Objectif : Ce travail s'inscrit dans le cadre d'une recherche étiologique sur les leucémies aigues (LA) de l'enfant, pathologies dont les facteurs de risque sont peu connus. Plusieurs hypothèses ont été testées : 1) le rôle protecteur d'une supplémentation maternelle en acide folique avant et pendant la grossesse et l'investigation par une approche gène-candidat du rôle de polymorphismes communs rs1801133 et 1801131 de MTHFR et rs1801394 et rs1532268 de MTRR supposés modifier le métabolisme des folates, 2) l'association entre la profession et des expositions professionnelles maternelles lors de la grossesse, 3) l'existence d'un lien positif avec l'exposition des enfants au trafic routier. Matériel et méthodes : Les données analysées proviennent d'une étude cas-témoins française, ESCALE, basée sur le Registre National des Hémopathies malignes de l'Enfant et réalisée en population générale sur la période 2003-2004. L'échantillon comportait 648 cas de leucémie aiguë lymphoblastique [LAL], 116 cas de leucémie aiguë non lymphoblastique [LANL], et 1681 témoins de moins de 15 ans. L'échantillonnage a été stratifié sur l'âge et le sexe. Les données ont été recueillies auprès des mères à l'aide d'un questionnaire téléphonique standardisé, identique pour les cas et les témoins. Les génotypes ont été obtenus par génotypage à haut débit, pangénomique pour les cas et à façon pour les témoins, et par imputation pour les polymorphismes non génotypés. Le géocodage des adresses et des indicateurs dérivés de données d'émission de trafic ont permis d'estimer l'exposition des enfants au trafic routier. Les odds ratios (OR) ont été estimés à l'aide de modèles de régression logistique non conditionnelle, incluant les facteurs de confusion potentiels. Résultats : Le risque de LA était significativement inversement associé à une supplémentation maternelle en acide folique avant ou pendant la grossesse (OR=0.4 [0.3-0.6]). Aucun des polymorphismes génétiques de MTHFR et de MTRR n'était associé au risque de LA. Cependant, le fait d'être à la fois porteur homozygote des allèles variants de l'un des polymorphismes de MTHFR, et porteur de deux allèles variants des polymorphismes de MTRR était positivement associé au risque de LA (OR=1.6 [0.9-3.1]). Nous n'observions pas d'interaction entre MTHFR, MTRR et une supplémentation maternelle en acide folique. Des associations positives et significatives on été mises en évidence entre le risque de LA et des expositions auto-déclarées professionnelles maternelles pendant la grossesse, aux teintures de cheveux (OR=3.0 [1.7-5.2]), à des peintures ou vernis et/ou colles (OR=1.5 [1.1-2.2]), et à des rayonnements ionisants (OR=2.4 [1.3-4.6]). Cependant, ces associations étaient limitées aux fréquences d'exposition de moins d'1 heure par semaine et peuvent refléter une sur-déclaration chez les cas. L'exposition maternelle professionnelle aux pesticides n'était pas associée aux LA dans notre étude.Les LA étaient significativement associées à des concentrations élevées de NO2 de fond liées au trafic estimées au lieu de résidence (OR=1.2 [1.0-1.5]) et avec la présence de routes à fort trafic dans un rayon de 500 m centré sur ce lieu (OR=2.0 [1.0-3.6]). Nous observions une association significative entre les LA et une densité élevée de routes à fort trafic dans un rayon de 500 m (OR=2.2 [1.1-4.2]), avec une tendance linéaire positive significative de l'association des LAL avec la longueur totale de routes à fort trafic dans un rayon de 500 m.Conclusion : Cette thèse apporte des arguments en faveur du rôle protecteur d'une supplémentation maternelle périconceptionnelle en acide folique. Elle suggère également un rôle des polymorphismes de MTHFR et MTRR dans le risque des LA, sans interaction toutefois avec la supplémentation. Enfin, elle renforce l'hypothèse que vivre près de routes à fort trafic pourrait augmenter le risque de LA.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

