Techn. Universiẗat, Diss., 2007--Darmstadt.

Thesis (M.S.)--Ohio University, March, 2006. / Title from PDF t.p. Includes bibliographical references (p. 113-116)

Techn. Universiẗat, Diss., 2000--Berlin.

Universiẗat, Diss., 2004--Stuttgart.

Techn. Hochsch., Diss., 2005--Aachen.

This thesis concerns the development of novel catalytic approaches for the construction of stereocentres bearing a nitrogen atom. In 2011, the Dixon group reported a Ag(I)/cinchona-derived amino phosphine catalytic system for the activation of isocyanoacetates in asymmetric aldol and Mannich reactions. During this thesis work it was sought to extend the scope of this catalytic system to Mannich additions of other isocyanide pronucleophiles, then the focus was broadened to include Reformatsky and α-alkylation reactions of ketimine substrates. Chapter 1 gives an overview of the state of the art with particular emphasis on catalytic enantioselective additions to ketimines and the use of activated isocyanides as pronucleophiles. Chapter 2 describes the application of the Ag-catalysed enantio- and diastereoselective aldol reaction of isocyanoacetates to the concise asymmetric synthesis of the antibiotic chloramphenicol, which possesses a chiral stereodefined α-amino β-hydroxy motif. Chapter 3 details our efforts to expand the scope of the Ag(I)/amino phosphine catalytic system to the activation of more challenging isocyanides lacking an electron-withdrawing group in the α-position by investigating aldol and Mannich reactions of benzyl isocyanide. Chapter 4 describes how the scope of the Ag(I)/amino phosphine catalytic system was successfully extended to another pronucleophile, the versatile p-toluenesulfonylmethyl isocyanide (TosMIC). The first catalytic enantio- and diastereoselective addition of TosMIC to N-diphenylphosphinoyl (N-DPP) ketimines was developed, affording 2-imidazolines possessing two contiguous stereocentres with high yields and excellent levels of stereocontrol. Chapter 5 describes the development of a Ni(II)-catalysed Reformatsky reaction of N-DPP ketimines with ethyl bromoacetate and diethylzinc, providing racemic amines bearing a quaternary stereocentre in the α-position in good yields. Chapter 6 reports the serendipitous discovery of the α-alkylation of N-DPP ketimines with ethyl bromoacetate using visible light photoredox catalysis. The transformation, catalysed by ruthenium(II) and nickel(II) complexes under mild conditions, was optimised, its scope assessed and the mechanism investigated.

Innehållet i studien handlar om att kategorisera olika typer av fel som elever i åk 2 gör i räknesättet addition. Data utgörs av matematiktester från en tidigare gjord studie där elevgrupper under tre veckor undervisades i antingen talsortsvis beräkningsprocedur eller uppställning. Jag har kategoriserat sex feltyper: 1. talfakta, 2. platsvärde, 3. skrivfel/läsfel, 4.procedurfel, 5. teckenfel och 6. övriga fel. Jag undersöker om det finns något samband mellan feltyper, andel felsvar och undervisad räknemetod. Det finns viss skillnad mellan talsort och uppställning i omfattning av några kategorier av felsvar. Jag diskuterar svårigheter och missuppfattningar som kan antas ligga bakom många fel och som därmed särskilt bör uppmärksammas i undervisningssituationer. Ur ett specialpedagogiskt perspektiv tydliggörs hur utvecklingen ser ut för elever med låga prestationer, om det finns faktorer av särskild betydelse just för den gruppen. Jag tydliggör också hur det ser ut för elever med höga prestationer. Nästan all undervisning har lett till att eleverna löser fler uppgifter totalt sett. Det finns skillnader mellan talsort och uppställning i resultat och i andel felsvar. Undervisad räknemetod verkar vara den faktor som hade störst inverkan på eleverna med låga resultat på förtestet. De som undervisades i talsortsmetoden blev mer osäkra i sina beräkningar medan de som undervisats i uppställning blev säkrare i sina beräkningar. För gruppen med låga prestationer gav uppställning en mer positiv utveckling i denna studie.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第13828号 / 工博第2932号 / 新制||工||1433(附属図書館) / 26044 / UT51-2008-C744 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 檜山 爲次郎, 教授 大嶌 幸一郎, 教授 松原 誠二郎 / 学位規則第4条第1項該当

