Made available in DSpace on 2014-10-09T12:49:38Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:17Z (GMT). No. of bitstreams: 1 10427.pdf: 11180152 bytes, checksum: f8294650781a8994bcbc91409d2cadb8 (MD5) / Tese (Doutoramento) / IPEN/T / Intituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP

Este trabalho apresenta a síntese e a caracterização de quatro complexos trinucleares de acetato de rutênio, de fórmula geral [Ru3O(CH3COO)6(L)2(CO)] nos quais L são ligantes N-heterocíclicos 4-aminopiridina, isonicotinamida, 4-(dimetil)aminopiridina e 2,6-dimetilpirazina com características -aceptoras ou -doadoras. Os derivados de rutênio foram sintetizados de acordo com adaptações de rotas sintéticas já reportadas na literatura, e caracterizados por meio de técnicas de cunho espectroscópico, eletroquímico e outras, a saber: análise elementar, 1H RMN, absorção UV-vis, infra-vermelho, voltametria cíclica e difração de raios-X. Foi investigada a liberação fotoinduzida de monóxido de carbono proveniente dos complexos trinucleares em acetonitrila, por meio de acompanhamento espectrofotométrico. O rendimento quântico envolvido na liberação do CO foi calculado por meio de actinometria química. Foi estudada a interação entre os complexos com as biomoléculas HSA e o DNA de timo de bezerro por meio das técnicas espectroscópicas de fluorescência, UV-vis e dicroísmo circular. Além disso, foram realizados ensaios preliminares in vitro para avaliar a citotoxicidade dos complexos frente a uma linhagem de células de melanoma murinho (B16F10) e foi avaliada a atividade tripanocida dos complexos sobre a forma amastigota do parasita Tripanossoma cruzi. / This work describes the synthesis and characterization of four ruthenium trinuclear complex of general formula [Ru3O(CH3COO)6(CO)(L)2] where L = 2,6-dimethylaminopyridine; isonicotinamide; 4-aminopyridine and 4-dimethylpyrazine (N-heterocyclic ligands with -acceptor or -donor characteristics). The ruthenium derivatives were synthesized according to adaptations of synthetic routes already reported in literature and characterized by spectroscopic and electrochemical techniques such as nuclear magnetic ressonance (NMR), UV-vis, infrared, cyclic voltammetry, X-ray diffraction and elemental analysis. The photoinduced release of carbon monoxide in acetonitrile was investigated by means of spectrophotometric monitoring. The quantum yield involved in the CO release was calculated by chemical actinometry. It was studied the interaction between the complexes with the biomolecules HSA and calf thymus DNA by spectroscopic techniques of fluorescence, UV-vis and circular dichroism. In addition, preliminary tests were performed in vitro in order to evaluate the cytotoxicity of the complexes against a murine melanoma cell line (B16F10) and trypanocidal activity of the complexes over the amastigote form of the parasite Trypanosoma cruzi.