Le travail de thèse propose d’éclaircir les dynamiques qui régissent les réactions d’hydrogénation du dioxyde d’azote (NO2) se déroulant à la surface de catalyseurs modèles de platine, de rhodium et de leur alliage Pt-Rh. Une meilleure compréhension de la réaction catalytique en conditions réactionnelles permettrait, à terme, un meilleur contrôle de la réaction. De manière similaire, le comportement du catalyseur permettrait d’orienter la synthèse de catalyseurs afin d’en augmenter la sélectivité et/ou activité. La structure de ces catalyseurs ainsi que l’analyse des processus sont effectuées à l’échelle nanométrique grâce à l’utilisation de microscopies à effet de champ :la microscopie ionique à effet de champ (FIM) et la microscopie d’émission d’électrons par effet de champ (FEM). La réaction NO2+H2 étudiée à 390 K sur le platine permet de mettre en évidence la présence de différents domaines réactionnels :dynamique monostable, oscillations périodiques auto-entretenues, oscillations périodiques bimodales, ainsi que des oscillations bruitées. Malgré la présence importante de fluctuations à l’échelle du nanomètre, les traitements de signaux mettent en évidence une importante robustesse qui se traduit par un temps de corrélation qui s’étend sur plusieurs centaines de périodes. Les données donnent matière à la reconstruction de l’attracteur dynamique consistant en un cycle limite. La pression d’hydrogène est le paramètre de contrôle qui est varié de sorte à provoquer l’apparition d’oscillations selon une bifurcation de type homocline dans ce cas-ci. Des mesures à haute-vitesse d’acquisition démontrent que l’ignition des différentes faces réactives s’effectue de manière désynchronisée, et la vitesse de propagation est de l’ordre de ~2 μm/s. Au sein d’une seule face, à l’échelle du nanomètre, des propagations de fronts d’ondes chimiques peuvent également être observées à une vitesse de ~2 μm/s, en accord avec les vitesses analysées lors d’expériences menées à l’échelle du micromètre et du millimètre. Sur base des observations, un mécanisme réactionnel de production d’H2O a été proposé. La réaction sur le rhodium à 450 K engendre également des oscillations périodiques qui diffèrent par une robustesse plus faible et par l’apparition d’un cycle limite selon une bifurcation de Hopf. Des mesures exploratoires à 500 K font ressortir la présence de chaos dans le système. Finalement, l’alliage Pt-Rh utilisé comme catalyseur permet d’obtenir des oscillations à 425 K de période comprise entre celles observées sur les deux métaux purs. L’ensemble des expériences et des résultats obtenus à l’échelle du nanomètre permet pour la première fois de valider la théorie des systèmes dynamiques à une telle échelle. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

In this thesis the oxidation of monoterpenes by O3 and NO2 and factors that influenced the oxidation were studied. In the environment both ozone (O3) and nitrogen dioxide (NO2) are present as oxidising gases, which causes sampling artefacts when using Tenax TA as an adsorbent to sample organic compounds in the air. A scrubber was developed to remove O3 and NO2 prior to the sampling tube, and artefacts during sampling were minimised when using the scrubber. The main organic compounds sampled in this thesis were two monoterpenes, alfa-pinene and delta-3-carene, due to their presence in both indoor and outdoor air. The recovery of the monoterpenes through the scrubber varied between 75-97% at relative humidities of 15-75%. The reactions of alfa-pinene and delta-3-carene with O 3, NO2 and nitric oxide (NO) at different relative humidities (RHs) and reaction times were studied in a dark reaction chamber. The experiments were planned and performed according to an experimental design were the factors influencing the reaction (O3, NO2, NO, RH and reaction times) were varied between high and low levels. In the experiments up to 13% of the monoterpenes reacted when O3, NO2, and reaction time were at high levels, and NO, and RH were at low levels. In the evaluation eight and seven factors (including both single and interaction factors) were found to influence the amount of alfa-pinene and delta-3-carene reacted, respectively. The three most influencing factors for both of the monoterpenes were the O 3 level, the reaction time, and the RH. Increased O3 level and reaction time increased the amount of monoterpene reacted, and increased RH decreased the amount reacted. A theoretical model of the reactions occurring in the reaction chamber was created. The amount of monoterpene reacted at different initial settings of O3, NO2, and NO were calculated, as well as the influence of different reaction pathways, and the concentrations of O3 and NO2, and NO at specific reaction times. The results of the theoretical model were that the reactivity of the gas mixture towards alfa-pinene and delta-3-carene was underestimated. But, the calculated concentrations of O3, NO2, and NO in the theoretical model were found to correspond to a high degree with experimental results performed under similar conditions. The possible associations between organic compounds in indoor air, building variables and the presence of sick building syndrome were studied using principal component analysis. The most complex model was able to separate 71% of the “sick” buildings from the “healthy” buildings. The most important variables that separated the “sick” buildings from the “healthy” buildings were a more frequent occurrence or a higher concentration of compounds with shorter retention times in the “sick” buildings. The outcome of this thesis could be summarised as follows; - - - -