In this thesis Direct Numerical Simulation (DNS) is used to investigate the development of turbulent premixed flame kernels during the early stages of growth typical of the period following spark ignition. Two distinct aspects of this phase are considered: the interaction of the expanding kernel with a field of decaying turbulence, and the chemical and thermo-diffusive response of the flame for different fresh-gas compositions. In the first part of the study, three-dimensional, repeated simulations with single-step chemistry are used to generate ensemble statistics of global flame growth. The surface-conditioned mean fluid-velocity magnitude is found to vary significantly across different isosurfaces of the reaction progress variable, and this is shown to lead to a bias in the distribution of the Surface Density Function (SDF) around the developing flame. Two-dimensional simulations in an extended domain indicate that this effect translates into a similar directional bias in the Flame Surface Density (FSD) at later stages in the kernel development. Properties of the fresh gas turbulence decay are assessed from an independent, non-reacting simulation database. In the second part of this study, two-dimensional simulations with a detailed 68-step reaction mechanism are used to investigate the thermo-diffusive response of pure methane-air, and hydrogen-enriched methane-air flames. The changes in local and global behaviour due to the different laminar flame characteristics, and the response of the flames to strain and curvature are examined at different equivalence ratios and turbulence intensities. Mechanisms leading to flame quenching are discussed and the effect of mean flame curvature is assessed through comparison with an equivalent planar flame. The effects of hydrogen addition are found to be particularly pronounced in flame kernels due to the higher positive stretch rates and reduced thermo-diffusive stability of hydrogen-enriched flames.

Orientador: Jorge Luís Akasaki / Banca: Haroldo de Mayo Bernardes / Banca: Malik Cheriaf / Resumo: O setor sucro-alcooleiro vem se expandindo nos últimos tempos, alavancado principalmente pelo advento da bioenergia. No Brasil, a produção de cana-de-açúcar vem avançando em áreas destinadas à pecuária extensiva e a outras culturas importantes como a soja, o milho e a laranja e concerne à geração de energia elétrica pela queima do bagaço (cogeração) e ao uso de etanol como combustível de veículos automotores. Contudo, a produção de açúcar, álcool e energia a partir da cana-de-açúcar pode causar problemas ambientais em decorrência da geração de resíduos como a cinza do bagaço de cana-de-açúcar. Diante do panorama mundial de crescimento do setor sucro-alcooleiro aliado ao desenvolvimento sustentável, é de grande importância a realização de estudos que visem o aproveitamento destes resíduos. Deste modo, este trabalho mostra a viabilidade técnica da utilização da cinza resultante do processo de queima do bagaço para a geração de energia como adição mineral, em argamassas. Foram realizados ensaios de caracterização química, difração de raios-X, microscopia eletrônica de varredura e atividade pozolânica da cinza do bagaço de cana-deaçúcar. Além disto, um estudo da moagem do material foi realizado, juntamente com a composição de argamassas contendo a cinza em diversos teores de substituição ao agregado miúdo. Através da resistência à compressão e à tração por compressão diametral e módulo de elasticidade, foram analisadas suas propriedades mecânicas. Também foram verificadas algumas propriedades relacionadas com a durabilidade do material, como a retração por secagem, absorção por capilaridade e reatividade acelerada pelo método acelerado de expansão em barras de argamassa / Abstract: The sugar-alcohol sector has expanding in the last years, mainly due to advent of the renewable energy sources and bioenergy. In Brazil, the sugarcane production has advancing towards areas of cattle creation and agriculture, such as soya bean, corn and orange and concerning to electrical energy production through the burning bagasse and alcohol used like vehicle fuel. However, sugar, alcohol and energy production from sugarcane could cause other environmental problems in result to the wastes production such as sugarcane bagasse ash. In the presence of worldwide growth of sugar and alcohol industry and the sustainable development, it is very important the achievement of studies that reuse these wastes. Thus, this work shows technical viability on using sugar-cane bagasse ash (SCBA) obtained from sugar-cane bagasse burnt, as mineral addition, in mortars. It was made some tests on the SCBA, such as the chemical characterization, X-ray diffraction, pozzolanic activity, and also, images obtained by scanning electron microscope. Moreover, grinding of SCBA was carried out, and mortars were prepared with some different amounts of SBCA as replacement of fine aggregate by mass. Through the compressive strength, splitting tensile strength and modulus of elasticity its mechanical properties were verified, and also some properties related to material durability as drying shrinkage, water absorption by capillarity, potential alkali reactivity of aggregates by mortar-bar method / Mestre