Oxidação de CO dissolvido em Pt(111) e Pt(110) foi realizada em soluções de ácido sulfúrico e perclórico em eletrodo rotatório em configuração de menisco (HMRDE). O uso de diferentes soluções eletrolíticas revelou a influência do anion na cinética de oxidação. Uma vez oxidada a camada de CO adsorvido, ânions podem adsorver na superfície do eletrodo provocando mudanças na corrente estacionária em potenciais anódicos. Na varredura negativa, os ânions adsorvidos são deslocados da superfície quando a velocidade de oxidação de CO é menor que a velocidade de adsorção de CO. A carga associada a esse deslocamento foi obtida para altas velocidades de varredura, resultado semelhante aos experimentos de deslocamento espécies adsorvidas só que a baixos potenciais. A oxidação de CO dissolvido também foi realizada em superfícies escalonadas pertencente à série Pt(s)[n(111)×(111)] usando a mesma configuração dos experimentos com eletrodos de baixo índice de Miller em solução de ácido sulfúrico. O perfil voltamétrico não foi significantemente modificado pela presença de defeitos (degraus). No entanto, as curvas são deslocadas para potencias negativos com o aumento da densidade de degraus. Assim, na varredura positiva, foi observada uma relação linear do potencial de inicio de oxidação (pico de ignição) e a densidade de degraus para os eletrodos com terraços de largura superior a 5 átomos de Pt. Na varredura negativa, o mesmo comportamento foi observado no potencial onde a reação não é mais favorecida. Neste caso, o eletrodo de Pt(111) mostrou um comportamento distinto das superfícies escalonadas, devido a formação e uma ordenada camada de (bi)sulfato adsorvido O processo de adsorção de ânion foi também observada na varredura negativa sob altas velocidades de varredura, com cargas relacionadas a dessorção do ânion similares a Pt(111). Apenas para o eletrodo com terraços de largura de 3 átomos mostrou valores similares a Pt(110). Todos os resultados foram analisados em função do mecanismo de reação e o possível efeito dos degraus na formação da camada de adsorção de CO. Para finalizar, um modelo para a oxidação de CO dissolvido foi proposto usando para isso equações diferenciais que descrevem o comportamento dos processos envolvidos na reação de oxidação. Através das voltametrias cíclicas obtidas pelas simulações foi possível investigar o papel da camada de adsorção de CO, a variação das constantes de velocidade das reações envolvidas e as condições do transporte de massa na resposta eletroquímica. Os resultados mostraram que a oxidação de CO dissolvido é um processo complexo com um delicado balanço das velocidades de reações envolvidas, e o deslocamento de ânions contribui para a velocidade da reação global. / Bulk CO oxidation experiments have been carried out in sulphuric and perchloric acid solutions on Pt(111) and Pt(110) electrodes under hanging meniscus rotating disk electrode (HMRDE) configuration. The comparison between the two different electrolytic media reveals an important influence of the anion in the oxidation kinetics. Once the adsorbed CO layer has been oxidized after the ignition peak, anions are re-adsorbed on the electrode surface and the presence of these anions affects the stationary currents measured at positive potentials. In the negative-going sweep, adsorbed anions are displaced from the surface when the CO oxidation rate is lower than the corresponding CO adsorption rate. The charge associated to this displacement has been measured at high scan rates and is in agreement with that expected from the CO displacement experiments performed at low potentials. Bulk CO oxidation has been studied on platinum stepped surfaces belonging to the series Pt(s)[n(111)×(111)] using the same configuration for low indice Miller electrodes. The general shape of the voltammograms is not significantly affected by the presence of the steps. However, the curves shift towards negative values as the step density increases. Thus, in the positive going scan, a linear relationship is observed for the dependence of the potential for the ignition peak with the step density for surfaces with terraces wider than 5 atoms. In the negative going scan a similar situation is observed for the potential where the current drops to zero. In this case, Pt(111) electrode deviates from the expected behavior, because the formation of the ordered bisulfate adlayer on the electrode. The anion adsorption process is also observed by recordings the voltammograms at high scan rate. All these results have been analyzed in light of the mechanism, discussing the possible effects of the steps and the defects in the CO adlayer. A simple model for the electrocatalytical carbon monoxide bulk oxidation on a platinum electrode was studied by Mean Field Approximation simulation. Under potentiodynamic conditions, the model enabled the investigation of the role of CO adlayer, rate constants and different mass transport conditions on the macroscopic electrochemical response. The results showed that the CO bulk oxidation is a complex process with a delicate balance between the three reaction rates and the displacement of anions by CO adsorption contributes to the overall reaction rate.

