinetics for the electrocatalyst-containing Li-O2 cells charged galvanostatically and potentiostatically was systematically investigated using operando SR-PXD. It was found that a small amount of Pt or Ru decoration on the MNTs enhanced the OER efficiency in a Li-O2 cell. The Li2O2 decomposition of an electrode with 5 wt% Pt/MNT, 2 wt% Ru/MNT or Li2C8H2O6 in a Li-O2 cell followed pseudo-zero-order kinetics. Finally, a novel binder-free NCPE for Li-O2 batteries was presented. It displayed a bird’s nest microstructure, which could provide the self-standing electrode with considerable mechanic durability, fast O2 diffusion and enough space for the discharge product deposition. The NCPE contained N-containing functional groups, which may promote the electrochemical reactions.

Hunting for improved energy storage devices based on rechargeable Li-ion batteries and other advanced rechargeable batteries is one of the hottest topics in today's society. Both Li- ion batteries and Li-O2 batteries have been studied within the thesis. The research work of this thesis contains two different parts. Part 1. The controlled synthesis of the extreme small sized nanoparticles and their application for Li-ion batteries; Part 2. The study of the O2 reduction mechanism in Li-O2 batteries with aprotic electrolytes. In the first part, two different types of extremely small-sized TiO2 nanoparticles with at lease on dimension less than 3 nm was synthesised via solvothermal/hydrothermal reaction, i.e., anatase nanosheets and TiO2(B). These nanoparticles were obtained without any contamination of long chain organic surfactants. A series of systematic characterisation methods were employed to analyse the size, phase purity, and surface condition. These extremely small-sized nanoparticles exhibit improved capacity, rate performance as anode materials for Li-ion batteries. The shapes of load curves of charge and discharge are significantly modified due to the reduced size of TiO2 nanoparticles. In chapter 3, we will see the variation of the capacity and the load curve shape of the anatase nanosheets according to their thickness and surface conditions. The origin of the excessive capacity is analysed based on the electrochemical data. It has been identified that both pseudocapacitive (interfacial) Li+ storage and the excessive Li+ -storage from the bulk contribute to the increased capacity. In chapter 4, the shape and size of the sub-3 nm TiO2(B) nanoparticles are studied, a method based the PXRD data is established. These nanoparticles demonstrate a reversible capacity of 221 mAh/g at a rate of 600 mA/g and remain 135 mAh/g at 18000 mA/g without significant capacity fading during cycling. In the last part, a systematic study of O2 reduction mechanism for aprotic Li-O2 batteries based on the combination of a series of electrochemical and spectroscopic data is presented. The novel mechanism unifies two previous models for the growth of Li2O2 during discharge, i.e., Li2O2 particle formation in the solution phase and Li2O2 film formation on the electrode surface. The new mechanism provides fundamental conceptions for the improvement of Li2O2 batteries and shed light on the future research of Li2O2 batteries.

En aquesta tesi s'han utilitzat diferents estratègies per obtenir control en la producció i detecció de diferents espècies reactives d'oxigen (ROS), especialment per a l'oxigen singlet (1O2). En la primera part de la tesi, l'enfoc principal consisteix en entendre la generació de ROS i intentar potenciar-ne el seu efecte. En primer lloc, demostrem que la modificació de diferents fotosensibilitzadors afegint-hi un catió de trifenilfosfoni com a element diana produeix derivats amb una excel·lent activitat fotoantimicrobiana contra bacteris Gram-positius (S. aureus i E. faecalis). En segon lloc, descobrim una sèrie de nous aspectes de la reacció de “-phenyl quenching” per derivats de 9-fenilfenalenona. La fototoxicitat d’aquests derivats ja es troba esmentada en el llibre: “L'origen de les espècies” de C. Darwin. També es suggereix una via metabòlica mediada per la reacció BPQ en la biosíntesi dels pigments vegetals derivats de fluorones. A més, si el grup fenil és substituït per altres grups arils, s'observa diferencies en la reacció de BPQ. En tercer lloc, s’ha demostrat que diferents antraquinones d’origen natural indueixen fototoxicitat en biofilms de C. tropicalis a causa de la generació de O2•, tenint l’1O2 un rol menor. En quart lloc, es demostra el fàrmac antitumoral Doxorubicina produeix quantitats significants d’1O2, però es redueix la seva generació quan es complexa amb el ADN. En cinquè lloc, s’ha estudiat l’efecte d’adsorció o unió covalent d’un fotosensibilitzador a nanopartícules mesoporoses de sílice. A més a més, s’han derivatitzat per afegir-hi elements diana. Sisè i últim, s’ha estudiat les propietats fotoquímiques d’una nova diada que conté un bromo-bodipy com a fotosensibilitzador i trampa química de ROS (que desactiva la capacitat del bromo-bodipy de generar 1O2). Un cop oxidada la trampa química, la diada recupera la capacitat de generar 1O2 i causar dany cel·lular. S’observa diferents propietats foto-antitumorals d’aquesta diada en funció de l’estrès cel·lular o de la localització cel·lular. En la segona part de la tesi, s'ha centrat en la detecció de ROS. En primer lloc, s’han dissenyat, sintetitzat i caracteritzat nanosondes fluorescents per la detecció d'1O2 en sistemes biològics. La nanovehiculització elimina algunes de les limitacions de les diferents sondes fluorescents d’1O2. En aquest sentit, diverses sondes tals com SOSG, ADPA o furil-vinil-naftooxazol s’han unit covalentment a nanopartícules utilitzant diferents cadenes espaiadores per tal d’optimitzar la seva reactivitat front 1O2. A diferència de quan es troben lliures en solució, les nanosondes són fàcilment internalitzades per cèl·lules eucariotes i procariotes i es minimitza la interacció amb proteïnes (com per exemple, l’albúmina de sèrum boví). Les diferents nanosondes responen a l’1O2 generat intracel·lular. Com a prova de concepte, també s’ha desenvolupat una nanosonda fluorescent per la detecció no selectiva de ROS, basada en 2’,7’-diclorodihidrofluoresceina. En segon lloc, s’ha caracteritzat la estructura i reactivitat de la sonda fluorescent: CellROX Deep Red. En tercer lloc, s’ha desenvolupat la primera sonda d’optoacústica per la detecció de ROS basada en l’oxidació de la tetrametilbenzidina. S’ha aconseguit detectar 1O2 produït per bacteris utilitzant tal sonda. Finalment i com a prova de concepte, s’ha dissenyat un “self-reporter” nanofotosensibilitzador. El nanosistema és capaç de produir i detectar 1O2 simultàniament. Aquest nanodispositiu s'ha utilitzat amb èxit per la fotoinactivació de S. aureus, observant-se una correlació entre el canvi de fluorescència de la sonda i la mort bacteriana.
En esta tesis se han utilizado distintas estrategias para obtener el control en la producción y detección de diferentes especies reactivas de oxígeno (ROS), especialmente para el oxígeno singlete (1O2). En la primera parte de la tesis, el enfoque principal consiste en entender la generación de ROS e intentar potenciar su efecto. En primer lugar, demostramos que la modificación de distintos fotosensibilizadores, añadiendo un catión de trifenilfosfonio como elemento diana, produce derivados con una excelente actividad fotoantimicrobiana contra bacterias Gram-positivas (S. aureus y E. faecalis). En segundo lugar, descubrimos una serie de nuevos aspectos de la reacción de "-phenyl quenching" por derivados de 9-fenilfenalenona. La fototoxicidad de estos derivados ya se encuentra mencionada en el libro: "el origen de las especies" de C. Darwin. También se sugiere una vía metabólica mediada por la reacción BPQ en la biosíntesis de los pigmentos vegetales derivados de fluorenonas. Además, si el grupo fenilo es sustituido por otros grupos arilos, se observan diferencias en la reacción de BPQ. En tercer lugar, se ha demostrado que distintas antraquinonas de origen natural inducen fototoxicidad en biofilms de C. tropicalis debido a la generación de O2•, teniendo el 1O2 un rol menor. En cuarto lugar, se demuestra que el fármaco antitumoral Doxorubicina produce cantidades significantes de 1O2, pero se reduce su generación cuando se compleja con el ADN. En quinto lugar, se ha estudiado el efecto de adsorción o unión covalente de un fotosensibilizador a nanopartículas mesoporosas de sílice. Además, se han derivatizado para añadir elementos diana. Sexto y último, se han estudiado las propiedades fotoquímicas de una nueva diada que contiene un bromo-bodipy como fotosensibilizador y trampa química de ROS (que desactiva la capacidad del bromo-bodipy para generar 1O2). Una vez oxidada la trampa química, la diada recupera la capacidad para generar 1O2 y causar daño celular. Se observan diferentes propiedades foto-antitumorales de esta diada en función del estrés celular o de la localización celular. La segunda parte de la tesis, se ha centrado en la detección de ROS. En primer lugar, se han diseñado, sintetizado y caracterizado nanosondas fluorescentes para la detección de 1O2 en sistemas biológicos. La nanovehiculización elimina algunas de las limitaciones de las distintas sondas fluorescentes de 1O2. En este sentido, varias sondas tales como SOSG, ADPA o furilo-vinilo-naftooxazol se han unido covalentemente a nanopartículas utilizando distintas cadenas espaciadoras para optimizar su reactividad frente 1O2. A diferencia de cuando se encuentran libres en solución, las nanosondas son fácilmente internalizadas por células eucariotas y procariotas y se minimiza la interacción con proteínas (como por ejemplo con la albúmina de suero bovino). Las distintas nanosondas responden al 1O2 generado intracelular. Como prueba de concepto, también se ha desarrollado una nanosonda fluorescente para la detección no selectiva de ROS, basada en 2',7'-diclorodihidrofluoresceina. En segundo lugar, se ha caracterizado la estructura y reactividad de la sonda fluorescente: CellROX Deep Red. En tercer lugar, se ha desarrollado la primera sonda de optoacústica para la detección de ROS basada en la oxidación de la tetrametilbenzidina. Se ha logrado detectar 1O2 producido por bacterias emprando tal sonda. Finalmente, y como prueba de concepto, se ha diseñado un "self-reporter" nanofotosensibilitzador. El nanosistema es capaz de producir y detectar 1O2 simultáneamente. Este nanodispositivo ha sido utilizado con éxito para la fotoinactivación de S. aureus, observándose una correlación entre el cambio de fluorescencia de la sonda y la muerte bacteriana.
In this thesis, different strategies have been used in order to gain control in reactive oxygen species (ROS) production and detection, especially for singlet oxygen (1O2). In the first part of the thesis, the main focus is towards understanding ROS generation and try to potentiate its effect. First, we demonstrate that modification of different photosensitisers with the triphenylphosphonium cation yields derivatives with an excellent photoantimicrobial activity against Gram‐positive bacteria (i.e., S. aureus and E. faecalis). Second, we uncover a number of new aspects of -phenyl quenching reaction in 9-phenylphenalenone scaffold, whose phototoxicity was already mentioned in Darwin’s Origin of Species. It is suggested an excited state-mediated metabolic pathway in the biosynthesis of fluorone plant pigments. Moreover, if phenyl moiety is substituted for other aryl groups, it is observed that the electrocyclic ring opening back to ground state ketones have lifetimes between miliseconds and picoseconds. Third, we demonstrate that the main photosensitizing mechanism, involved in the photo-induced C. tropicalis antibiofilm activity by natural anthraquinones, is via O2• production, whereas 1O2 participation seems of lesser importance. Fourth, we demonstrate that doxorubicin produces significant amounts of 1O2, however, this is largely suppressed when bound to DNA. Fifth, we studied the effect of PS adsorption or covalently bond onto the surface of mesoporous silica nanoparticles. Moreover, we further derivatitze them for attach targeting elements. Sixth and last, we studied the activation a new dyad comprising a bromo-bodipy, which acts as PS, plus a non-selective ROS chemical trap, which quenches the ability of bromo-bodipy to produce 1O2. For that aPS we observe a differential behaviour in function of the cellular stress or even in function of the organelle. In the second part of the thesis, focus has been shifted towards ROS detection. First, we designed, synthesized, and characterized biocompatible fluorescent nanoprobes for 1O2 detection in biological systems that circumvents many of the limitations of the different molecular 1O2 fluorescent probes. Under that purpose different 1O2 probes (Singlet Oxygen Sensor Green, anthracene dipropionic acid and furyl-vinyl-naphthoxazole) were covalently linked to nanoparticles core using different architectures to optimize their response to 1O2. In contrast to its molecular counterpart, the optimum nanoprobes are readily internalized by prokaryotic and eukaryotic cells and they do not interact with proteins (i.e. bovine serum albumin). Furthermore, the spectral characteristics do not change inside cells, and the probe responds to intracellular generated 1O2 with the corresponding change in fluorescence. As a proof of concept, a non-selective ROS fluorescent nanoprobe, based on diacetyl 2’,7’-dichlorodihydrofluorescein, has been synthetized and successfully used for detecting intracellular ROS. Second, we have performed the chemical characterization of the CellROX Deep Red, a new commercial non-selective ROS fluorescent probe, ascertained its putative chemical structure and evaluated its reactivity towards different reactive oxygen/nitrogen species and light in solution. Third, we developed the first ROS optoacoustic probe based on the oxidation of tetramethylbenzidine and successfully used for detecting 1O2 produced by bacteria. Finally, as proof of concept we have designed a self-reporter nanophotosensitizer. The nanosystem is capable to produce and detect the 1O2 generated simultaneously. It has been successfully used for S. aureus photoinactivation in which a correlation was observed between fluorescent change of the probe and bacterial cellular death.

