Please read the abstract in the section 00front of this document / Dissertation (MSC (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

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京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22246号 / 理博第4560号 / 新制||理||1655(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 永江 知文, 教授 田中 貴浩, 教授 萩野 浩一 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Abstract In this thesis, different spectroscopic methods are used for studying metals. Electron spectroscopy is applied for the study of binding energy shifts between atomic vapor and solid metals. Photoionization and Auger decay of high temperature aluminum vapors are investigated. Ionization of atomic chromium metal vapor by light absorption is studied with synchrotron radiation and time-of-flight ion mass spectroscopy. Optical spectroscopy is used for studying light emission from electric arc furnace plasma in experimental apparatuses developed during this work. Experimental techniques and sample preparation methods are presented. / Original papers The original publications are not included in the electronic version of the dissertation. Huttula, M., Jänkälä, K., Mäkinen, A., Aksela, H., & Aksela, S. (2008). Core shell electron spectroscopy on high temperature vapors: 2s photoionization and Auger decay of atomic aluminium. New Journal of Physics, 10(1), 13009. https://doi.org/10.1088/1367-2630/10/1/013009 Huttula, M., Partanen, L., Mäkinen, A., Kantia, T., Aksela, H., & Aksela, S. (2009). KLL Auger decay in free aluminum atoms. Physical Review A, 79(2). https://doi.org/10.1103/physreva.79.023412 Aksela, S., Kantia, T., Patanen, M., Mäkinen, A., Urpelainen, S., & Aksela, H. (2012). Accurate free atom–solid binding energy shifts for Au and Ag. Journal of Electron Spectroscopy and Related Phenomena, 185(8–9), 273–277. https://doi.org/10.1016/j.elspec.2012.05.007 Mäkinen, A., Patanen, M., Aksela, S., & Aksela, H. (2012). Atom-solid 3p level binding energy shift of transition metals Cr, Mn, Fe, Co, and Ni. Journal of Electron Spectroscopy and Related Phenomena, 185(12), 573–577. https://doi.org/10.1016/j.elspec.2012.12.006 Mäkinen, A., Niskanen, J., & Aksela, H. (2012). Relative photoionization cross section of Cr atoms in the valence region. Physical Review A, 85(5). https://doi.org/10.1103/physreva.85.053411 Mäkinen, A., Niskanen, J., Tikkala, H., & Aksela, H. (2013). Optical emission from a small scale model electric arc furnace in 250–600 nm region. Review of Scientific Instruments, 84(4), 43111. https://doi.org/10.1063/1.4802833

Lipids are important for the structural and physiological functions of neuronal cell membranes. Alterations in their lipid composition may result in membrane dysfunction and subsequent neuronal deficits that characterise various disorders. This study focused on profiling lipids of aged and LPS-treated rat brain and liver tissue with a view to explore the effect of atorvastatin in neuroinflammation, and examining lipid changes in different areas of rat brain of the Flinders Sensitive Line (FSL) rats, a genetic model of depression. Lipids and other analytes extracted from tissue samples were analysed with proton nuclear magnetic resonance spectroscopy (1H-NMR), gas chromatography (GC) and liquid chromatography-tandem mass spectroscopy (LC/ESI-MS/MS). Changes in the lipid profiles suggested that brain and liver responded differently to ageing and LPS-induced neuroinflammation. In the aged animals, n-3 PUFA were reduced in the brain but were increased in the liver. However, following treatment with LPS, these effects were not observed. Nevertheless, in both models, brain concentration of monounsaturated fatty acids was increased while the liver was able to maintain its monounsaturated fatty acid concentration. Atorvastatin reversed the reduction in n-3 PUFA in the aged brain without reducing brain and liver concentration of cholesterol. These findings further highlight alterations in lipid metabolism in agerelated neuroinflammation and show that the anti-inflammatory actions of atorvastatin may include a modulation of fatty acid metabolism. When studying the FSL model, there were differences in the lipid profile of different brain areas of FSL rats compared to Sprague-Dawley controls. In all brain areas, arachidonic acid was increased in the FSL rats. Docosahexaenoic acid and ether lipids were reduced, while cholesterol and sphingolipids were increased in the hypothalamus of the FSL rats. Furthermore, total diacylglycerophospholipids were reduced in the prefrontal cortex and hypothalamus of the FSL rats. These results show differences in the lipid metabolism of the FSL rat brain and may be suggestive of changes occurring in the brain tissue in depression.

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A busca por fontes alternativas de energia é uma tendência mundial e, neste contexto, as células a combustível alimentadas com hidrogênio obtido pela reforma de biocombustíveis constitui uma das alternativas mais promissoras. Entretanto, o desempenho das células a combustível de membrana de troca protônica (PEMFC) com ânodos baseados em Pt é drasticamente reduzido quando se utiliza hidrogênio contaminado por CO, o qual é produzido no processo de reforma. Neste trabalho, a eletrocatálise da tolerância ao CO e a estabilidade de Pt/C, PtRu/C, PtFe/C, PtMo/C e PtW/C como eletrocatlisadores anódicos de célula a combustível PEM foram investigadas através de curvas de polarização e medidas on line de espectrometria de massas (EMS), análises de voltametria cíclica, difração de raios X (DRX) e absorção de raios X (XAS). Para todos os eletrocatalisadores bimetálicos, os quais apresentaram alta tolerância ao CO, os resultado de EMS mostraram que a produção de CO2 inicia-se a menores sobrepotenciais em relação ao eletrodo de hidrogênio quando comparado a Pt/C, confirmando a ocorrência do conhecido mecanismo bifuncional. Por outro lado, os resultados de XANES indicam um aumento de vacância da banda 5d da Pt para todos os catalisadores bimetálicos, particularmente para PtFe/C, o que leva a um enfraquecimento da ligação Pt-CO e conseqüente aumento da tolerância ao CO (efeito eletrônico). Para PtMo/C e PtRu/C alimentado com H2/CO, a formação de CO2 é observada mesmo quando a célula opera em circuito aberto, confirmando alguma eliminação de CO por um processo químico, muito provavelmente uma reação de deslocamento gás-água. Uma deterioração do desempenho de célula a combustível foi observada em uma função do tempo de operação. As causas desta degradação durante a operação a longo prazo fazem parte de um processo complexo que envolve diversos mecanismos paralelos, tais como: perda ou redistribuição do eletrocatalisador, corrosão do suporte de carbono e degradação do eletrólito (Nafion®). / The search for alternative sources of energy is a global trend, and in this context, the fuel cell supplied with hydrogen obtained by biofuels reforming is one of the most promising alternative. However, the performance of proton exchange membrane fuel cells (PEMFC) with Pt-based anode is drastically lowered when using CO-contain hydrogen, as that produced by reform. In this work, the electrocatalysis of CO tolerance and the stability of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C electrocatalysts at a PEM fuel cell anode has been investigated using single cell polarization and on line electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO2 starts at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particularly for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H2/CO, the formation of CO2 is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. A decay of the fuel cell performance was observed as a function of the operation time. The causes of degradation during long-term operation were found to be a complex process that involves several parallel mechanisms, including: electrocatalyst loss or redistribution, carbon corrosion, and electrolyte (Nafion®) degradation.