Neste trabalho foi estudada a reação de metanação do CO em catalisador de Ru/C e sua aplicação em purificação de hidrogênio para utilização em célula a combustível. Tendo como meta a otimização da produção de metano em baixas temperaturas foram preparados materiais de RuxPd(1-x)/C, que também foram tratados termicamente em atmosfera úmida e redutora. Ao final do estudo com CO, também foi investigado o efeito da presença de CO2 no fluxo de hidrogênio, tal qual num sistema real utilizando-se gás de síntese. Os dados obtidos por espectroscopia de energia dispersiva de Raio-X (EDX) mostraram uma boa correspondência entre as composições teóricas e as obtidas experimentalmente dos catalisadores preparados neste trabalho. Analisando-se os difratogramas de Raio-X (DRX) foi possível observar a presença de fases metálicas principalmente de Ru, observando-se também o aumento da cristalinidade do material, promovido pelo tratamento térmico. Além disso, os tamanhos médios de cristalito (TMC) dos materiais foram obtidos com a equação de Scherrer e situaram-se em torno de 2,5 nm. As micrografias de TEM confirmaram o tamanho reduzido das partículas, mas apontaram para uma baixa dispersão dos materiais sobre o suporte, principalmente no caso do Ru/C. Com as medidas de XPS foram identificadas espécies de Ru metálico, Ru(IV), Ru(VII), RuOxHy e Ru.xH2O. O tratamento térmico somente afetou a população de espécies do material Ru/C, que passou a apresentar maior percentual de Ru metálico, em detrimento aos óxidos. Os catalisadores Ru/C e Ru7Pd3/C antes e após o tratamento térmico foram acomodados em filtro de linha gasosa (reator de leito fixo), sendo possível concluir que o tratamento térmico somente promoveu melhora no desempenho metanador para o catalisador Ru/C. Quando utilizados em camada difusora anódica este efeito foi ainda mais pronunciado, sendo observada a produção de CH4 em regime estacionário em Ru/C tratado termicamente quando a temperatura de metanação foi 85 °C. O material mais eficiente foi o de Ru/C após o tratamento térmico, sendo capaz inclusive de hidrogenar seletivamente o CO na presença de CO2. A melhora no desempenho da célula que utilizou este material foi mais notável a 105 °C, possibilitando a operação com 33 mV de sobrepotencial a 1 A.cm-2 quando alimentada com H2 contendo 75 ppm de CO. / In this work the CO methanation reaction over Ru/C catalyst and its practical applications for use as hydrogen purifier for low temperature fuel cell anodes were studied. Aiming at optimizing the low temperature methane production, two main procedures were proposed: The use of RuxPd(1-x)/C materials and its corresponding thermal treatment of the Ru/C catalyst under wet and reductive atmosphere. The effect of the presence of CO2 was then investigated under the same conditions as for CO in order to establish the catalysts selectivity for the CO methanation in the presence of CO2, as in a real system using syngas. EDX data showed a good agreement between the expected compositions and that actually obtained for catalysts prepared in this work. DRX spectra have indicated the presence of metallic phases, particularly of Ru, and the increase of the material crystallinity, promoted by the thermal treatment. Furthermore, the materials mean crystallite sizes were obtained by the use of the Scherer equation and they resulted around 2,5 nm for all samples. TEM micrographs confirmed the small particle size but also showed a poor material dispersion of the metals over the carbon support, especially in the case of Ru/C. XPS measurements have evidenced the presence of ruthenium species such as Ru(IV), Ru(VII), RuOxHy and Ru.xH2O in the prepared ruthenium material. The thermal treatment only affected the Ru species population, showing more metallic ruthenium and less oxides. The Ru/C and Ru7Pd3/C, prior and after the treatment, were accommodated inside a gas filter, and mass spectrometry investigations indicated that the thermal treatment only increased the methanation performance for the Ru/C catalyst. When used in anodic gas diffusion layer, this improvement was even more pronounced, and resulted in stationary methane production even at 85 °C. The most efficient material for CO methanation was Ru/C thermally treated, that promoted the CO methanation in a preferable way even when CO2 was present with percentages as high as 25%. The increase of the electrochemical performance of the fuel cell with this catalyst in the diffusion layer was better when at 105 °C.

No description available.

Observé quotidiennement par des instruments à bord de satellites depuis les années 2000, le monoxyde de carbone (CO) est utilisé comme un traceur du transport de la pollution du fait de sa longue durée de vie (1 à 2 mois) dans la troposphère. Ce gaz est émis principalement par les activités anthropiques (transport, chauffage, industrie) et par les feux (naturels ou provoqués pour le brûlage de la biomasse). Le CO joue un rôle central dans la chimie troposphérique car il est détruit par le radical OH, et régule dès lors la capacité oxydante de l'atmosphère. La première partie de mon travail de thèse a consisté à valider les mesures de CO obtenues par l'instrument en occultation solaire ACE-FTS, en utilisant des observations indépendantes d'instruments sol, avion et satellite. Le deuxième volet de mon travail repose sur les données obtenues par la mission IASI, lancée en 2006 à bord du satellite MetOp-A. Nous disposons de 6 ans de données CO IASI qui sont utilisées afin d'étudier les épisodes de feux, de suivre les panaches de pollution lors de campagnes de mesures, d'établir des tendances, d'élaborer des prévisions de pollution (projet MACC), ou encore d'améliorer les inventaires d'émission. Mes travaux de thèse ont surtout concerné l'étude des variabilités temporelles et spatiales, et j'ai contribué à la validation des restitutions qui sont distribuées à une large communauté d'utilisateurs scientifiques. Enfin, le dernier volet de mon travail a consisté à quantifier et expliquer les différences entre les produits CO de MOPITT et de IASI, qui se place comme son successeur. Le poids du choix des hypothèses a priori inhérent aux algorithmes d'inversion est étudié : un nouveau produit MOPITT utilisant le profil et la matrice de variance-covariance a priori de IASI a été élaboré. Alors que les colonnes totales de ce nouveau produit se comparent bien au produit initial, l’influence du profil mais surtout de la matrice de variance-covariance a priori (qui autorise plus ou moins de variabilité lors de l’inversion) est démontrée lors de l’étude des profils. / Carbon monoxide (CO) is measured from space since the year 2000 by several instruments. CO plays an important role in atmospheric chemistry and climate as it is the largest sink of the hydroxyl radical (OH), and thus impacts the oxidizing power of the atmosphere and the concentrations of greenhouse gases (such as methane and ozone). CO is mainly formed by the incomplete combustion of fossil, bio-fuels and biomass burning. Due to its long lifetime (1 to 2 months) it is therefore used as a pollution tracer in the troposphere.The first part of this PhD work consists of validating CO measurements from the limb- viewing ACE-FTS instrument using a set of independent data measured by instruments onboard aircraft, satellites and at ground-based stations.The second part of my work consists of studying the temporal and spatial variability of CO and focuses on studying 6 years of CO data measured by IASI (Infrared Atmospheric Sounding Interferometer), launched in 2006 onboard the MetOp-A satellite. I contributed to the validation of the retrieved data, which are now widely distributed to the scientific community, with different applications. For example the study of fire events, the follow-up of pollution plumes during measurements campaigns, building inter-annual trends, generating pollution forecasts (MACC project), and improving emission inventories.The last part of my PhD work consists of quantifying and explaining the differences between MOPITT (Measurements Of Pollution In The Troposphere) and IASI CO products. Due to the fact that IASI will likely outlive MOPITT, it is essential to evaluate the CO retrievals from these instruments against each other. I studied the impact of the a priori assumptions choice which is a major component of the retrieval algorithms. A new MOPITT product using IASI a priori profile and covariance matrix is built. Total CO columns of this new product are globally in good agreement with the initial MOPITT product. Local differences are investigated and shown to be due to the influence of the a priori profile and mainly its a priori covariance matrix which can be seen when studying the shape of the retrieved profiles.