<p>In this thesis the oxidation of monoterpenes by O3 and NO2 and factors that influenced the oxidation were studied. In the environment both ozone (O3) and nitrogen dioxide (NO2) are present as oxidising gases, which causes sampling artefacts when using Tenax TA as an adsorbent to sample organic compounds in the air. A scrubber was developed to remove O3 and NO2 prior to the sampling tube, and artefacts during sampling were minimised when using the scrubber. The main organic compounds sampled in this thesis were two monoterpenes, alfa-pinene and delta-3-carene, due to their presence in both indoor and outdoor air. The recovery of the monoterpenes through the scrubber varied between 75-97% at relative humidities of 15-75%.</p><p>The reactions of alfa-pinene and delta-3-carene with O 3, NO2 and nitric oxide (NO) at different relative humidities (RHs) and reaction times were studied in a dark reaction chamber. The experiments were planned and performed according to an experimental design were the factors influencing the reaction (O3, NO2, NO, RH and reaction times) were varied between high and low levels. In the experiments up to 13% of the monoterpenes reacted when O3, NO2, and reaction time were at high levels, and NO, and RH were at low levels. In the evaluation eight and seven factors (including both single and interaction factors) were found to influence the amount of alfa-pinene and delta-3-carene reacted, respectively. The three most influencing factors for both of the monoterpenes were the O 3 level, the reaction time, and the RH. Increased O3 level and reaction time increased the amount of monoterpene reacted, and increased RH decreased the amount reacted.</p><p>A theoretical model of the reactions occurring in the reaction chamber was created. The amount of monoterpene reacted at different initial settings of O3, NO2, and NO were calculated, as well as the influence of different reaction pathways, and the concentrations of O3 and NO2, and NO at specific reaction times. The results of the theoretical model were that the reactivity of the gas mixture towards alfa-pinene and delta-3-carene was underestimated. But, the calculated concentrations of O3, NO2, and NO in the theoretical model were found to correspond to a high degree with experimental results performed under similar conditions. The possible associations between organic compounds in indoor air, building variables and the presence of sick building syndrome were studied using principal component analysis. The most complex model was able to separate 71% of the “sick” buildings from the “healthy” buildings. The most important variables that separated the “sick” buildings from the “healthy” buildings were a more frequent occurrence or a higher concentration of compounds with shorter retention times in the “sick” buildings.</p><p>The outcome of this thesis could be summarised as follows;</p><p>-</p><p>-</p><p>-</p><p>-</p>

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.

<div>Since as early as the 1920s, dinitrogen tetroxide (N2O4) has been regarded as a promising oxidizer in rocket propulsion systems. In more recent times, its predecessor, mixed oxides of nitrogen (MON), remains a top contender among oxidizers, due to its unique characteristics such as low freezing temperature and compatibility with common spacecraft materials. Today, these N2O4-based oxidizers are the preferred choice in many upper stages, launch escape systems, reaction control systems, liquid apogee engines, and in-space primary propulsion systems. N2O4-based oxidizers are a key factor in rocket propulsion, and thoroughly understanding their history, development, characteristics, synthesis, and composition analysis are crucial for space exploration today and into the future.<br><br></div><div>To fully understand and predict the physical properties of a MON sample, it is important to measure and quantify its chemical composition. The recommended method for MON composition analysis, as prescribed by the Department of Defense’s Defense Specification (MIL-SPEC) document on N2O4, involves the oxidation of NO and dinitrogen trioxide (N2O3) in the MON sample to determine their amounts. An equation unofficially called the “MIL-SPEC equation” is then used to determine the amount of NO needed to mix with N2O4 to synthesize that particular MON sample. However, no explanation is given as to how the equation was derived, or its significance.<br><br></div><div>This thesis aims to collect and organize key information on the synthesis, handling, and composition analysis of MON propellant. First, the history of development of N2O4-based oxidizers was researched, and current and future uses of N2O4 and MON propellants were identified. Then a method for synthesis and composition analysis was devised and tested. Water contamination was expected of skewing the results, so the process of water contamination was examined analytically. Then a detailed derivation of the MIL-SPEC equation was conducted, to fully understand its mechanics. An attempt was then made to reverse-engineer an unexplained numerical value in the equation, labeled by the author as the “solubility factor”. Several derivations were provided with varying degrees of complexity, producing alternative solubility factors of varying accuracies. Finally, experimental data was applied to these derived, hypothetical solubility factors and the MIL-SPEC solubility factor, with the intent of determining whether improvements could be made to the MON composition determination process.<br><br></div><div>The results suggest that the MIL-SPEC equation is sufficient for providing a relatively accurate measurement of the composition of a MON sample, while also being easy to implement, both in taking the necessary measurements and in conducting the numerical calculation. However, some minor adjustments to the equation could produce consistently more accurate composition measurements without adding any more difficulty or complication.</div>