In order to reduce the amount of pollution that is generated by burning fossil fuels alternative energy sources should be explored. Hydrogen has been identified as the most promising replacement for fossil fuels and can be produced by using the Hybrid Sulphur (HyS) cycle. Currently the SO2/O2 separation step in the HyS process has a large amount of knock out drums. The aim of this study was to investigate new technology to separate the SO2 and O2. The technology that was identified and investigated was to separate the SO2 and O2 by absorbing the SO2 into an ionic liquid. In this study the maximum absorption, absorption rate and desorption rate of SO2 from the ionic liquid [BMIm][MeSO4] with purities of 95% and 98% was investigated. These ionic liquid properties were investigated for pure O2 at pressures ranging from 1.5 to 9 bar(a) and for pure SO2 at pressures from 1.5 to 3 bar(a) at ambient temperature. Experiments were also carried out where the composition of the feed-stream to the ionic liquid was varied with compositions of 0, 25, 50, 75 and 100 mol% SO2 with O2 as the balance. For each of these compositions the temperature of the ionic liquid was changed from 30oC to 60oC, in increments of 10oC. The absorption rate of SO2 in the ionic liquid increased when the mole percentage SO2 in the feed stream was increased. When the temperature of the ionic liquid was decreased the maximum amount of SO2 that the ionic liquid absorbed increased dramatically. However, the absorption rate was not influenced by a change in the absorption temperature. The experimental results for the maximum SO2 absorption were modelled with the Langmuir absorption model. The model fitted the data well, with an average standard deviation of 17.07% over all the experiments. In order to determine if the absorption reaction was endothermic or exothermic the Clausius-Clapeyron equation was used to calculate the heat of desorption for the desorption step. The heat of desorption data indicated that the desorption of SO2 from this ionic liquid was an endothermic reaction because the heat of desorption values was positive. Therefore the absorption reaction was exothermic. From the pressure-change experiments the results showed that the mole percentage of O2 gas that was absorbed into the ionic liquid was independent of the pressure of the O2 feed.On the other hand, there was a clear correlation between the mole percentage SO2 that was absorbed into the ionic liquid and the feed pressure of the SO2. When the feed pressure of the SO2 was increased the amount of SO2 absorbed also increased, this trend was explained with Fick’s law. In the study the effect of the ionic liquid purity on the SO2 absorption capacity was investigated. The experimental results for the pressure experiments showed that the 95% and 98% pure ionic liquid absorbed about the same amount of SO2. During the temperature experiments the 95% pure ionic liquid absorbed more SO2 than the 98% pure ionic liquid for all but two of the experiments. However the 95% pure ionic liquid also absorbed small amounts of O2 at 30 and 40oC which indicated that the 95% pure ionic liquid had a lower selectivity than the 98% pure ionic liquid. Therefore, the 95% pure ionic liquid had better SO2 absorption capabilities than the 98% pure ionic liquid. These result showed that the 98% pure ionic liquid did not absorb more SO2 than the 95% pure ionic liquid, but it did, however, show that the 98% pure ionic liquid had a better selectivity towards the SO2. Hence, it can be concluded that even with the O2 that is absorbed it would be economically more advantageous to use the less expensive 95% pure ionic liquid rather than the expensive 98% pure ionic liquid, because the O2 would not influence the performance of the process negatively in such low quantities.
Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013

Non-aqueous metal-air (Li-O2 and Na-O2) batteries have been emerging as one of the most promising high-energy storage systems to meet the requirements for demanding applications due to their high theoretical specific energy. In the present thesis work, advanced characterization techniques are demonstrated for the exploration of metal-O2 batteries. Prominently, the electrochemical reactions occurring within the Li-O2 and Na-O2 batteries upon cycling are studied by in operando powder X-ray diffraction (XRD). In the first part, a new in operando cell with a combined form of coin cell and pouch cell is designed. In operando synchrotron radiation powder X-ray diffraction (SR-PXD) is applied to investigate the evolution of Li2O2 inside the Li-O2 cells with carbon and Ru-TiC cathodes. By quantitatively tracking the Li2O2 evolution, a two-step process during growth and oxidation is observed. This newly developed analysis technique is further applied to the Na-O2 battery system. The formation of NaO2 and the influence of the electrolyte salt are followed quantitatively by in operando SR-PXD. The results indicate that the discharge capacity of Na-O2 cells containing a weak solvating ether solvent depends heavily on the choice of the conducting salt anion, which also has impact on the growth of NaO2 particles. In addition, the stability of the discharge product in Na-O2 cells is studied. Using both ex situ and in operando XRD, the influence of sodium anode, solvent, salt and oxygen on the stability of NaO2 are quantitatively identified. These findings bring new insights into the understanding of conflicting observations of different discharge products in previous studies. In the last part, a binder-free graphene based cathode concept is developed for Li-O2 cells. The formation of discharge products and their decomposition upon charge, as well as different morphologies of the discharge products on the electrode, are demonstrated. Moreover, considering the instability of carbon based cathode materials, a new type of titanium carbide on carbon cloth cathode is designed and fabricated. With a surface modification by loading Ru nanoparticles, the titanium carbide shows enhanced oxygen reduction/evolution activity and stability. Compared with the carbon based cathode materials, titanium carbide demonstrated a higher discharge and charge efficiency.

Neste trabalho avaliamos a formação de oxigênio singlete in vitro em fagócitos, (células mononucleares e neutrófilos) isolados de sangue periférico humano, e eosinófilos, de lavado bronco alveolar de camundongos balb/c, ativados por estímulo partículado: zimosan opsonizado contendo o 9,10difenilantraceno (DPA) adsorvido como sonda captadora de 1O2. Por este método, a formação do 1O2 pode ser verificada pela formação do 9,10-difenilantraceno endoperóxido (DPAO2), que é detectado por HPLC. Observamos, que os fagócitos formam 1O2 e que esta formação parece ocorrer de forma diferenciada para os dois tipos celulares (neutrófilos e células mononucleares). Visando ampliar os estudos anteriores sobre o papel da melatonina (MLT) no processo inflamatório, foi testado seu efeito em fagócitos e a relação na produção de 1O2 destas células. Observamos que MLT inibe a formação de 1O2 totalmente no caso de neutrófilos e parcialmente no caso de células mononucleares e eosinófilos. Paralelamente, foi desenvolvida a síntese de um novo captador químico de 1O2, o éster 9,10-antracenil-3-bispropionato de etila (ABPE), cuja finalidade principal é o acúmulo no interior da célula, depois de sofrer hidrólise enzimática. Esta sonda, terá facil acesso ao interior das células em sua forma ester. Este novo captador de 1O2 foi testado em células mononucleares e neutrófilos estimulados de formas diferentes: via receptor independente e dependente. Os resultados demonstraram produção equivalente de 1O2 nestes fagócitos.
In this study, we evaluated the singlet oxygen (1O2) formation in vitro from phagocytes (neutrophils and mononuclear cells) isolated from human blood cells and eosinophils isolated from bronchoalveolar lavage fluid of mice balb/c activated, by opsonized zymosan. To determine whether singlet oxygen is produced by phagocytes, zymosan particles were coated with a specific chemical trap for 1O2, 9,10-diphenylanthracene (DPA). The production of 1O2 was followed using HPLC, to measure its product, 9,10-diphenylanthracene endoperoxide (DPAO2). We also noticed that the 1O2 production occurs at different levels of for two cell types, neutrophils and mononuclear cells. In order to broaden previous studies on the role of melatonin (MLT) in inflammatory processes, its effect was tested in phagocytes was tested in relation to 1O2 formation by these cells. We observed that MLT inhibits the 1O2 formation totallymt neutrophils and partiallym mononuclear cells and eosinophils. At the some time, it was also developed the synthesis of a new probe for 1O2, the 9,10-anthracene-bis-3-ethyl-propionate (ABEP), with the purpose to accumulate inside the cells, after its enzymatic hydrolysis. This probe presents easy acess to the inferior of the cells in its ester form. This new probe for trapping 1O2 was tested in mononuclear cells and neutrophils stimulated in two ways: via independent and dependent receptor. The results showed equivalent production of 1O2 for both cell types.

World oceans cover more than 70% of the earth surface and constitutes a major sink of atmospheric CO2. Two of the most important gases in the marine carbon cycling are O2 and CO2 and hence accurate descriptions of the air-sea gas exchange of these gases are crucial. Still there is a lack of knowledge of the relative importance of processes controlling the efficiency of the air-sea gas transfer. This is especially true for Arctic and high latitude seas were studies on air-sea gas exchange are few. By studying processes causing water-side turbulence, using gases of different solubility and various measurement techniques, more knowledge on the governing processes can be obtained. Here we present the very first air-sea fluxes of O2 using atmospheric eddy covariance measurements and investigate the dependence between the gas transfer velocity of O2 and turbulence generated by the mean wind. The instrument was found to suffer from the limited precision and time response, causing significant corrections on the O2 flux. After correcting for this, the O2 fluxes displays an anti-correlation with the air-sea fluxes of CO2 in agreement with the measured air-sea gradient of O2. The transfer velocities for O2 indicates a stronger wind dependence than other commonly used parameterizations of the transfer velocity for CO2 and O2, this especially for wind speeds > 5 m s-1 where the typical onset of wave breaking occur. During two winter months eddy covariance measurements were taken over a high Arctic fjord. The data revealed a significant enhancement of the gas transfer velocity for CO2 from water-side convection, generated by cooling of surface waters. The dependence between water-side convection and gas transfer velocity were found for winds as high as 9 m s-1, but were strongest for wind speeds< 7  m s-1.  The data also showed on enhanced air-sea gas transfer of CO2 when conditions were unstable very close to neutral. This enhanced transfer were associated to increased contribution to the CO2 flux from downdraft of air with higher concentrations of CO2.  The combined effect of water-side convection and turbulence generated by wind results in a very effective transfer, thus the air-sea gas exchange at these latitudes may be significantly underestimated.

The oxidation of Pd single crystals: Pd(111), Pd(100) and Pd(110) was studied using Temperature Programmed Desorption (TPD), X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Low Electron Energy Diffraction (LEED) and Scanning Tunneling Microscopy (STM) as they were subjected to O2 in the pressure range between 1 and 150 Torr at temperatures 600-900 K. The oxygen species formed during oxidation, the oxygen uptake dependence on the sample history, the Pd single crystal surface morphology transformations, and the catalytic methane combustion over Pd single crystals were investigated in detail. The Pd single crystal oxidation proceeded through a three-step mechanism. Namely, (1) oxygen dissociatively adsorbed on Pd surface, forming chemisorbed oxygen and then surface oxide; (2) atomic oxygen diffused through a thin surface oxide layer into Pd metal, forming near surface and bulk oxygen; (3) bulk PdO formed when a critical oxygen concentration was reached in the near surface region. The diffusion of oxygen through thin surface oxide layer into Pd metal decreased in the order: Pd(110)>Pd(100)>Pd(111). The oxygen diffusion coefficient was estimated to be around 10-16 cm2 s-1 at 600 K, with an activation energy of 80 kJ mol-1. Once bulk PdO was formed, the diffusion of oxygen through the bulk oxide layer was the rate-determining step for the palladium oxidation. The diffusion coefficient was equal to 10-18 cm2 s-1 at 600 K and the activation energy was approximately 120 kJ mol-1. The oxygen diffusion through thin surface oxide layer and bulk PdO followed the Mott-Cabrera parabolic diffusion law. The oxygen uptake on Pd single crystals depended on the sample history. The uptake amount increased with the population of the bulk oxygen species, which was achieved by high oxygen exposure at elevated temperatures, for example in 1 Torr O2 at above 820 K. Ar+ sputtering or annealing in vacuum at 1300 K depleted the bulk oxygen. The Pd single crystal surface morphology was determined by the oxidation conditions: O2 pressure, treatment temperature and exposure time. When bulk PdO was formed, the single crystal surface was covered with semi-spherical agglomerates 2-4 nm in size, which tended to aggregate to form a“cauliflower-like" superstructure. The single crystal surface area during oxidation, determined by integrating the STM image, experienced three major expansions in consistent with a three-step oxidation mechanism. The surface area on the oxidized single crystals increased in the order: Pd(110)

Serotonin (5-HT)-containing neuroepithelial cells (NECs) of the gill filament are believed to be the primary O2 chemosensors in fish. In the mammalian carotid body (CB), 5-HT is one of many neurotransmitters believed to play a role in transduction of hypoxic stimuli, with acetylcholine (ACh) being the primary fast-acting excitatory neurotransmitter. Immunohistochemistry and confocal microscopy was used to observe the presence of the vesicular acetylcholine transporter (VAChT), a marker for the presence of ACh, and its associated innervation in the gills of zebrafish. VAChT-positive cells were observed primarily along the afferent side of the filament, with some cells receiving extrabranchial innervation. No VAChT-positive cells were observed in the gills of goldfish; however, certain key morphological differences in the innervation of goldfish gills was observed, as compared to zebrafish. In addition, in zebrafish NECs, whole-cell current is dominated by an O2-sensitive background K+ current; however, this is just one of several currents observed in the mammalian CB. In zebrafish NECs and the CB, membrane depolarization in response to hypoxia, mediated by inhibition of the background K+ (KB) channels, is believed to lead to activation of voltage-gated Ca2+ (CaV) channels and Ca2+-dependent neurosecretion. Using patch-clamp electrophysiology, I discovered several ion channel types not previously observed in the gill chemosensors, including Ca2+-activated K+ (KCa), voltage-dependent K+ (KV), and voltage-activated Ca2+ (CaV) channels. Under whole-cell patch-clamp conditions, the goldfish NECs did not respond to hypoxia (PO2 ~ 11 mmHg). Employing ratiometric calcium imaging and an activity-dependent fluorescent vital dye, I observed that intact goldfish NECs respond to hypoxia (PO2 ~ 11 mmHg) with an increase in intracellular Ca2+ ([Ca2+]i) and increased synaptic vesicle activity. The results of these experiments demonstrate that (1) ACh appears to play a role in the zebrafish, but not goldfish gill, (2) goldfish NECs likely signal hypoxic stimuli primarily via the central nervous system (CNS), (3) goldfish NECs express a broad range of ion channels as compared to the NECs of zebrafish, and (4) goldfish NECs rely on some cytosolic factor(s) when responding to hypoxia (PO2 ~ 11 mmHg). This thesis represents a further step in the study of neurochemical and physiological adaptations to tolerance of extreme hypoxia.

Introduction: Oxygen consumption during prolonged cycling exercise has been extensively studied at different work rates and durations, but with the focus primarily on pulmonary oxygen consumption (pVO2). The purpose of this study was to use near-infrared spectroscopy (NIRS) to investigate the relationship between pVO2 and local oxygenation responses in six active leg muscles during prolonged constant-load cycling at different intensities. Methods: 26 recreational male cyclists performed a constant-load high-intensity cycling test at 75% maximal aerobic power (MAP) for 30 min duration or until exhaustion. Of the 26 subjects, 14 performed a constant-load low-intensity cycling test for the same duration as well, at 50% of the work rate found to elicit blood lactate levels of 4 mmol∙l-1 during incremental exercise. Pulmonary gas exchange (pVO2, RER, VE), heart rate, and NIRS measurements of the muscles vastus lateralis (VL), vastus medialis (VM), biceps femoris (BF), gluteus maximus (GMax), gastrocnemius lateralis (GL), and tibialis anterior (TA) were obtained continuously through both tests, while blood lactate and RPE was measured at specific time intervals. Results: Local oxygenation measurement for all the muscles collectively behaved in a similar manner as pVO2 at both intensities with an increase in O2 utilization only found in the initial phase, and additionally showed a surprisingly homogenous response. However, differences were found between the muscle groups with heterogeneity in regard to the amount of desaturation at low- and high-intensity. Discussion: Although the local responses were similar to each other and that of pVO2, differences were found between the muscles with heterogeneity in regard to the amount of saturation. The distal muscles TA and GL showed less difference in saturation between low-intensity and high-intensity than the more proximal muscles (VL, VM, BF, and GMax). Also the BF and GMax muscles were found to behave different with a lack of TSI steady-state during high-intensity.  Conclusion: The use of NIRS might provide a noninvasive and direct way of measuring local oxygenation responses in muscles and provide an indication of the work contribution of various muscles during cycling exercise. Although local oxygenation responses across the muscles were in agreement with pVO2, difference in amount of saturation was found between muscle groups in the present study. Also peripheral differences were found between the subjects able to complete 30-min constant-load high-intensity cycling and those who did not. Key words: Near-infrared spectroscopy, NIRS, cycling, constant-load, VO2, local oxygenation, tissue saturation, SmO2, muscle, muscle groups.

Utilizando a Teoria do Funcional da Densidade junto com o formalismo do pseudopotencial de primeiros princípios, realizamos um estudo sistemático do processo de adsorção da molécula de oxigênio sobre a superfície livre de CdTe (110) nas reconstruções 1x1, 1x2 e 2x1. Este estudo consistiu na determinação das adsorções energeticamente favoráveis e na viabilidade de suas formações através da análise das barreiras de ativação. Nossas análises indicam que apenas uma molécula de oxigênio adsorve sobre a superfície livre em uma reconstrução 1x1 e que não ocorre a quebra da molécula durante o processo de adsorção. As estruturas formadas foram divididas nos regimes de baixas e altas temperaturas. Do estudo das barreiras de ativação verificamos que no regime de baixas temperaturas a molécula de oxigênio liga-se exclusivamente ao Cd da primeira camada através de ligações Cd-O-O ou Cd-O2. A configuração da superfície de CdTe com a molécula adsorvida, se assemelha a configuração do cristal. As estruturas de faixas de energia neste regime apresentam um estado característico de defeito duplo aceitador. Para o regime de altas temperaturas, a molécula adsorve entre o Cd da primeira camada e o Te da segunda camada, quebrando esta ligação Cd-Te e também quebrando a ligação que o Cd da segunda camada realiza com o Te da terceira camada. O complexo formado apresenta ligações Cd-O, Cd-O2, Te-O e O-O e as estruturas de faixas de energia apresentam um gap indireto entre os pontos gama e X de 1.30 eV.
Density Functional Theory with first-principles pseudopotential formalism have been used to a systematic research of the oxygen molecule adsorption on the free surface of CdTe(110) in the 1x1, 1x2 and 2x1 reconstructions. This research was based on the determination of the adsorptions energetically favorables and the viability of each formation through their activation barriers analysis. This analysis indicates that only one oxygen molecule adsorbs over the free surface of the CdTe(110) in the 1x1 reconstruction and that the dissociation of the molecule does not occur during the adsorption process. The structures were divided on the high and low temperature regimes. From the activation barriers study it was verified that on the regime of low temperatures the oxygen molecule bind exclusively to the Cd of the first layer through the Cd-O-O or Cd-O$_2$ bonds. The CdTe surface configuration with the adsorbed molecule looks like a crystal configuration. The energy band structure, on this regime, shows a characteristic state of double acceptor defect. For the high temperature regime the molecule adsorbs between the Cd of the first layer and the Te of second layer, breaking the Cd-Te bond between them and also breaking the bonds that the Cd of the second layer does with the third layer. The complex shows Cd-O, Cd-O2, Te-O and O-O bonds and the energy band structure shows an indirect gap between the gamma and X points of 1.30eV.

Les travaux présentés dans cette thèse visent à étudier les interfaces "nanocatalyseur/glucose" et "enzyme/O2" d'une biopile hybride. Dans ce cadre, une nouvelle méthode de synthèse de nanoparticules à base d'or et de platine a été développée. Ces nanomatériaux ont été caractérisés par différentes méthodes physicochimiques pour connaître leur taille, leur morphologie et leur dispersion dans un substrat carboné (Vulcan XC72R). La surface active de chaque électrode a été déterminée par voltammétrie cyclique et par CO stripping. Il a été montré que dans les catalyseurs AuxPty, l'or a un effet promoteur sur le platine vis-à-vis de l'oxydation du glucose. Le catalyseur Au70Pt30 présente la meilleure activité catalytique. L'étude par spectroélectrochimie a permis de déterminer que la B–gluconolactone est le produit primaire de l'oxydation du glucose qui procède à bas potentiel par la déshydrogénation du carbone anomérique sur le platine. La réaction de réduction de O2 a été catalysée par une enzyme, la bilirubine oxydase (BOD). Pour faciliter le transfert électronique, deux médiateurs : ABTS et un complexe d'osmium ont été encapsulés avec l'enzyme dans une matrice de Nafion® pour créer les interfaces : BOD/ABTS/O2 et BOD/Os/O2. L'étude voltammétrique des deux médiateurs en milieu tampon phosphate a révélé deux systèmes quasi-réversibles avec des potentiels apparents proches du potentiel redox du site T1 de la BOD. Bien que difficilement comparables en termes de densité de courant au catalyseur constitué de nanoparticules de platine, les cathodes enzymatiques permettent de catalyser à quatre électrons la réduction de O2 à des potentiels très proches du potentiel de Nernst
The work developed in this thesis concerns the study of the behavior of redox reactions at the interfaces "nanocatalyst/glucose" and "enzyme/O2" for a hybrid Biofuel Cell. In this framework, a novel synthesis method of based gold and platinum nanoparticles has been achieved. These synthesized nanomaterials were characterized by different physicochemical techniques to determine their size, morphology and their dispersion in Vulcan XC72R used as substrate. The active surface area of each electrode material was determined by cyclic voltammetry and CO stripping. It has been shown that in the bimetallic catalyst gold promotes platinum activity towards the glucose oxidation. The bimetallic composition Au70Pt30 exhibits the better efficiency. The study by spectroelectrochemistry determined that the B-gluconolactone is the primary product of the glucose oxidation which proceeds at low potential by the dehydrogenation of anomeric carbon on platinum. The reduction reaction of O2 was catalyzed by an enzyme, bilirubin oxidase (BOD). Mediated electronic transfer was performed with two redox mediators, ABTS and an Osmium complex (Os). They have been encapsulated with the enzyme in a Nafion® matrix to construct the interfaces: BOD/ABTS/O2 and BOD/Os/O2. The voltammetric study of the mediators in phosphate buffer revealed two quasi-reversible systems with an apparent potential close to the theoretical potential of the T1 BOD center. Although hardly comparable in terms of current density with the Pt nanocatalyst the O2 reduction is a four electron reaction at the cathodes BOD/ABTS and BOD/Os which deliver an electrode potential close to the Nernst one

Dans ce travail de thèse, nous avons étudié l'effet des rayonnements ionisants (rayons X et γ) jusqu'à une dose maximale de 1 Grad sur différents types de fibres multimodes (dopées -P, -P-Ce, -Ge, -Ge-F, -Ge-Ce et -N). Les caractérisations ont été réalisées principalement avec trois techniques expérimentales : online Atténuation Induite par Radiation en temps réel (RIA), Résonance Paramagnétique Electronique (EPR), Micro-Luminescence (ML). Dans la première partie du travail de cette thèse, nous avons étudié la réponse aux radiations de différents types de fibres optiques. L'absorption liée aux défauts du phosphore induits par irradiation a été étudiée par des mesures RIA dans le domaine spectral UV-Visible. Les mesures EPR nous permis de détecter les défauts POHC, P1 et P2. En particulier, pour la détection de P1 et P2, nous avons utilisé le mode de détection de la seconde harmonique pour déterminer la cinétique de croissance des P1 et P2 en fonction de la dose. Nous avons également étudié les effets dus au changement des conditions de fibrage et ceux liés à la variation de la température d'irradiation (25-280 ° C). Nous avons aussi étudié l’effet du codopage du coeur de la fibre avec du Cérium. Dans ce cas, nous avons observé une production moins importante de centres POHC et P2 sous irradiation. De plus, les mesures EPR ont montré que la génération des défauts P1 n’est pas sensiblement influencée par le codopage avec le Cérium. En ce qui concerne les fibres optiques dopées Ge, on a étudié trois types de dopage : Ge seul, co-dopage Ge-F et Ge-Ce. Pour chaque type, nous avons examiné trois conditions de fibrage. La réponse à l’irradiation de ces fibres a été étudiée par les trois techniques utilisées. Plus particulièrement la ML, nous a permis d'obtenir une vision plus complète du rôle du codopant et des précurseurs dans la formation des défauts induits par l'irradiation. Nous avons également étudié la réponse au rayonnement de la fibre dopée N avec trois différentes conditions de fibrage. Les réponses à l’irradiation dans les régions spectrales UV-visible ont été obtenues par des mesures RIA. Par EPR, nous avons pu détecter deux défauts liés à l'azote pour les doses élevées de radiation. Enfin, les mesures ML sur les fibres irradiées ont montré trois bandes d'émission dans le visible qui ont été attribuées clairement à des centres émetteurs liés à l'azote. Dans la deuxième partie de la thèse, nous avons étudié les effets liés au chargement en oxygène des fibres étudiées. Par des mesures en microspectroscopie Raman, nous démontrons qu'un traitement à haute température et haute pression peut favoriser l’introduction d’une grande quantité de O2 dans les fibres optiques à cœur de silice pure (PSC) ou dopées F, Ge ou P. Les réponses à l’irradiation de certaines des fibres optiques chargées en O2 ont été étudiés (et en particulier PSC et celle dopée F. Sur la base des données de la littérature, nous avons effectué les décompositions des spectres RIA en fonction de la dose. De plus, l'étude EPR des fibres optiques dopées P et chargées en O2 a montré une forte réduction des défauts P1 et P2 comparées aux fibres non traitées. Dans cette partie de la thèse, j’ai également présenté les résultats concernant la radioluminescence infrarouge (1272 nm) des molécules O2 dans la fibre optique. La faisabilité d'un capteur de radiation pour des environnements sous fortes doses et forts débits de dose a été discutée
In this Thesis work we have investigated the effect of ionizing irradiation (X and γ rays) up to 1 Grad on different types of multimode optical fibers (P-doped, P-Ce-doped , Ge-doped, Ge-F-doped, Ge-Ce-doped, and N-doped). The experiments were carried out by three main experimental techniques: online Radiation Induced Attenuation (RIA), Electron Paramagnetic Resonance (EPR) and Confocal Micro-Luminescence (CML). In the first part of the Thesis work we report on the radiation response of several types of optical fibers. The absorption due to radiation induced P-related defects was studied by RIA in the UV-Visible domain. Moreover, by EPR measurements we were able to detect POHC, P1 and P2 defects. In particular, for the detection of P1 and P2 defects we have validated the use of EPR second-harmonic detection mode which allowed us to obtain the growth kinetics of P1 and P2 with the dose. The effects due to the variation of the drawing conditions of the fibers were investigated as well as the ones due to the change of the temperature of irradiation (from 25 to 280 °C). Finally, concerning the P-doped OFs, we report on the effects due to the Cerium codoping of the core of the optical fiber. We observed a reduced generation of POHC and P2 centers under irradiation. However, EPR investigation has shown that the generation of P1 defects is essentially unaffected by the Ce-codoping. Regarding Ge-doped optical fibers we report on three basic typologies: Ge-doped, Ge-F-doped and Ge-Ce-doped. For each fiber typology we investigated three drawing conditions. The radiation responses of these fibers were characterized by RIA and EPR measurements. Furthermore, performing CML measurements we were able to obtain further insight on the role of the co-dopants and of the defect precursors in determining the radiation induced defects. We have also investigated the radiation response of N-doped OFs (three drawing conditions). The radiation responses in the UV-Visible domains were obtained by RIA, and by EPR measurements we were able to detect the signals of two N-related defects at high radiation doses. Finally, CML measurements on irradiated samples have shown three emission bands in the visible domain which are tentatively assigned to N-related centers. In the second part of the Thesis we report on the effects of an O2 loading treatment produces on some of the investigated samples. By micro-Raman measurements we demonstrate that a high pressure high temperature treatment can incorporate high quantity of O2 into Pure-Silica-Core (PSC), F, Ge and P doped optical fibers. The radiation responses of some of the O2-loaded optical fibers were investigated with particular regard to the fluorine doped and pure-silica-core optical fibers. On the basis of literature data we performed band decompositions of the RIA spectra as a function of the dose. Moreover, the EPR study of the O2 loaded P-doped optical fiber have shown a strong reduction of the signals associated to the P1 and P2 defects as compared to the untreated fibers. In this part of the thesis we also report on the characterization of the near infrared radioluminescence (1272 nm) of O2 molecules embedded in the optical fiber matrix and the feasibility of a radiation sensor based on this phenomenon for environments characterized by high radiation doses and high dose-rates

A oxidação do DNA por espécies reativas de oxigênio, como o oxigênio molecular singlete [O2 (1Δg)] , pode estar relacionada ao aparecimento de mutações e ao desenvolvimento de doenças. O O2 (1Δg) pode ser gerado biologicamente por reação de fotossensibilização, pela reação de H2O2 e HOCl e pela decomposição de peróxidos orgânicos contendo hidrogênio alfa (α-ROOH), na presença de metais de transição (Fe2+, Cu2+) ou HOCl. A decomposição de α-ROOH, como hidroperóxidos de lipídeos ou proteínas na presença de metais de transição, pode gerar O2 (1Δg) via mecanismo de Russell. Neste mecanismo, a oxidação de α -ROOH gera radicais peroxila, que podem reagir entre si, formando um intermediário tetraóxido linear. Este intermediário tetraóxido linear pode decompor através de um mecanismo cíclico e produzir O2 (1Δg), um álcool e um composto carbonílico. Como a decomposição de α-ROOH pelo mecanismo de Russell pode ser uma importante fonte biológica de O2 (1Δg) decidimos investigar se o α-hidroperóxido de timina, 5-(hidroperoximetil)uracil (5-HMPU), poderia gerar esta espécie reativa na presença de metais (Ce4+, Fe2+, Cu2+) e HOCl. Outro objetivo foi avaliar os efeitos oxidativos, em DNA plasmidial (pBR322), da decomposição de 5-HPMU na presença de Cu2+. A geração de O2 (1Δg) na reação de 5-HPMU e Ce4+ ou HOCl foi demonstrada por meio do monitoramento da emissão de luz monomolecular de O2 (1Δg) na região do infravermelho próximo (IR-próximo, λ = 1270 nm) e bimolecular na região do visível (λ = 634 e 703 nm). A aquisição do espectro de emissão de O2 (1Δg) forneceu evidências inequívocas da geração desta espécie reativa na reação de 5-HPMU e Ce4+ ou HOCl. Além disto, a formação de O2 (1Δg) na reação de 5-HPMU e Fe2+, Cu2+ ou HOCl foi demonstrada através da captação química de O2 (1Δg) utilizando 9,10- divinilsulfonatoantraceno (AVS) e detecção por HPLC/MS/MS do endoperóxido (AVSO2) formado. A detecção por HPLC/MS/MS dos produtos de decomposição de 5-HPMU, 5- (hidroximetil)uracila (5-HMU) e 5-formiluracila (5-FoU), reforçaram a hipótese de geração de O2 (1Δg) pelo mecanismo de Russell. A análise dos resultados da incubação de pBR322, 5-HPMU e crescente concentração de Cu2+ mostraram o aumento da forma circular aberta (OC), indicando a formação de quebra de fita simples do DNA, provavelmente proveniente da presença dos radicais peroxila e alcoxila de 5-HPMU. Já a utilização das enzimas de reparo FPG e NTH na incubação de pBR322, 5-HPMU e Cu2+ forneceu evidências da formação preferencial de purinas oxidadas, especialmente de 2’-desoxiguanosina (dGuo). O aumento significativo da forma OC na presença de FPG indicou a formação de 8-oxo-2’-desoxiguanosina, resultante da oxidação da dGuo por O2 (1Δg) e/ou pelos radicais derivados de 5-HPMU. Podemos concluir que 5-HPMU pode ser uma importante fonte biológica de O2 (1Δg) . Além disto, a presença de 5-HPMU pode levar a propagação dos danos oxidativos no DNA, pois sua decomposição pode gerar radicais peroxila e alcoxila
Oxidation of DNA by singlet molecular oxygen O2 (1Δg) can be involved in the development of mutations and diseases. In vivo, O2 (1Δg) can be generated by photosensitization reaction, H2O2 and HOCl reaction and decomposition of organic hydroperoxides with α-hydrogen (α-ROOH) in the presence of metal ions (Fe2+, Cu2+) or HOCl. The α-ROOH decomposition, such as lipid or protein hydroperoxides in the presence of metal ions or HOCl can generate O2 (1Δg) by Russell mechanism. In this mechanism, the self-reaction of peroxyl radicals generates a linear tetraoxide intermediate that decomposes to O2 (1Δg) , an alcohol and an aldehyde. Therefore, the purpose of this work is to investigate if O2 (1Δg) can be generated by α-thymine hydroperoxide, 5- (hydroperoxymethyl)uracil (5-HPMU) in the presence of Ce4+, Fe2+, Cu2+ or HOCl. Another purpose is to study base modification and strand breaks formation in plasmid DNA (pBR322) by 5-HPMU decomposition in the presence of Cu2+. The generation of O2 (1Δg) in the reaction of 5- HPMU and Ce4+ or HOCl was monitored by monomol light emission in the near-infrared region (NIR, λ = 1270 nm) and dimol light emission in the visible region (λ = 634 e 703 nm). The generation of O2 (1Δg) during the reaction of 5-HPMU and Ce4+ or HOCl was confirmed by acquisition of the light emission spectrum in the NIR. Furthermore, the generation of O2 (1Δg) produced by 5-HPMU and Fe2+, Cu2+ or HOCl was also confirmed by chemical trapping using anthracene-9,10-divinylsulfonate (AVS) and HPLC/MS/MS detection of the corresponding endoperoxide (AVSO2). The detection by HPLC/MS/MS of 5-(hydroxymethyl)uracil (5-HMU) and 5-formyluracil (5-FoU), two 5-HPMU decomposition products, support the Russell mechanism. Plasmid results from pBR322, 5-HPMU and Cu2+ reaction showed formation of DNA open circular form (OC), probably produced by 5-HPMU peroxyl and alkoxyl radicals. Additionally, the reaction of pBR322, 5-HPMU and Cu2+ following by Fpg and NTH enzyme treatment demonstrated evidences of purine modification, especially 2’-deoxyguanosine (dGuo). The use of FPG enzyme indicated the formation of 8-oxo-7,8-dihydro-2’-deoxyguanosine, a dGuo oxidation product formed by O2 (1Δg) and/or 5-HPMU peroxyl and alkoxyl radicals. We can conclude that 5-HPMU can be a biological source of O2 (1Δg)] and 5-HPMU decomposition can lead to an enhancing of DNA oxidative damage by 5-HPMU peroxyl and alkoxyl radicals formation

Este trabalho apresenta o desenvolvimento de membranas sensoras para a detecção de oxigênio gasoso através da fosforescência resolvida no tempo, além de descrever um sistema de medição para avaliação de desempenho destes elementos. Os transdutores são formados a partir da imobilização em matrizes poliméricas, de poli(cloreto de vinila) e poliestireno, das seguintes metaloporfirinas de paládio: Coproporfirina I, Mesoporfirina IX, Deuteroporfirina IX e meso-Tetrapenta(fluorofenil)porfirina. O feixe de excitação das membranas é proveniente de um LED violeta, sendo que a fosforescência emitida pelos luminóforos é detectada por uma miniválvula fotomultiplicadora. Relatam-se a produção das membranas sensoras e seus principais parâmetros, como curvas de calibração, envelhecimento, tempos de resposta e fotoestabilidade. As membranas de PVC apresentaram sensibilidade moderada, com razões τ0/τar próximas a 4, permitindo medições com uma resolução média de 10 μs.%-1 para a faixa de 16% de O2 a ar. No caso das membranas em PS, as razões τ0/τar chegam a atingir 50, com resoluções acima de 900 μs.%-1 para concentrações entre 0% e 1% de O2; no entanto, mostram-se de difícil aplicação para concentrações acima de 16%. De modo geral, os elementos produzidos apresentaram tempos de resposta inferiores a 1 s. Assim, possíveis aplicações para estes dispositivos incluem o monitoramento da respiração humana e a detecção de oxigênio residual (e.g.: embalagens alimentícias). Evidenciou-se ainda, uma elevada fotodegradação das membranas perante a excitação na banda B, sendo que o indicador PdTFPP mostrou-se superior aos demais quanto à fotoestabilidade.
This research presents the development of sensing membranes for detection of gaseous oxygen by time-resolved phosphorescence as well as the description of a measurement system for performance evaluation of those elements. The transducers are formed by the immobilisation of palladium metalloporphyrins probes (coproporphyrin I, mesoporphyrin IX, deuteroporphyrin IX and meso-Tetrapenta(fluorophenyl) porphyrin) in polymers of poly(vinyl chloride) and polystyrene. A light emitting diode is employed for dye excitation and the phosphorescence is detected by a miniature photomultiplier tube. The production of the membranes as well as their practical parameters such as calibration curves, ageing, response times and light stability are reported. PVC membranes exhibited moderate sensitivity, with ratios τ0/τair near 4, enabling measurements with a resolution of 10 μs.%-1 for the range of 16% of O2 up to 20,5%. For PS membranes, the ratios τ0/τair reached up to 50, with resolutions of up to 900 μs.%-1 considering concentrations between 0% and 1% of O2, however they proved to be of difficult application for concentrations above 16%. Some sensor membranes showed response times below 1 s. Thus, possible applications for these devices include monitoring of human respiration and detection of residual oxygen (e.g.: food packaging). Also, it was observed a high signal degradation when the dyes are excited around their B bands. PdTFPP dye presented more light stability than the others.

The transition from fossil fuels to renewable resources has created more demand for energy storage devices. Lithium-oxygen (Li-O2) batteries have attracted much attention due to their high theoretical energy densities. They, however, are still in their infancy and several fundamental challenges remain to be addressed. Advanced analytical techniques have revealed that all components of a Li-O2 battery undergo undesirable degradation during discharge/charge cycling, contributing to reduced cyclability. Despite many attempts to minimize the anode and cathode degradation, the electrolyte remains as the leading cause for rapid capacity fading and poor cyclability in Li-O2 batteries. In this dissertation, composite gel polymer electrolytes (cGPEs) consisting of a UV-curable polymer, tetragylme based electrolyte, and glass microfibers with a diameter of ~1 µm and an aspect ratio of >100 have been developed for their use in Li-O2 battery application. The Li-O2 batteries containing cGPEs showed superior charge/discharge cycling for 500 mAh.g-1 cycle capacity with as high as 400% increase in cycles for cGPE over gel polymer electrolytes (GPEs). Results using in-situ electrochemical impedance spectroscopy (EIS), Raman spectroscopy, and scanning electron microscopy revealed that the source of the improvement was the reduction of the rate of lithium carbonates formation on the surface of the cathode. This decrease in formation rate afforded by cGPE-containing batteries was possible due to the decrease of the rate of electrolyte decomposition. The increase in solvated to the paired Li+ ratio at the cathode, afforded by increased lithium transference number, helped lessen the probability of superoxide radicals reacting with the tetraglyme solvent. This stabilization during cycling helped prolong the cycling life of the batteries. The effect of ion complexes on the stability of liquid glyme based electrolytes with various lithium salt concentrations has also been investigated for Li-O2 batteries. Charge/discharge cycling with a cycle capacity of 500 mAh·g-1 showed an improvement as high as 300% for electrolytes containing higher lithium salt concentrations. Analysis of the Raman spectroscopy data of the electrolytes suggested that the increase in lithium salt concentration afforded the formation of cation-solvent complexes, which in turn, mitigated the tetragylme degradation.

Hydrogenasen sind essentielle Enzyme im mikrobiellen H2-Kreislauf und werden als vielversprechende Katalysatoren in biologisch basierten H2-Technologien angesehen. Ein entscheidender Nachteil vieler Hydrogenasen ist ihre hohe O2-Sensitivität. Die membrangebundene Hydrogenase (MBH) aus Ralstonia eutropha ist eines der wenigen Beispiele für Hydrogenasen, die in Gegenwart von O2 katalytisch aktiv sind. Die molekularen Ursachen dieser O2 Toleranz sind bislang ungeklärt. In bisherigen Studien wurde lediglich das [NiFe]-Zentrum und dessen Umgebung auf Faktoren untersucht, die die O2-Toleranz des Enzyms hervorrufen könnten. In dieser Arbeit wurde daher der Fokus auf die kleine Untereinheit der MBH gelegt, in der sich drei elektronentransferierende Fe-S Cluster befinden. Die ligandierenden Aminosäuren dieser Fe-S Cluster wurden mittels ortsspezifischer Mutagenese verändert und die resultierenden MBH-Varianten physiologisch, biochemisch, spektroskopisch und elektrochemisch charakterisiert. Dabei wurde gezeigt, dass die O2-Toleranz der MBH maßgeblich auf einer Modifikation eines dieser drei Fe-S Cluster beruht. In der direkten Umgebung des zum aktiven Zentrum nächstgelegenen Fe-S Clusters befinden sich sechs statt vier Cysteine, wie in O2 sensitiven [NiFe]-Hydrogenasen. Die beiden zusätzlichen Cysteine um dieses proximale Cluster wurden gegen Glycine ausgetauscht, die an der entsprechenden Position in O2-sensitiven Hydrogenasen zu finden sind. Der Austausch der zusätzlichen Cysteine führte in vivo und in vitro zu einer erhöhten O2 Sensitivität der MBH. In EPR-spektroskopischen Untersuchungen wurde beobachtet, dass diese MBH-Variante veränderte elektronische Eigenschaften aufweist. Statt des für O2-tolerante Hydrogenasen typischen EPR-Spektrums wurde ein Signal detektiert, welches in O2-sensitiven Hydrogenasen zu finden ist. Anhand der Ergebnisse wurde ein Modell erstellt, das erklärt, wie eine modifizierte Fe-S Clusterkette zur O2-Toleranz von Hydrogenasen beiträgt.
Hydrogenases are essential for H2 cycling in microbial metabolism and serve as valuable blueprints for H2-based biotechnological application. Like many metalloproteins, most hydrogenases are extremely oxygen-sensitive and prone to inactivation by even traces of O2. The O2-tolerant membrane-bound [NiFe]-hydrogenase of Ralstonia eutropha is one of the few examples that have established a mechanism enabling H2 uptake in the presence of ambient O2. The molecular mechanisms of this O2 tolerance are not yet unravelled. However, up to date, only the large subunit harbouring the [NiFe] active site has been in the focus of studies on O2 tolerance. In the present study, the role of the small subunit with its electron relay, consisting of three Fe-S clusters, was investigated. Amino acid residues involved in coordination of all three clusters were exchanged, and the resulting MBH variants were investigated with physiological, biochemical, electrochemical and spectroscopic methods. It is shown that the rare feature of O2 tolerance is crucially related to a modification of the electron transfer chain. The Fe-S cluster proximal to the catalytic centre is surrounded by six instead of the four conserved coordinating cysteines. Removal of the two additional cysteines renders the protein O2-sensitive in vivo and in vitro. Electron paramagnetic resonance spectroscopy of this MBH variant revealed a signal resembling the spectrum usually detected in O2-sensitive [NiFe]-hydrogenases. The data imply that the major mechanism of O2 tolerance is based on the reductive removal of oxygenic species guided by the unique architecture of the electron transport chain rather than a restricted access of O2 to the active site.

Atmosferas com altas concentrações de O2, bem como atmosferas enriquecidas com N2O têm sido sugeridas como alternativas para as atmosferas com baixo O2 e alto CO2. O armazenamento de frutos em atmosferas com alto CO2 por um longo período pode ocasionar desordens fisiológicas. Além disso, existe pouca informação na literatura sobre os efeitos de altas concentrações de O2 no metabolismo oxidativo em frutos. O N2O é um gás de ocorrência natural, não tóxico descrito como um potente antagonista à produção e à ação do etileno. Este trabalho teve como objetivo estudar a influência da atmosfera controlada com altas concentrações de O2 associadas ou não a CO2 e N2O sobre a fisiologia, o metabolismo oxidativo e o comportamento pós-colheita de bananas e goiabas. Bananas Nanicão e goiabas Kumagai foram submetidas aos tratamentos com atmosfera controlada em sistema de fluxo contínuo. Os frutos foram dispostos em câmaras sob o fluxo de 200 mL min-1. Todos os tratamentos foram mantidos em câmara com temperatura controlada de 22°C. A umidade em torno dos frutos foi mantida em 95%UR. Os frutos foram avaliados quanto à qualidade, produção de CO2, etileno e atividade enzimática. O alto O2 acelerou o início da senescência em ambos os frutos. Porém, foram observadas diferenças entre a banana e a goiaba, sendo que na banana o pico climatérico e o processo de amadurecimento foram antecipados. Na goiaba, o efeito marcante foi a perda da cor verde da casca. Provavelmente, as respostas observadas estão diretamente relacionadas à influência do oxigênio no metabolismo do etileno e as capacidades antioxidantes da banana e goiaba. Quando o alto O2 foi associado ao CO2 e ao N2O também foi verificada antecipação do início da senescência, porém foram verificadas diferenças entre os tratamentos com CO2 e aqueles com N2O. O alto O2 associado ao CO2 evitou a ocorrência de processos fermentativos mesmo nas concentrações mais elevadas de CO2. Com relação ao N2O, a associação deste gás ao alto O2 não reteve o amadurecimento. Por outro lado, sua associação ao baixo O2 permitiu aumento na vida pós-colheita de ambos os frutos, sem a ocorrência de processos fermentativos. Em relação ao metabolismo oxidativo a banana com alto O2 desencadeou acúmulo de oxigênio reativo com conseqüente alteração na atividade das enzimas oxidativas, diferindo da goiaba na qual os teores de oxigênio reativo se mantiveram baixos durante todo armazenamento. Isso ocorre, provavelmente devido às diferenças na capacidade antioxidante entre estas frutas a qual é consideravelmente maior na goiaba.
Atmospheres with high O2 levels and N2O enriched atmospheres have been suggested as an alternative to the atmospheres of low O2 and high CO2. Fruit storage under atmospheres with high CO2 for a long period may develop physiological disorders. In addition, there is not enough information about the effects of high O2 concentrations on fruits oxidative metabolism. N2O is a gas present on nature, non-toxic described as a powerful antagonist to production and action of ethylene. This work aimed to study the influence of controlled atmosphere with high O2 concentrations, associated or not to CO2 and N2O on the physiology, oxidative metabolism and post-harvest behavior of bananas and guavas. Bananas Nanicão and guava Kumagai were treated under continuous flow system. The fruits were placed into chambers under flow of 200 mL min-1. All treatments were maintained in a chamber with controlled temperature of 22°C. The humidity around the fruits was kept at 95% UR. It was quality evaluated CO2 and ethylene production and enzyme activity. The high O2 accelerated the onset of senescence in both fruits. However, differences were observed between the banana and guava, banana anticipated the occurrence of the climacteric peak by changing all the variables related to maturity. The main effect observed over guavas was the loss of peel green color. Probably, the observed responses are related to oxygen effect on ethylene and antioxidant capacity of banana and guava. When the O2 was associated with high CO2 and N2O was also observed an anticipation of the beginning of senescence, but differences were observed between CO2 and N2O treatments. The high O2 associated with CO2 prevented the occurrence of fermentative processes even at the highest concentrations of CO2. The N2O associations with high O2 do not increase postharvest life too. On the other hand, the N2O associations with low O2 allow delay ripening process. In relation to oxidative metabolism at high O2 banana triggered accumulation of reactive oxygen and consequent change in the activity of enzymes involved, differing from guava in which the levels remained low throughout storage. This is probably due to differences in the antioxidant activity of these fruits and which is considerably higher in guava. Keywords: High oxygen; Nitrous oxide;

Les systèmes à énergies renouvelables couplés à un stockage hydrogène apportent des solutions nouvelles et innovantes à l'alimentation électrique des milieux peu ou non électrifiés. Le concept de batterie H2 qui équipe ce type de système est une forme de stockage originale qui apporte l'autonomie et l'indépendance électrique pour des longues durées (typiquement stockage saisonnier). Le fonctionnement de cette batterie H2 est le suivant : un électrolyseur produit des gaz (H2 et O2) avec les surplus d'énergie de la source renouvelable ; l'hydrogène, voire l'oxygène, est ensuite stocké dans des réservoirs pour être utilisé ultérieurement grâce à une pile à combustible lorsque la source renouvelable est insuffisante. Dans cette étude, nous nous intéresserons spécifiquement au couplage entre des générateurs photovoltaïques avec une batterie H2/O2 pour l'alimentation d'un site isolé sans interruption. Ces travaux de recherche s'inscrivent dans le projet ANR PEPITE (ANR-PanH 2007-2012) et ont été menés en partenariat avec HELION Hydrogen Power, le CEA Liten et l'Université de Corse. Le projet est également labellisé par les pôles de compétitivité CAPENERGIES et TENERRDIS. Tout d'abord, une réflexion générale s'appuyant sur les propriétés d'une batterie H2/O2 démontre la nécessité d'introduire une batterie (ici au plomb) pour garantir un fonctionnement instantané et sans interruption. Puis, une étude qualitative sur les architectures électriques possibles (bus de tension DC, AC…) a été menée pour s'achever sur une étude quantitative réalisée spécifiquement pour le projet PEPITE. Parallèlement à cela, différentes stratégies de gestions énergétiques ont été proposées afin d'utiliser les deux stockages dans les meilleures conditions, de limiter leur vieillissement ainsi que les pertes. Deux bancs d'essais à échelle réduite (un premier à bus DC et un second à bus AC) ont été réalisés au sein du laboratoire LAPLACE afin de valider les études et de préparer le prototype final qui sera testé sur le site de HELION Hydrogen Power au cours de l'été 2011.

O estudo do processo da peroxidação de lipídios tem aumentado nos últimos anos, principalmente devido à implicação dos hidroperóxidos de lipídios (LOOH) em diversos processos patológicos. A decomposição destes LOOH é capaz de gerar subprodutos capazes de promover danos em biomoléculas, incluindo proteínas e DNA. No presente trabalho, utilizando hidroperóxidos de ácido linoléico isotopicamente marcado com átomo de oxigênio-18 (LA18O18OH), fomos capazes de demonstrar que estas moléculas gerararam oxigênio singlete marcado [18(1O2)] em células em cultura. A detecção de tal espécie foi possível através da utilização de uma nova metodologia utilizando um derivado antracenico. Para este propósito foi utilizado o derivado de antraceno 3,3\'-(9,10-antracenodiil) bisacrilato (DADB), cujo produto especifico da reação com o 1O2 (o endoperóxido do DADB DADBO2) do pode ser facilmente detectado por HPLC-MS/MS. De forma a expandir a compreensão dos efeitos tóxicos desses LOOH, investigamos o efeito destes compostos gerados intracelularmente. Para tal, foi utilizado o Rosa bengala (RB), um fotosensibilizador que tem afinidade por espaços apolares como membranas e lisossomos. A fotosenssibilização deste composto foi capaz de induzir a morte celular, e esta morte estaria relacionada a uma maior formação de 1O2 e a um maior acumulo de peróxidos. Nestes estudos foi possível demonstrar que carotenóides e sistemas antioxidantes dependentes de glutationa foram capazes de proteger contra os efeitos tóxicos da fotosensibilização na presença de RB. Adicionalmente foram avaliados os efeitos da hemoglobina (Hb) e do hidroperóxido do ácido linoléico (LAOOH) em uma série de parâmetros toxicológicos, como citotoxicidade, estado redox, a peroxidação lipídica e dano ao DNA. Nós demonstramos que a pré-incubação das células com Hb e sua posterior exposição à LAOOH (Hb + LAOOH) levou a um aumento na morte celular, a oxidação do DCFH, formação de malonaldeído e fragmentação do DNA e que esses efeitos estavam relacionados com o grupo peróxido e ao heme presentes na Hb. Foi demonstrado que as células incubadas com LAOOH e Hb apresentaram um nível maior das lesões de DNA; 8-oxo-7,8-diidro-2 \'desoxiguanosina e 1,N2-etheno-2\'-desoxiguanosina. Além disso, as incubações com Hb levaram a um aumento nos níveis de ferro intracelular, e este alto nível de ferro correlacionada com a oxidação do DNA, avaliadas através da medida de sitios EndoIII e Fpg sensíveis. Nossos resultados comprovam que os LAOOHs apresentaram efeito citotóxico e genotóxico, mesmo em concentrações muito baixas, podendo contribuir para o desencadeamento de processos patologicos como o câncer e doenças cardiovasculares e neurodegenerativas.
The study of the process of lipid peroxidation has increased in recent years, mainly due to the involvement of lipid hydroperoxide (LOOH) in a series of pathological processes. The decomposition of LOOH is able to generate products that can promote damage to biomolecules, including proteins and DNA. In the present work, using linoleic acid hydroperoxide isotopically labeled with 18O2 (LA18O18OH), we demonstrate that these molecules were able to generate labeled singlet oxygen [18(1O2)] in cultured cells. The detection of such species was possible using a new methodology using an anthracene derivative .For this purpose we used the anthracene derivative of 3,3\'-(9,10-antracendiil) bisacrilate (DADB), whose specific reaction product with 1O2 (DADB endoperoxide DADBO2) can be easily detected by HPLC-MS/MS. In order to expand the understanding of the toxic effects of LOOH, we investigated the effect of these compounds generated intracellularly. For this porpoise, we used Rose Bengal (RB), a photosensitizer that has affinity for apolar spaces such as membranes and lysosomes. The photosensitization of this compound was able to induce cell death, and this death was related to increased formation of 1O2 and a higher accumulation of peroxides. In these studies we have shown that carotenoids and glutathione-dependent antioxidant systems were capable of protecting against the toxic effects of photosensitization in the presence of RB. Additionally, we evaluated the effects of hemoglobin (Hb) and linoleic acid hydroperoxide (LAOOH) in a series of toxicological endpoints such as cytotoxicity, redox status, lipid peroxidation and DNA damage. We demonstrated that preincubation of cells with Hb and its subsequent exposure to LAOOH (Hb + LAOOH) led to an increase in cell death, DCFH oxidation, formation of malonaldehyde and DNA fragmentation, and that these effects were related to the peroxide and the heme group. It was demonstrated that cells incubated with LAOOH and Hb showed a higher level of the DNA lesions, 8-oxo-7,8-dihydro-2\'deoxyguanosine and 1,N2-etheno-2\'-deoxyguanosine. Furthermore, incubations with Hb led to an increase in intracellular iron levels, and this high level of iron correlates with the oxidation of DNA, measured as EndoIII and Fpg-sensitive sites. Our results show that the LOOHs showed cytotoxic and genotoxic, even at very low concentrations and may contribute to the onset of chronic malignancies like cancer, cardiovascular and neurodegenerative diseases.

As proteínas são consideradas importantes alvos para os oxidantes, devido à abundância em sistemas biológicos e às altas constantes de reações com estas espécies. Adicionalmente, têmse demonstrado que o triptofano (W) é um aminoácido extremamente susceptível a oxidação, inclusive pelo oxigênio singlete (1O2). A reação do W com o 1O2 tem despertado o interesse de diversos pesquisadores. Recentemente, esta reação tem atraído mais atenção, uma vez que produtos de oxidação do W tais como N-formilquinurenina (FMK) e quinurenina (kn) têm sido associados com algumas condições patológicas, tais como o desenvolvimento de catarata e a formação de agregados covalentes da superóxido dismutase envolvidos na esclerose lateral amiotrófica. Entretanto, há poucos trabalhos enfocando detalhadamente as reações, com estudos de estabilidade, identificação de subprodutos e propostas mecanísticas. Desta forma, pretendemos com este trabalho contribuir no esclarecimento do mecanismo de oxidação do triptofano pelo 1O2, através da análise e caracterização de produtos de oxidação gerados. Com este intuito, dois hidroperóxidos de triptofano isômeros (WOOH cis e trans, em relação ao grupamento carboxila) foram completamente caracterizados por análises de HPLC/espectrometria de massa e RMN como os principais produtos de oxidação do W pelo 1O2. Estes hidroperóxidos demonstraram ser relativamente estáveis às temperaturas ambiente e fisiológica, decompondo lentamente para os alcoóis correspondentes. O aumento do pH e/ou o aquecimento das soluções contendo os WOOH leva a decomposição quimiluminescente dos WOOH à FMK. Utilizando hidroperóxidos isotopicamente marcados com [18O] (W18O18OH) foi possível confirmar que a FMK formada durante esta decomposição era marcada com dois átomos de oxigênio. Este resultado demonstra que os dois átomos da FMK são derivados do grupamento hidroperóxido. Em adição, estas reações são quimiluminescentes, sugerindo o envolvimento de um intermediário dioxetano. Este mecanismo foi confirmado uma vez que o espectro de quimiluminescência da decomposição dos WOOH pode ser sobreposto ao espectro de fluorescência da FMK, inequivocamente identificado a FMK como a espécie emissora. Dioxindoilalaninas diastereoisoméricas também foram caracterizadas como produtos de oxidação do triptofano pelo 102; uma possível via radicalar foi excluída. Em suma, este estudo contribuiu na elucidação das bases químicas envolvidas na oxidação do triptofano por 102, através da caracterização dos produtos formados e da investigação detalhada dos mecanismos de decomposição destes produtos.
Proteins have been considered important targets for reactive oxygen species. Indeed, tryptophan (W) has been shown to be a highly susceptible amino acid to many oxidizing agents, including singlet molecular oxygen (1O2). The reaction of 1O2 with W has long been a matter of concern, and has recently attracted considerably more attention because W-derived oxidation products such as N-formylkynurenine (FMK) and kynurenine (kn) have been associated with some pathological conditions such as the development of cataracts and the formation of covalent aggregates of superoxide dismutase, which has been implicated in amyotrophic lateral sclerosis. Despite the intense interest in the mechanism of W oxidation, there are a lot of gaps that remains to be elucidated. In this context, the current study was undertaken to investigate the chemical basis involved in W oxidation by 1O2. We are concerned about the chemistry of the initially formed hydroperoxides, their stability, further reactions and the mechanism leading to FMK conversion. With this purpose, two cis and trans tryptophan hydroperoxide (WOOH) isomers were completely characterized by HPLC/mass spectrometry and NMR analyses as the major W-oxidation photoproducts. Also, they were shown to be relatively stable at ambient and physiological temperatures, leading to a slow decomposition to the corresponding alcohols. Increasing the pH or heating the solutions gives rise to a luminescent decomposition of the WOOH to FMK. Using 18O-labeled hydroperoxides (W18O18OH), it was possible to confirm the formation of a two-oxygen-labeled FMK molecule derived from W18O18OH decomposition. This result shows that both oxygen atoms in FMK are derived from the hydroperoxide group. In addition, these reactions are chemiluminescent (CL), indicating a dioxetane cleavage pathway. This mechanism was confirmed since the CL spectrum of the WOOH decomposition matched the FMK fluorescence spectrum, unequivocally identifying FMK as the emitting species. Diastereoisomeric dioxindoyalanine were also characterized as oxidation products derived from the reaction of W with 1O2. The involvement of radicals in this reaction was excluded. In summary, this work offers further insights into the chemistry involved in W-oxidation, through the characterization of photoproducts and the detailed investigation about the decomposition mechanism of these products.

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)

Dissertação de Mestrado Integrado em Medicina Veterinária
A terapia hiperbárica é uma modalidade terapêutica onde o doente beneficia do aumento da pressão atmosférica para melhorar a distribuição e o aproveitamento do oxigénio (O2) pelos tecidos corporais. Para tal, é necessário recorrer-se a câmaras capazes de elevar a pressão atmosférica no seu interior, aumentando opcionalmente a concentração de O2 inalada pelo doente. Se a concentração inalada de O2 for aumentada através do fornecimento de O2 a 100%, denomina-se de Oxigenoterapia Hiperbárica; mas se a concentração inalada de O2 for igual à pressão atmosférica, denomina-se de Terapia com Ar Hiperbárico. A terapêutica hiperbárica é ainda incipiente na Medicina Veterinária, apesar das suas conhecidas vantagens na Medicina Humana. O presente trabalho procura explicar um pouco sobre como funciona a Terapia Hiperbárica em pequenos animais, considerando os seus princípios físicos funcionais, indicações e contraindicações, ilustrando no final com o relato de um caso clínico de um canídeo, fêmea, 9 anos de idade, com diagnóstico diferencial primário de isquémica cerebral difusa, sujeita a terapêutica médica e hiperbárica. A medicina hiperbárica é uma modalidade terapêutica promissora com indicação para uma grande variedade de doenças mas ainda carece de mais estudos para que possa ser melhor entendida.
ABSTRACT - The hyperbaric medicine is a therapy modality where the patient benefits from the increase of the atmospheric pressure to improve the distribution and utilization of the oxygen (O2) by the body tissues. For this, it is necessary to resort to special chambers, capable of raising the atmospheric pressure inside itself, optionally increasing the O2 concentration inhaled by the patient. If the concentration of inhaled oxygen increases by the supply of O2 on 100%, it is called Hyperbaric Oxygen Therapy, if the concentration of O2 inhaled is equal to the atmosphere, it is called Hyperbaric Air Therapy. The hyperbaric medicine is still insipient in Veterinary Medicine, despite its known advantages in Human Medicine. This work seeks to explain a little how the Hyperbaric Therapy works in small animals, considering its functional physical principles, indications and contraindications. For this, it illustrates the story of a clinical case, a 9-year-old female canine with primary differential diagnosis of defuse cerebral ischemic, subject to medical and hyperbaric therapy. Hyperbaric medicine is a promising therapeutic modality, applicable in the veterinary clinical routine, with an indication for a wide variety of diseases, but which still requires further studies in the veterinary medicine.
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La pile à combustible H+-SOFC (Protonic Conducting Solid Oxide Fuel Cell) basée surl'utilisation d'un électrolyte conducteur protonique peut représenter une alternative intéressanteà la pile SOFC qui présente actuellement le meilleur rendement. Cependant, la surtension à lacathode reste élevée et ce travail est dédié à la compréhension du mécanisme de réductionl'oxygène à cette électrode.Différents matériaux conducteurs mixtes O2- / e- de structures dérivées de la perovskite ABO3,tels que les doubles perovskites LnBaM2O5+d (Ln = Pr, Nd et Gd et M = Co et Fe) ainsi que lesphases de Ruddlesden-Popper A2MO4+d (Ln = Pr et Sr et M = Ni), ont été étudiés. Leur niveaude conductivité électronique ainsi que leur non-stoechiométrie en oxygène ont d'abord étédéterminées. Puis, à l'aide de la détermination des coefficients de diffusion de l'oxygène par laméthode de relaxation de conductivité électrique, leur conductivité ionique O2- a été estimée.Une étude électrochimique et plus spécialement la détermination des étapes limitant la réactionde réduction de l'oxygène à la cathode de pile H+-SOFC a ensuite permis de démontrer le rôledu proton dans le mécanisme de réaction pour les matériaux présentant les meilleuresperformances électrochimiques.Enfin, dans le cadre d'un projet ANR HPAC 2009 " CONDOR ", des mono-cellules de piles H+-SOFC ont été mises en forme et des densités de puissance proche de 180 mW/cm² à 0.6 V à600°C ont été obtenues.

Este trabalho teve como objetivo estudar a atividade eletrocatalítica da matriz Printex 6L contendo o modificador organometálico ftalocianina de prata nos percentuais 0,5; 1,0; 3,0 e 5,0% m/m para a Reação de Redução de Oxigênio (RRO). Para isso, fezse a constatação da incorporação do modificador por Fluorescência de Raios - X (FRX), o estudo da estabilidade dos catalisadores pela técnica de voltametria cíclica, bem como a avaliação da eficiência de corrente para eletrogeração de H2O2 a partir dos dados coletados na voltametria de varredura linear utilizando um sistema de eletrodo de discoanel rotatório (RRDE). A análise dos 40 ciclos obtidos para a voltametria cíclica revelou que os materiais contendo 0,5; 1,0; 3,0 e 5,0% m/m de ftalocianina de prata suportados na matriz de carbono amorfo apresentaram picos correspondentes a reações redox atribuídos à presença de impurezas, os quais desapareceram logo nos primeiros ciclos. O estudo da eficiência de corrente e número de elétrons envolvidos na RRO para os catalisadores avaliados mostraram uma queda na eficiência de corrente em relação ao padrão 2 elétrons Printex 6L (H2O2% = 92% e nt = 2,1), para os catalisadores contendo 0,5% (H2O2% = 62%), 1,0% (H2O2% = 76%) e 5% (H2O2% = 69%) de ftalocianina de prata, bem como aumento no número de elétrons envolvidos na RRO (nt = 2,8, 2,4, 2,6, respectivamente). Para o material contendo 3,0% de ftalocianina de prata, obteve-se eficiência de corrente para peróxido de hidrogênio e número de elétrons envolvidos na reação semelhante aos do padrão 2 elétrons, Printex 6L (3% Ft-Ag: H2O2% = 89% e nt = 2,2) . Avaliando as curvas de Koutecký-Levich obtidas para os materiais modificados, observou-se a semelhança da inclinação das retas correspondentes ao Printex 6L e ao material 3% Ft-Ag, mostrando que estes possuem comportamento similar, o que também é observado nos resultados obtidos anteriormente. No entanto, os materiais estudados apresentaram rendimento para a RRO via 2 elétrons inferiores ao Printex não modificado, indicando que a modificação do Printex com a Ft-Ag não é interessante para a obtenção de H2O2.
The objective of this work was to study the electrocatalytic activity of the carbon black containing the organometallic modifier silver phthalocyanine in the percentages 0.5, 1.0, 3.0 and 5.0% m / m for the Oxygen Reduction Reaction (ORR). For this, I studied the incorporation of the modifier by X-Ray Fluorescence, the stability of the catalysts by the cyclic voltammetry technique, as well as the evaluation of the current efficiency for H2O2 electrogeneration from the data Collected in linear scanning voltammetry using a rotatory disc-ring electrode system (RRDE). The analysis of the 40 cycles obtained for cyclic voltammetry showed that carbon materials containing 0.5, 1.0, 3.0 and 5.0% w/w of silver phthalocyanine had peaks corresponding to redox reactions of impurities, which disappeared as early as the first cycles. The study of the current efficiency and number of electrons involved in the RRO for the catalysts evaluated showed a decrease in the current efficiency in relation to the 2 Printex 6L (H2O2% = 92% and nt = 2.1) electrons for the catalysts containing 0.5% (H2O2% = 62%), 1.0% (H2O2% = 76%) and 5% (H2O2% = 69%) of silver phthalocyanine, as well as increase in the number of electrons involved in RRO (nt = 2.8, 2.4, 2.6, respectively). For the material containing 3.0% silver phthalocyanine, it was obtained current efficiency for hydrogen peroxide and the number of electrons involved in the reaction similar to the standard 2 electrons, Printex 6L (3% Ft-Ag: H2O2% = 89% e nt = 2.2). By evaluating the Koutecký-Levich curves obtained for the modified materials, we observed the similarity of the inclination of the lines corresponding to Printex 6L and the material 3% Ft-Ag, showing that they have similar behavior, which is also observed in the obtained results previously. However, the materials studied presented yield for the RRO via 2 electrons lower than the unmodified Printex, indicating that the modification of the Printex with the Ft-Ag is not interesting to obtain H2O2.

Doped ZnO nanoparticles were synthesized by three different methods – electrochemical deposition under oxidizing conditions (EDOC) , combustion method and wet chemical synthesis – for investigating the oxygen gas sensing response. Ga-doped ZnO was mostly synthesized but also In-doped ZnO was made. The samples were analyzed by XRD, SEM, EDX and TEM. Gas response curves are given alongside with Langmuir fitted curves and data for pure ZnO and Ga-doped ZnO. DFT quantum chemical investigation of cluster models ZnO nanoparticles were performed to evaluate defect effects and oxygen and nitrogen dioxide reactions with the ZnO surface. Defects were investigated by DOS and HOMO-LUMO plots , and are oxygen vacancy, zinc vacancy, zinc interstitial and gallium doping by replacing zinc with gallium. Oxygen and nitrogen dioxide reactions were investigated by computing Mulliken charges, bond lengths, DOS spectra and HOMO-LUMO plots.

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Universidade Federal de Sao Carlos
Tropical fish generally inhabit environments with high temperatures and low dissolved oxygen. Along the evolutionary process several species developed mechanisms of air-breathing in order to compensate the oxygen demands caused by the aquatic hypoxia. These mechanisms required anatomical, physiological and biochemical adaptations. Studies on the effects of hypoxia and temperature changes on fish involve the comprehension of the cardio-respiratory mechanisms of compensation. The present study was addressed to determine the cardio-respiratory and air-breathing responses of jeju, Hoplerythrinus unitaeniatus, which utilize the swimming bladder as an organ for accessory respiration in the air, submitted to gradual hypoxia after acclimation to 15, 20, 25 and 30oC. The oxygen uptake ( &VO2 ), gill ventilation ( G V& ) breathing frequency (fR), ventilation volume (VT) and the O2 extraction from the ventilatory current (EO2) were obtained for specimens of jeju (Wt = 209,7 ± 5 g) by flow-trough respirometry. The air-breathing frequency (fRA) and time spent in air-breathing (TRA) were determined by means of an experimental chamber specially constructed for this purpose. Independently of the acclimation temperature, jeju responded to hypoxia as an oxyregulator, i. e., the species was able to keep constant &VO2 in response to graded hypoxia until reach a critical oxygen tension (PcO2). The mean &VO2 values at each acclimation temperature, before reaching the PcO2, were: 47 ± 0,8 mlO2.kg-1h-1 (15°C), 82 ± 0,3 mlO2.kg-1h-1 (20°C), 104 ± 2,6 mlO2.kg-1h-1 (25°C) and 112 mlO2.kg-1h-1 (30°C). The PcO2 for each acclimation temperature were 28, 33, 41 e 52 mmHg, respectively. The increased reductions on PcO2 as acclimation temperatures rose from 15 to 30oC showed that this species presents partial compensation (or type 3 compensation) to temperature increases. Jeju increased the G V& to compensate the graded hypoxia due to higher increments on VT than in fR. This kind of compensation, however, was not enough to keep a constant EO2, which decreased gradually in response to graded hypoxia in all acclimation temperature. At 25 and 30°C the fH were significantly higher than at 15 and 20oC. Hypoxic bradicardia was not recorded at 15 and 20oC and at 25 and 30°C it only occurred below the PcO2. The different PcO2 were also the threshold for the development of accessory air-breathing in all acclimation temperatures. Increases in both fRA and TRA were inversely proportional to the water PO2 reductions and directly proportional to the acclimation temperature.
Peixes de água doce tropical vivem em ambientes de altas temperaturas e baixas concentrações de O2. Isto resultou, ao longo do processo evolutivo, na necessidade da tomada do ar atmosférico em várias espécies de peixes, a fim de compensar seus requerimentos metabólicos, o que requereu modificações anatômicas, fisiológicas e bioquímicas. Estudos sobre o efeito da hipóxia e da variação da temperatura ambiental nos peixes devem envolver o conhecimento dos mecanismos de compensação cardiorespiratória. Assim, o objetivo deste estudo foi determinar as respostas cardiorespiratórios e da respiração aérea de jeju (Hoplerythrinus unitaeniatus), que utiliza a bexiga natatória como órgão acessório de troca gasosa, após período de aclimatação nas temperaturas de 15, 20, 25 e 30°C e submetido à hipóxia gradual. As medidas do consumo de O2 ( &VO2 ), ventilação branquial ( G V& ), freqüência respiratória (fR), volume ventilatório (VT) e extração de O2 da corrente ventilatória (EO2) foram obtidas de exemplares de jeju (Wt = 209,7 ± 5 g) por meio de respirometria de fluxo constante. A freqüência (fRA) e o tempo da respiração aérea (TRA) também foram determinados utilizando-se de uma câmara especialmente desenvolvida para esta finalidade. Independentemente da temperatura de aclimatação, H. unitaeniatus comportou-se como um oxi-regulador, mantendo uma &VO2 constante por amplos intervalos de reduções de O2 até atingir a tensão crítica de O2 (PcO2). Nas diferentes temperaturas a &VO2 foi de 47 ± 0,8 mlO2.kg-1h-1 a 15°C, 82 ± 0,3 mlO2.kg-1h-1 a 20°C, 104 ± 2,6 mlO2.kg-1h-1 a 25°C e 112 mlO2.kg-1h-1 a 30°C. As PcO2 nas respectivas temperaturas foram de 28, 33, 41 e 52 mmHg. A redução crescente das PcO2 mostrou que esta espécie apresenta uma compensação parcial ou do tipo 3 aos aumentos crescentes na temperaturas de aclimatação. O jeju aumentou a G V& em resposta à hipóxia gradual valendo-se de maiores incrementos no VT do que na fR. Entretanto, este tipo de compensação não foi suficiente para manter uma constante EO2, a qual decresceu gradualmente em função da hipóxia. A fH a 25 e 30°C foi significativamente mais elevada do que a 15 e 20°C. A bradicardia hipóxica só foi registrada nas temperaturas de 25 e 30°C e somente ocorreu em tensão abaixo das respectivas PcO2. As PcO2 foram o limiar para o início da respiração aérea acessória em todas as temperaturas estudadas. Os aumentos na fRA, assim como da TRA foram inversamente proporcionais às reduções da PO2 da água e diretamente proporcionais às temperaturas de aclimatação.

Ce travail de thèse porte sur l’analyse des effets de la recirculation des gaz de combustion, via l’étude de la dilution par le dioxyde de carbone et plus particulièrement de la vapeur d’eau sur des flammes méthane/air enrichi en dioxygène, dans le cas d’une combustion prémélangée pressurisée rencontrée dans les turbines à gaz. Des mesures de vitesses de flammes CH4/O2/H2O/N2 laminaires pressurisées ont été obtenues à l’aide d’une flamme sphérique se propageant librement dans une enceinte close. L’analyse des résultats expérimentaux a permis de vérifier la validité du schéma cinétique GRIMech ?3.0 au travers des calculs numériques de flammes libres monodimensionnelles. Des calculs complémentaires ont permis l’établissement d’une base de données (vitesse de flamme laminaire, longueur de Markstein et nombre de Lewis, température adiabatique de combustion et épaisseur de flamme) en fonction des paramètres d’entrées de la combustion (température, pression, X(H2O), richesse et enrichissement en dioxygène. L’étude expérimentale complémentaire en régime turbulent des flammes diluées à l’H2O ou au CO2 a permis de mettre en avant l’effet de la vitesse laminaire de flamme sur les structures moyennes et la stabilité des flammes turbulentes. Elle a également permis d’analyser les paramètres (température adiabatique, X(H2O), X(CO2), X(N2), Vitesse de flamme laminaire) ayant un rôle important sur la production des polluants CO et NO
This PhD thesis deals with the analysis of the effects of exhaust gas recirculation (EGR) through the study of the dilution by carbon dioxide and more particularly of the water steam on dioxygen enriched methane/air flames, in the case of a premixed pressurized combustion encountered in gas turbines. CH4/O2/H2O/N2 pressurized laminar burning velocity measurement were obtained using a spherical flame propagating freely in a closed chamber. The analysis of the experimental results made it possible to check the validity of the kinetic scheme GRIMech.3.0 through numerical calculations of one-dimensional free flames. Further calculations allowed the establishment of a database (laminar burning velocity, Markstein length and Lewis number, adiabatic combustion temperature and flame thickness) as a function of combustion input parameters (temperature, pressure, X(H2O), equivalence ratio and dioxygen enrichment). The additional experimental study under turbulent regime, the flames diluted with H2O and CO2 allowed to highlight the effect of the laminar burning velocity on the average structures and the stability of turbulent flames. It also allowed to analyze the parameters (adiabatic flame temperature, pressure, X(H2O), X(CO2), X(N2), laminar burning velocity) which have an important role in the production of CO pollutants and NO

The thesis is focused on the experimental investigation of the oxygen enhanced combustion technology (OEC), which uses the combustion air with higher concentration of oxygen, i.e. more than 21 %. The OEC technology is used in those industrial applications, which requires higher thermal efficiency, increased productivity, improved character of the flame, reduced equipment cost, lower volume of exhaust gases and improved product quality. Although this technology involves a number of advantages, it is appropriate to mention some of its disadvantages such as refractory damage, inconsistent heating, increased pollutant emission or flame disturbance and/or flashback. The combustion tests of OEC were carried out at the burners testing facility that enables to test many types of burners (gaseous, liquid, or combined). The two-staged low-NOx burner fired by natural gas was used during the tests. The observed parameters include the effect of oxygen concentration in the combustion air on the NOx emissions, heat flux into the wall of the combustion chamber, in-flame temperature distribution in the horizontal symmetry plane of the combustion chamber and also the shape and dimensions of the flame. The combustion tests of the air-enrichment, air-oxy/fuel and O 2 lancing OEC methods were carried out at the burner thermal input of 750 kW and air excess of 1,1 for two combustion regimes, namely one-staged and two-staged fuel supply.

Le développement de technologies de l’énergie alternatives à la combustion des ressources fossiles est un enjeu majeur pour réduire l’émission des gaz à effet de serre et développer une économie durable. Dans cette optique, les piles à combustible à membrane échangeuses de protons (PEMFC) utilisent le platine en tant que catalyseur pour transformer l’énergie chimique en énergie électrique, en réduisant l’oxygène de l’air en eau et en oxydant l’hydrogène en protons. Dans la nature, les enzymes à cuivre et les hydrogénases catalysent respectivement ces réactions. Ces dernières, ainsi que des complexes bio-inspirés de leur site actif, ont été envisagés en tant qu’alternatives au platine, métal noble et coûteux. Ainsi, un complexe mononucléaire bisdiphosphine de nickel renfermant des acides aminés arginines en troisième sphère de coordination a été immobilisé sur une matrice de nanotubes de carbone (NTCs). Cette anode a démontré d’excellentes performances pour oxyder l’hydrogène avec des densités de courant élevées et sur une large gamme de pH. Son utilisation dans une PEMFC a permis d’obtenir une densité de puissance de 15 mW.cm-2, seulement cinq fois inférieure à celle d’une pile classique à base de platine préparée dans les mêmes conditions. Concernant la catalyse de réduction de l’oxygène, des méthodes covalentes ont été développéespour réaliser la connexion électronique directe de laccase de Trametes sp C30, ainsi qu’un mutant de cetten enzymesur matrice de NTCs L’’association du catalyseur de nickel avec une cathode à base de bilirubine oxydase immobilisée sur NTCs a permis de proposer un nouveau concept de pile hybride enzymatique/bio-inspirée. Une densité de puissance de l’ordre de 1,8 mW.cm-2 et une force électromotrice proche de 1V ont ainsi été mesurées pour cette pile sans métaux nobles. Le greffage de complexes de cuivre mono- et dinucléaires, bio-inspirés du site actif d’enzymes à cuivre et actifs vis-à-vis de la réduction de l’oxygène a enfin permis d’élaborer la première pile H2/air ne renfermant que des catalyseurs moléculaires et sans métaux nobles. Cette dernière délivre une densité de puissance de 160 µW.cm-2
New energy technologies alternative to fossil fuels utilization is a key issue to mitigate greenhouse gases emission and develop a sustainable economy. In this context, platinum-based proton exchange membrane fuel cells use oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) to convert chemical energy into electrical energy. In nature multicopper oxidases and hydrogenases catalyze these two reactions, respectively. These enzymes and corresponding bioinspired catalysts have been used as alternatives to the rare and expensive platinum metal. First, a mononuclear bis-diphosphine nickel complex surrounded by arginine residues was immobilized onto carbon nanotubes (CNTs) and demonstrated excellent performances for HOR developing high current densities over a wide range of pH. This anode was integrated in a PEMFC, which achieved high power densities (15 mW cm-2), only five times lower as compared to classical PEMFC prepared under similar conditions. Regarding ORR catalysis, we covalently grafted LLaccases from Trametes sp C30 multicopper oxidases onto NTCs electrodes and achieved direct electron transfer. Using, bilirubin oxidase deposited on CNTs at the cathode side, we proposed a new concept of hybrid enzymatic/bio-inspired H2/air fuel cell. This hydrogen fuel cell delivered 1.8 mW.cm-2 and a high open circuit voltage of 1V. Finally, various copper complexes inspired from the active sites of copper enzymes were assessed for ORR and the first H2/air fuel cell containing noble metal-free molecular catalysts at both electrodes is reported, achieving 160 µW.cm-2 power density

O uso do peróxido de hidrogênio eletrogerado in situ em Processos Oxidativos Avançados (POAs) é um promissor método para o tratamento de efluentes orgânicos. Neste contexto, o desenvolvimento de materiais mais eficientes para viabilizar a reação de redução do oxigênio (RRO) pelo mecanismo envolvendo a transferência de dois elétrons ainda é de grande importância. O presente estudo objetiva a obtenção e a avaliação da atividade catalítica de nanopartículas de óxidos metálicos, Ta2O5, MoO3, Nb2O5 ou ZrO2, incorporadas em carbono Printex 6L e em grafeno no estudo da redução do oxigênio visando a eletrogeração de peróxido de hidrogênio. A caracterização morfológica e microestrutural desses materiais foi investigada por difração de raios X, microscopia eletrônica de transmissão e espectroscopia de fotoelétrons excitados por raios X. O mecanismo da RRO foi analisado pela técnica do eletrodo de disco-anel rotatório. O carbono Printex 6L apresentou uma eficiência de corrente para a eletrogeração de H2O2 (I(H2O2)%) igual a 65,3% em K2SO4 0,1 mol L-1 (pH =2). Após o tratamento térmico desse substrato pelo método dos precursores poliméricos, a eficiência de corrente aumentou 17,1%, ou seja, I(H2O2)% igual a 76,5%. A modificação do carbono Printex 6L com nanopartículas cristalinas de Ta2O5, MoO3, Nb2O5 ou ZrO2 deslocou o potencial de meia-onda para a RRO para valores menos negativos e aumentou a I(H2O2)%. O Nb2O5/C apresentou a maior I(H2O2)%, 87,1%, enquanto o ZrO2/C deslocou o potencial em 137 mV. O estudo comparativo entre três substratos de carbono para a redução do oxigênio, revelou que o óxido de grafeno reduzido apresentou maior atividade para a RRO comparado ao óxido de grafeno e ao carbono Printex 6L, tanto em eletrólito ácido quanto em eletrólito alcalino. A modificação do rGO com Nb2O5 ou ZrO2 pelo método hidrotermal aumentou a atividade catalítica desse substrato para a RRO. A maior eletrogeração de H2O2 foi observada na presença do ZrO2. De fato, um aumento de 73,7% para 88,5% em K2SO4 0,1 mol L-1 (pH =2), e de 72,9% para 83,1% em NaOH 0,1 mol L-1, foi observado em rGO e ZrO2-rGO, respectivamente. Além disso, o ZrO2-rGO apresentou menor sobrepotencial para a RRO comparado ao rGO sem modificador. Portanto, a presença das nanopartículas de óxidos metálicos na matriz condutora de carbono amorfo intensificou a atividade catalítica para a eletrogeração do H2O2, tanto em carbono Printex 6L quanto em óxido de grafeno reduzido, indicando o efeito sinérgico entre as nanopartículas e o subtrato de carbono. Consequentemente, os catalisadores avaliados neste trabalho são promissores para a eletrogeração de espécies oxidantes in situ e sua aplicaçao em POAs.
In situ electrogeneration of hydrogen peroxide has been greatly application in Advanced Oxidation Processes (AOPs) as an effective water treatment technology. In this context, the development of electrode materials that enable the oxygen reduction reaction (ORR) mechanism through a two-electron pathway with high selectivity at low overpotential has a pronounced importance. In the present study, we investigate the properties of Ta2O5, MoO3, Nb2O5 or ZrO2 nanoparticles supported on Printex 6L carbon and reduced graphene oxide for the electrocatalysis of oxygen reduction to H2O2. The structures and morphologies of these materials were characterized by X-ray diffraction analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. Electrochemical activities toward the ORR were evaluated using a rotating ring-disk electrode system. Printex 6L carbon showed a current efficiency for H2O2 production (I(H2O2)%) of 65.3% in K2SO4 0.1 mol L-1 (pH =2) whereas the carbon heat-treated by the polymeric precursor method displayed 76.5% yield of H2O2 electrogeneration. Carbon Printex 6L modified with Ta2O5, MoO3, Nb2O5 or ZrO2 nanoparticles shifted the half-wave potential for the ORR to less negative potential and increased the I(H2O2)%. The Nb2O5/C showed the highest I(H2O2)%, 87,1%, and the ZrO2/C shifted the potential 137 mV. The comparative study of ORR in acid and alkaline media for the three different conductive carbon pigment showed that the reduced graphene oxide displayed higher activity to oxygen reduction than graphene oxide and Printex 6L carbon. Reduced graphene oxide modified with Nb2O5 or ZrO2 nanoparticles by hydrothermal method increased the catalytic activity of this substrate for ORR which the highest H2O2 electrogeneration was observed for ZrO2-rGO. Indeed, an increase from 73.7% to 88.5% in K2SO4 0.1 mol L-1 (pH =2) and from 72.9% to 83.1% in NaOH 0.1 mol L-1 was obtained for rGO and ZrO2-rGO, respectively. Additionally, the ZrO2-rGO electrocatalyst exhibited overpotential lower than that of rGO unmodified. Therefore, the metallic oxides nanoparticles in both carbon Printex 6L and reduced graphene oxide enhanced the catalytic activity for H2O2 electrogeneration indicating the synergistic effect between the nanoparticles and the amorphous carbon. The catalysts evaluated in this study are promising for in situ electrogeneration of oxidizing agents to be used in the degradation of organic pollutants.

Le but de cette thèse est d’identifier les paramètres pertinents pour la synthèse de nouveaux matériaux par pression à partir de mélanges de gaz moléculaires. Nous avons choisi un système école : les mélanges N2/O2. Dans une première partie, nous avons déterminé le diagramme de démixtion binaire à 300 K des mélanges N2/O2 sous pression. Une miscibilité totale en phase fluide est observée ainsi qu’une large miscibilité en phase solide. La phase solide présente une grande richesse allotropique. A partir des données de diffraction de rayons X, nous montrons que les structures de ces différentes solutions solides sont dérivées de celles des composants purs. Une dissymétrie du diagramme binaire indique cependant que les interactions N2-O2 sont très similaires de celles de N2-N2, mais sont très dissemblables de celles de O2-O2. Dans une deuxième partie, nous avons observé à partir des phases solides N2/O2, sous irradiation laser Nd :YAG, la synthèse du composé ionique NO+NO3-. Un nouveau type de structure en couche est affiné à partir des données de diffraction X. De plus, nous montrons que cette structure ouverte peut piéger des molécules O2 ce qui constitue une nouvelle classe de ‘clathrate’. Enfin, ce composé peut être récupéré à pression ambiante sous forme amorphe. Dans une dernière partie, nous montrons par des mesures de luminescence que le couplage du laser Nd:YAG avec les molécules O2 en phase condensée se fait par résonance avec la transition électronique de l’état triplet vers l’état singulet. Cet état excité est très réactif ce qui devrait permettre la synthèse d’autres matériaux sous pression à partir des mélanges contenant O2
The aim of this thesis is to identify the relevant parameters for the high-pressure synthesis of new materials from mixtures of molecular gases. We have chosen a model system: N2/O2 mixtures. In the first part of this document, we determined the binary phase diagram of N2/O2 under pressure at 300 K. In the fluid, a total miscibility is observed, and a large miscibility exists in the solid phases. The solid phase presents numerous allotropic forms. From the x-ray diffraction data, we show that the structures of those different solid solutions are related to those of pure components. A dissymmetry of the binary phase diagram however indicates that the N2-O2 interactions are very similar to the N2-N2 ones but are very different from the O2-O2 ones. In the second part of this document, we observed the synthesis of the ionic compound NO+NO3- from N2/O2 solid phases under Nd: YAG laser irradiation. A new type of layered structure is refined from the x-ray data. Moreover, we show that this opened structurecan trap O2 molecules what constitutes a new class of “clathrate”. Finally, this compound can be recovered at ambient pressure as an amorphous. In the last part of this document, we show from a luminescence study that the coupling of the Nd: YAG laser with O2 molecules in condensed phase is a resonant phenomenon with the electronic transition from the triplet state to the singlet state. This excited state is very reactive and the high-pressure synthesis of other materials should be possible from mixtures containing O2 molecules

Les matériaux d'électrodes positive pour batteries lithium-ion : O3-LiNi 0. 30 Co 0. 70 O2 et O2-LiCoO2 (préparé par chimie- douce), ainsi que des matériaux obtenus après désintercalation électrochimique ont été caractérisés par DRX, RMN, mesures de conductivité électrique et de pouvoir thermoélectrique. Des processus redox complexes et/ou des changements structuraux interviennent lors de la désintercalation du lithium. Grâce à l'exploitation des interactions hyperfines, la RMN permet de caractériser l'environnement local du lithium dans ces phases: présence de défauts, distribution de cations praramagnétiques (nature et/ou degré d'oxydation), présence d'électrons localisés ou itinérants. . . Et détudier les processus redox liés à la désintercalation du lithium. En parallèle, des calculs ab initio ont permis de mieux comprendre les propriétés structurales et physiques des matér aux étudiés.

L'interaction de l'eau avec les surfaces d'oxyde d'actinides demeure relativement peu étudiée. L'adsorption d'eau à la surface de PuO2 et (U,Pu)O2 conduit à la génération de H2 par radiolyse mais également à l'évolution de l'état de surface. L'étude de l'interaction de l'eau avec les surfaces d'oxydes mixtes (U,Pu)O2 requiert de mettre en œuvre des techniques d'analyses peu intrusives. L'étude de l'hydratation de la surface de CeO2 permet d'étudier la pertinence de différentes techniques d'analyses. Les résultats montrent que l'adsorption d'eau à la surface de CeO2 conduit à une évolution de l'état de surface et la formation d'une couche superficielle de type hydroxyde. La réactivité de l'eau à la surface de CeO2 dépend de la température de calcination du précurseur de l'oxyde. Le traitement thermique des surfaces hydratées permet de régénérer l'état de surface. Cette étude sur CeO2 souligne l'intérêt des techniques d'analyse mises en œuvre quant à l'étude de l'hydratation des surfaces. La génération de dihydrogène par radiolyse de l'eau adsorbée est étudiée par une méthode expérimentale fondée sur le renouvellement d'eau à la surface du matériau. L'accumulation de H2 est linéaire durant les premières heures puis tend vers un état stationnaire. Un mécanisme de consommation de H2 est proposé pour expliquer cet équilibre et également l'évolution des surfaces d'oxyde mixtes (U,Pu)O2 témoignée par l'évolution des cinétiques d'accumulation de H2. La cinétique d'accumulation dépend du débit de dose, de la surface spécifique de l'oxyde, de l'humidité relative de l'atmosphère en équilibre ainsi que du taux de plutonium et de l'état de surface
The interaction of water with actinides oxide surfaces remains poorly understood. The adsorption of water on PuO2 surface and (U,Pu)O2 surface leads to hydrogen generation through radiolysis but also surface evolution.The study of water interaction with mixed oxide (U,Pu)O2 and PuO2 surfaces requires the implementation of non intrusive techniques. The study of the hydration of CeO2 surface is used to study the effectiveness of different techniques. The results show that the water adsorption leads to the surface evolution through the formation of a hydroxide superficial layer. The reactivity of water on the surface depends on the calcination temperature of the oxide precursor. The thermal treatment of hydrated surfaces can regenerate the surface. The study on CeO2 hydration emphasizes the relevancies of these techniques in studying the hydration of surfaces.The hydrogen generation through water radiolysis is studied with an experimental methodology based on constant relative humidity in the radiolysis cell. The hydrogen accumulation is linear for the first hours and then tends to a steady state content. A mechanism of hydrogen consumption is proposed to explain the existence of the steady state of hydrogen content. This mechanism enables to explain also the evolution of the oxide surface during hydrogen generation experiments as shown by the evolution of hydrogen accumulation kinetics. The accumulation kinetics depends on the dose rate, specific surface area and the relative humidity but also on the oxide aging. The plutonium percentage appears to be a crucial parameter in hydrogen accumulation kinetics

Le chapitre 1 présente le contexte des piles à combustibles et des conducteurs par ions 02-@ puis les techniques expérimentales utilisées, dont la spectroscopie d'impédance complexe. Le chapitre Il est dédié à l'étude de l'effet des substitutions de La par R=Nd,Gd,Y et de Mo par W sur les propriétés de La2MO209, nouveau conducteur par ions 02-. L'effet stabilisateur de W et destabilisateur de R sur la réductibilité du molybdate est montré. La sensibilité de la conduction aux conditions de frittage est abordée au chapitre 111, s'ouvrant sur l'étude de la densification des phases par broyage et frittage optirnisé par dilatométrie. L'influence de la porosité sur la conduction est interprétée en terme d'effet de surface, et un comportement de type VTF est postulé à haute T. La forte mobilité anionique de ces phases est montrée par mesure de coefficient de diffusion de traceurs. Le chapitre IV explore le potentiel du concept LPS pour la découverte de nouveaux conducteurs avioniques
Chapter 1 presents the thesis context relative to fuel cells and fast oxide-ion conductors, together with the various techniques used, among which complex irnpedance spectroscopy. Chapter Il is devoted to the study of the substitution effect of La by R=Nd,Gd,Y and of Mo by W on the properties of La2Mo2O9, a new fast oxide-ion conductor. The stabilizing effect of W and destabilizing effect of R on the molybdate reducibility is dernonstrated. The sensitivily of conduction to sintering conditions is explored in chapter In, which opens up on a study of the phases densification through milling, then sintering as optirnised through dilatometry. The influence of porosity on conduction is interpreted in terni of surface effect, and a VTF-type behaviour is postulated at high T. The high anion mobility of these phases is evidenced through tracer diffusion coefficient rneasurements. Chapter IV explores the possibility to use the so-called LPS concept to discover new oxide-ion conductors

Aim The main aim of this study was to investigate the longitudinal effects on cycling performance using a polarized and periodized scheme that was highly supervised and controlled. The second aim was to investigate the effect of using Hyperoxia. The questions used to address the aim were: (1) How does overall performance change after a six-week training intervention? (2) What is the time-course and pattern of performance changes to the training scheme? (3) How does the performance change within the groups?   Method Nineteen male and female cyclists started the study (13 male and 6 female), however only 12 completed it (8 male and 4 female). The characteristics for the 12 subjects were:  age (year) 33.6 ± 6.8, height (cm) 177 ± 9.1, body mass (kg) 73.4 ± 8.8. Using a randomized, double blind design, the test subjects were divided in to hyperoxia (HOT) (n = 6) and normoxia (NOT) (n = 6) training groups.  Over a six week period the subjects followed a controlled polarized periodization that included 15 high intensity interval training (HIIT) sessions (3 x 8 min, 3 x 8 + 4 min, 4 x 8 min & 4 x 4 min) on maximal sustainable intensity (isoeffort) on a cycle ergometer. The dosage of oxygen was administered intermittently by the oxelerate device. A 20 min all out test was performed as pre- and post test.    Results The whole group (n = 12) increased mean power output (W) by 6.4 % (P = 0.002). The relative power output (W/kg) increased significantly 8.2 % (P = 0.0011). The HOT group (n = 6) increased their power output by 8.3 % (P = 0.028) and their relative power output increased by 9.4 % (P=0.011). The whole group (P = 12) significantly increased their VO2mean by 4.1 % (P = 0.03) and in the relative value by 5.4 % (P = 0.01) on the 20 min all out test. The whole group also had a significant increase in VO2peak of 3.7 % (P = 0.04). A very strong correlation could be found between the training data and the performance test.   Conclusions The training intervention was favourable for increasing performance and VO2peak in cycling. Usage of hyperoxia during the training intervention increases the performance.
Syfte och frågeställningar Huvudsyftet med denna studie var att undersöka de longitudinella effekter på prestation i cykling med hjälp av ett polariserat och periodiserat träningsupplägg som var väl övervakat och kontrollerat. Det andra syftet var att undersöka effekten av att använda hyperoxi. De frågeställningar som hjälpte att besvara syftet var: (1) Hur förändras prestationen efter en sex veckors träningsintervention? (2) Hur anpassar sig försökspersonerna till träningsschemat över tid?  (3) Hur förändras prestationen inom grupperna?   Metod 19 manliga och kvinnliga cyklister deltog i studien (13 manliga och 6 kvinnliga), 12 fullföljde hela studien (8 manliga och 4 kvinnliga). Karaktäristiken för de 12 försökspersonerna var: ålder (år) 33.6 ± 6.8, längd (cm) 177 ± 9.1, vikt (kg) 73.4 ± 8.8. Försökspersonerna delades in i hyperoxi (HOT) (n = 6) och normoxi (NOT) (n = 6), studien var dubbelblind. Under sex veckor följde försökspersonerna en kontrollerad polariserad periodisering som inkluderade 15 högintensiva intervallträningspass (HIIT) (3 x 8 min, 3 x 8 + 4 min, 4 x 8 min & 4 x 4 min) på högsta genomförbara intensitet (isoeffort) på cykelergometer. Doseringen av syre administrerades intermittent genom Oxelerate-enheten. Ett 20 min all-out test utfördes som för- och eftertest.   Resultat Hela gruppen (n = 12) ökade signifikant på prestationstestet (W) med 6.4 % (P = 0.002). Den relativa effekten (W/kg) ökade signifikant med 8.2% (P = 0.0011). HOT (n = 6) ökade signifikant på prestationstestet med 8.3% (P = 0.028) och den relativa effekten ökade med 9.4% (P = 0.011). Hela gruppen (n = 12) ökade signifikant i VO2medel under prestationstestet med 4.1 % (P = 0.03) och i det relativa värdet med 5.4 % (P = 0.01). Hela gruppen hade också en signifikant ökning av VO2peak med 3.7 % (P = 0.04). En mycket stark korrelation hittades mellan träningspassdata och prestationstestet.   Slutsats Träningsupplägget är gynnsamt för ökning av prestation och VO2peak i cykling. Användning av hyperoxi under träningsupplägget ökar prestationen.

Le principal objectif de cette étude est d'acquérir des données de base sur la dissolution de composés (U,Pu)O2 en appui à la compréhension des phénomènes intervenant lors des étapes de dissolution des combustibles MOX des filières de réacteurs à eaux légères et à neutrons rapides sodium. Les études antérieures, en particulier sur des combustibles MOX non irradiés, ont mis en évidence la complexité d'une compréhension des mécanismes de dissolution par une approche directe. En effet, la dissolution dépend d'un grand nombre de paramètres, qui sont principalement les conditions chimiques d'attaque (acidité, température, ...), mais surtout les caractéristiques physico-chimiques de la pastille considérée (teneur en plutonium, homogénéité de la teneur en plutonium, microstructure, géométrie, ...), la majorité d'entre elles étant fortement dépendantes du procédé de fabrication utilisé. Pour éviter l'obtention de réponses moyennées du fait de la présence d'une hétérogénéité de la répartition en Pu au sein des pastilles, on se propose de réaliser une étude sur des poudres de composés monophasés de stœchiométrie parfaitement définie (U et Pu) et de morphologie parfaitement déterminée. Une approche par étapes a permis de déterminer les différents paramètres clé déterminant les cinétiques de dissolution de ces oxydes d’actinides (surface spécifique, taille des cristallites, teneur en Pu, activité des ions nitrate, température de dissolution, énergie d’activation).Une loi cinétique globale permettant de décrire les cinétiques de dissolution des oxydes U1-xPuxO2 a été établie à partir de 45 essais différents (avec 0≤x≤1). Elle décrit les cinétiques de dissolution obtenues à toutes teneurs en plutonium et morphologies de l’oxyde, dans des gammes de températures variant de 50 à 95°C et des intervalles d’acidités variant de 1,5 à 8,5 mol/L. Le modèle ainsi créé décrit assez précisément la cinétique de dissolution de n’importe quel oxyde U1-xPuxO2 alors qu’il existe plus de cinq ordres de grandeurs d’écart entre les cinétiques de dissolution de l’UO2 et du PuO2. Des essais complémentaires sur des composés monophasés ont été menés validant le caractère prédictif du modèle
The main objective of this study is to acquire data on the dissolution of (U, Pu)O2 compounds to support the understanding of the phenomena occurring during the dissolution steps of MOX fuels irradiated in light water or sodium fast reactors. Previous studies, in particular on unirradiated MOX fuel, have highlighted the complexity of understanding the dissolution mechanisms through a direct approach. Indeed, the dissolution depends on a large number of parameters, which are mainly chemical dissolution parameters (acidity, temperature…). But it also depends on the physico-chemical characteristics of the fuel pellets (plutonium content, homogeneity of the plutonium content, microstructure, geometry...), a majority of which being highly dependent on the manufacturing process used. To avoid getting averaged responses due to the presence of heterogeneity in the Pu distribution in pellets, it is proposed to carry out a study on single-phase compounds in the shape of powders characterized by a well-defined stoichiometry (U and Pu) and a perfectly determined morphology. A step approach allowed the determination of the key parameters controlling the dissolution kinetics of these actinide oxides (specific surface area, crystal size, Pu content, activity of nitrate ions, dissolution temperature).A global kinetics law describing the dissolution kinetics of U1-xPuxO2 oxides was established from 45 dissolution tests (with 0≤x≤1, [HNO3] and temperature ranging from 1.5 to 8.5M and from 50 to 95°C respectively). Despite the 5 orders of magnitude between dissolution kinetics of UO2 and PuO2, the model shows a good precision. Additional dissolution tests were conducted on different single-phase oxide powders to validate the predictive quality of this model

La magnétite, Fe3O4, est un oxyde de fer naturel à valence mixte Fe(II-III), qui sous sa forme nanométrique, a un fort potentiel d’applications technologiques dans des domaines allant de la biomédecine au traitement des eaux. Les nano-magnétites sont très efficaces pour l’adsorption ainsi que la réduction et l’oxydation de divers polluants environnementaux. Elles peuvent catalyser l’oxydation de type Fenton hétérogène induisant une dégradation efficace des polluants organiques et ceci dans un large domaine de pH. Cependant, les mécanismes impliqués restent mal connus. L’objectif principal de cette étude est d’explorer la capacité de la nano-magnétite à catalyser des réactions radicalaires de type Fenton hétérogène sans ajout d’oxydants forts, mais en utilisant uniquement l’oxygène de l’air. Ces réactions pourraient par la suite constituer la base de nouveaux procédés de remédiation efficace et éco-compatible pour l’élimination des polluants organiques dans différents compartiments de l’environnement. L’acide nalidixique, un antibiotique appartenant à la famille des quinolones, a été utilisé comme contaminant modèle, car ce composé polaire et ionisable se révèle persistant dans l’environnement et récalcitrant aux traitements classiques.Après synthèse de nano-magnétite offrant une surface spécifique élevée, la sorption de l’acide nalidixique sur ce support a été étudiée en conditions anoxiques et une adsorption supérieure à 98 % a été obtenue. En présence d’oxygène, cette sorption est suivie d’une transformation du contaminant modèle. Après désorption selon un protocole qui a été développé, un taux de dégradation d’environ 60 % a été évalué après seulement 30 minutes d’oxygénation, et 80% après 90 minutes. Cinq sous-produits de NAL ont été identifiés par chromatographie liquide couplée à la spectrométrie de masse (UHPLC-MS/MS) et un schéma de dégradation a été proposé. L’analyse de la phase solide par la diffraction des rayons X et par spectroscopie d’absorption au seuil K du fer (XANES et EXAFS) démontre une oxydation significative de la magnétite en maghémite (jusqu’à 40 %). Complétés d’une part par le suivi de la teneur en Fe(II) dissous, et des expériences réalisées en présence d’un piège à radicaux hydroxyles, et d’autres part par l’interprétation des effets du pH et de son évolution lors de la réaction, ces résultats ont permis de proposer un mécanisme réactionnel qui implique la formation des espèces réactives d’oxygène suite à l’oxydation de la magnétite.Les conclusions tirées des résultats expérimentaux prouvent les potentialités prometteuses des oxydes de fer mixte dans la remédiation des sols et eaux contaminés par des composés organiques
Magnetite, Fe3O4, is a natural mixed iron oxide Fe(II-III), that has a wide range of applications in biomedicine as well as in water treatment. Nanosized magnetite presents high capacities to adsorb and transform a wide range of contaminants via oxidative or reductive reactions. It was shown as an active catalyst for heterogeneous Fenton reactions in the removal of organic compounds under a broad range of pH. However, the mechanisms of these reactions are not well defined.The main objective of this study was to explore the nanomagnetite capacity to catalyze heterogeneous Fenton reactions in presence of dissolved oxygen, thus avoiding the use of strong chemical oxidants. These reactions could form the basis of a new efficient and eco-friendly process for the removal of organic pollutants. Nalidixic acid (NAL), an ionizable quinolone antibiotic known for being persistent and recalcitrant to classical treatments, was used as a model contaminant.We synthesized large surface area single-cristalline nanomagnetite with high NAL sorption ability (98%) under anoxic conditions. Furthermore, a desorption protocol was developed to recover the sorbed amount of NAL in order to measure the degradation percentage.Moreover, under oxic conditions, the model contaminant was transformed, up to nearly 60% and 80 % after a 30 and 90 minutes exposure to air bubbling, respectively. Five by-products issuing from the nalidixic acid oxidative degradation were identified by liquid chromatography-mass spectrometry and a degradation pathway was suggested. X-ray powder diffraction and Iron K-edge X-ray absorption spectroscopy were used to investigate mineralogical and iron redox changes in the solid phase over the course of the reaction. Magnetite was oxidized (up to about 40%) into maghemite, -Fe2O3, as the sole product of the oxidation, and without significant change in the size of the particles. These results, in addition to the monitoring of dissolved Fe(II), and experiences conducted in the presence of ethanol as hydroxyl radicals scavenger and at static pH, lead to a better understanding of the reaction mechanism and on the role of pH in the reaction efficiency. In conclusion, this study points out the promising potentialities of mixed valence iron oxides for the treatment of contaminated soils and wastewater by organic pollutants

Le plutonium issu des reacteurs nucleaires a eau sous pression est partiellement integre dans le cycle du combustible sous forme de combustible mixte (u,pu)o 2 (mox). Le retraitement de ces oxydes dans les usines actuelles impose de les dissoudre dans l'acide nitrique. La difficulte principale de cette etude reside dans le fait que la dissolution est un phenomene dependant a la fois des caracteristiques de la solution d'attaque mais aussi des proprietes structurales de la pastille, elles memes influencees par le procede de fabrication du materiau. Apres une presentation des donnees cinetiques et thermodynamiques de la dissolution des oxydes mixtes en milieu nitrique, les parametres influencant la dissolution ont ete recensees. Le concept de la separation des variables a permis de decrire ce processus en etudiant independamment le role des parametres chimiques de la solution d'attaque et les parametres geometriques du materiau. La premiere partie de l'etude a permis d'estimer l'influence des parametres chimiques de la solution nitrique (concentrations des especes en solution, acidite, temperature) sur la dissolution et de mettre en evidence le role de l'etape de protonation de la surface de l'oxyde. La seconde partie de ce travail concerne l'etude de l'evolution de la surface de materiaux a heterogeneites plutoniferes controlees. Les resultats experimentaux montrent un phenomene d'erosion de surface de la pastille accompagne d'une fragilisation par creusement suivi de la mise en solution de fragments par sub-millimetriques. Un modele de cinetique heterogene issu de l'etude des systemes a l'interface solide-gaz a ete applique a la dissolution de pastilles de combustible. Un mecanisme a alors ete propose, base sur la dissolution en surface de l'oxyde ainsi que dans le volume par la creation de failles. Cette deuxieme voie differe suivant la microstructure et la tenue mecanique de la pastille.

Les travaux présentés portent sur l’étude et l’élaboration de la synthèse de nanoparticules d’oxyde de cérium CeO2 et l’oxyde mixte CexZr(1-x)O2 avec une morphologie contrôlée. Différentes morphologies telles que; nanocubes, nanobarres et nanopolyhèdre ont été obtenues dépendamment des conditions de synthèse. Un dépôt d'or à la surface des nanoparticules synthétisées a été effectué. Le choix de l'or s'est fait étant donné son grand pouvoir catalytique à basse température. Ces catalyseurs ont été caractérisés par différentes techniques (TEM, BET) et ont fait l’objet d’essais catalytiques pour l’oxydation du CO. Les résultats montrent que les nanocatalyseurs sous forme cubique donnent un meilleur résultat comparé aux nanobarres et nanopolyhèdre. Ceci s’explique par le fait que leur surface spécifique est supérieure et par la préférence des sites actifs d’or à se déposer sur la face (100) des nanocubes. Ce résultat est corroboré par les énergies d’activation calculées. Afin d’améliorer l’activité catalytique et la stabilité de ce type de nanocatalyseurs, on a substitué une partie du cérium du zirconium. Les résultats des tests catalytiques montrent que la limite de substitution ne peut excéder 10% en zirconium. Au-delà de ce taux, la conversion complète du CO en CO2 est nettement inférieure à celle du nanocatalyseur à base de simples nanocubes de CeO2.
The presented works involve the study and the elaboration of the synthesis of cerium oxide CeO2 and oxide mixed CexZr(1-x)O2 nanoparticles with a controlled morphology. Various morphologies including nanocube, nanobar and nanopolyhedron have been obtained depending on the synthesis conditions. A deposit of gold on the surface of synthesized nanoparticles has been carried out. The choice of gold nanoparticles as active phase is due to their high catalytic activity at low temperatures. These catalysts had been characterized by various techniques (TEM, BET) and subjected to catalytic tests for CO oxidation. The results show that the cubic form of nanocatalysts give a better result compared to nanobars and nanopolyhedron. This is explained by the fact that their specific surface is greater and preferably gold nanoclusters to be deposited on the face (100) nanocubes. The obtained result is supported by the activation energy calculation. In order to improve the catalytic activity and stability of this type of Nanocatalyst, a portion of the cerium zirconium has been substituted. The catalytic test results show that the substitution limit shall not exceed 10% zirconium. Beyond this level, the complete conversion of CO to CO2 is significantly smaller than the nanocatalysts based on simple nanocubes CeO2.