Indoor air quality is a growing concern in the world. People spend a considerable amount of time in indoor environments such as homes, workplaces, shopping malls, stores, and so on. Indoor sources like incense and candle burning, cooking contribute a significant amount of indoor air pollutants such as particulate matter, carbon monoxide (CO), volatile organic compounds. Exposure to these kinds of pollutants can result in adverse health effects. The purpose of this research is to determine the particulate matter and carbon monoxide emission factors (EFs) from incense stick burning. A test chamber with a rectangular exhaust duct, a fan to exhaust air with pollutants in it, and pollutant sensors were used to achieve the project goals. Several experiments were performed with different cases/scenarios to accurately estimate the EFs and several test runs were conducted for each case to test the repeatability of the results. The CO, PM2.5 (mass), PM2.5 (number), PM10 (mass), PM10 (number) EFs developed in this research are between 110-120 mg/g of incense, 2.5-3 mg/g of incense, 800-1100 #particles/µg of incense, 32-33 mg/g of incense, 1200-1400 #particles/µg of incense respectively.

Carbon monoxide (CO) is an endogenous signaling molecule and has therapeutic values. However, the application of CO in the development of therapeutic options is hampered by the lack of pharmaceutically acceptable delivery methods. Inhalation of CO is not an ideal option for wide-spread clinical applications. Existing CO releasing molecules (CORMs) are mostly metal complexes, which have toxicity concerns to overcome. Some metal free CORMs have been developed. However, they all require light as a trigger to release CO, which limits their applications in vivo. Herein, we describe a metal-free CO prodrug approach using an intramolecular inverse electron-demanded Diels-Alder reaction. Such prodrugs can release CO spontaneously under physiological conditions with tunable release rates with the concomitant formation of a fluorescent reporter after CO releases. This intramolecular “click and release” strategy represents a milestone in the development of CO based therapeutics.

In this research project, adsorption is considered for the separation of CO2 from CO for applications such as industrial syngas production and in particular to improve the conversion of the Reverse Water Gas Shift (RWGS) process. The use of adsorption technology for these applications requires an adsorbent that can effectively separate out CO2 from a gas mixture containing CO2, CO, and H2. However, adsorption of H2 is insignificant when compared to both CO2 and CO, with only CO2 and CO being the adsorbed species. The adsorption of CO2 and CO was investigated in this work for four major types of industrial adsorbents which include: activated aluminas, activated carbons, silica gels, and zeolites. Zeolites, with their ability to be fine tuned many parameters which may affect adsorption, were investigated in terms of the effect of the cations present, SiO2/Al2O3 ratios, and structure to determine how to optimize adsorption of CO2 while decreasing adsorption of CO. This will help to determine a promising adsorbent for this separation with focus on maximizing the selective adsorption of CO2 over CO. To investigate this separation three scientific experimental methods were used; gravimetric adsorption isotherm analysis, volumetric adsorption isotherm analysis, and packed bed adsorption desorption breakthrough analysis. Gravimetric and volumetric methods allow for testing the adsorbent with the individual species of CO2 and CO. This investigation will let us determine the pure component adsorption capacity, heats of adsorption, regenerability, and basic selectivity. Packed bed adsorption breakthrough experimentation was then carried out on promising adsorbents for the CO2 separation from a mixture of CO2, CO, and H2. These experiments used a gas mixture that would be comparable to that produced from the RWGS reaction to determine the multicomponent gas mixture behaviour for adsorption. Temperature swing adsorption (TSA) with a purge gas stream of H2 was then used to regenerate the adsorbent.

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第22550号 / 人博第953号 / 新制||人||226(附属図書館) / 2019||人博||953(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 吉田 寿雄, 教授 内本 喜晴, 教授 田部 勢津久 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM