Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15389号 / 工博第3268号 / 新制||工||1492(附属図書館) / 27867 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 井上 正志, 教授 垣内 隆 / 学位規則第4条第1項該当

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18300号 / 工博第3892号 / 新制||工||1597(附属図書館) / 31158 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 村上 正浩, 教授 吉田 潤一, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(薬科学) / 甲第18928号 / 薬科博第42号 / 新制||薬||5(附属図書館) / 31879 / 京都大学大学院薬学研究科医薬創成情報科学専攻 / (主査)教授 大野 浩章, 教授 高須 清誠, 教授 竹本 佳司 / 学位規則第4条第1項該当 / Doctor of Pharmaceutical Sciences / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21781号 / 工博第4598号 / 新制||工||1716(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 辻 康之, 教授 大江 浩一, 教授 近藤 輝幸 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

>Magister Scientiae - MSc / Solar cells offer SA an additional energy source. While Si cells are abundantly available they are not at an optimal efficiency and the cost is still high. One technology that can enhance their performance is SiNW. However, material properties such as the diameter, porosity and length determine their effectiveness during application to solar cell technology. One method of growing SiNW uses Sn catalysts on a Si substrate. As the properties of the Sn nanoparticle govern the properties of the SiNW, this thesis investigates their formation and properties by depositing a Sn layer on a Si wafer and then subjecting it to different temperatures, during process the layer forms into nanoparticles. At each temperature the morphology, composition and crystallinity will be determined using XPS, SEM, TEM and EDS. Thus, in Chapter 1 there is an overview, Chapter 2 deals with techniques used in this study, Chapter 3 will give the quantitative and qualitative results on the XPS analysis and Chapter 4 will illustrate the structural behaviour of the annealed Sn film samples.

Having access to mild and operationally simple techniques for attaining carbohydrate targets will be necessary to facilitate advancement in biological, medicinal, and pharmacological research. Even with the abundance of elegant reports for generating glycosidic linkages, the stereoselective construction of alpha- and beta-oligosaccharides and glycoconjugates is by no means trivial. In an era when expanded awareness of the impact we are having on the environment drives the state-of-the-art, synthetic chemists are tasked with developing cleaner and more efficient reactions for achieving their transformations. This movement imparts the value that prevention of waste is always superior to its treatment or cleanup. Chapter 1 of this thesis will highlight recent advancement, in this regard, by examining strategies that employ transition metal catalysis in the synthesis of oligosaccharides and glycoconjugates. These methods are mild and effective for constructing glycosidic bonds with reduced levels of waste through utilization of sub-stoichiometric amounts of transition metals to promote the glycosylation. The development of a general and practical method for the stereoselective synthesis of beta-O-aryl-glycosides that exploits the nature of a cationic palladium(II) catalyst, instead of a C(2)-ester directing group, to control the beta-selectivity is described in chapter 2. The beta-glycosylation protocol is highly diastereoselective and requires 2-3 mol % of Pd(CH3CN)4(BF4)2 to activate glycosyl trichloroacetimidate donors at room temperature. The method has been applied to D-glucose, D-galactose, and D-xylose donors with a non-directing group incorporated at the C(2)-position to provide the O-aryl glycosides with good to excellent beta-selectivity. In addition, its application is widespread to electron-donating, electron-withdrawing, and hindered phenols. The glycosylation is likely to proceed through a seven-member ring intermediate, wherein the palladium catalyst coordinates both the C(1)-trichloroacetimidate nitrogen and C(2)-ether oxygen, blocking the alpha-face. As a result, the phenol nucleophile preferentially approaches from the top face of the activated donor, leading to the formation of the beta-O-aryl glycoside. The area of sugar urea derivatives has received considerable attention in recent years because of the unique structural properties and activities that these compounds display. The urea-linkage at the anomeric center is a robust alternative to the naturally occurring O- and N-glycosidic linkages of oligosaccharides and glycoconjugates, and the natural products that have been identified to contain these structures show remarkable biological activity. While methods for installing the beta-urea-linkage at the anomeric center have been around for decades, the first synthesis of alpha-urea glycosides has been much more recent. In either case, the selective synthesis of glycosyl ureas can be quite challenging, and a mixture of alph- and beta-isomers will often result. Chapter 3 provides a comprehensive review of the synthetic approaches to alpha- and beta-urea glycosides and examines the structure and activity of the natural products, and their analogues, that have been identified to contain them. There are only a handful of reports for the construction of beta-urea glycosides, and even fewer that are able to attain the alpha-urea structures. Chapter 4 will cover two of these methods, where a transition metal catalyst is employed to facilitate the alpha-selective transformation. The 1st-generation process, covered in section 4.1, involves the cationic palladium(II)-catalyzed rearrangement of glycal trichloroacetimidate to alpha-glycal trichloroacetamide in its key step. The transformation is carried out with only 0.5 mol% Pd(CH3CN)4(BF4)2 catalyst and is both highly alpha-selective and tolerant to a diverse array of protecting groups. The glycal product of the rearrangement is functionalized to pyranoside, protected, and then converted to glycosyl urea in 3-steps. A diverse array of primary and hindered secondary nitrogen nucleophiles have been coupled with the alpha-acetamide products, generating alpha-urea glycosides with retention of stereochemical integrity at the anomeric center. This is the first synthesis of alpha-glycosyl urea to rely on the nature of the catalyst/ligand complex, rather than substrate, to control selectivity. This method, however, suffers from limitations in scope and a dependence on toxic osmium tetroxide to functionalize the glycal. In section 4.2, the development and mechanistic investigation of a 2nd-generation process, able to overcome the limitations of the glycal methodology to provide an efficient and highly stereoselective access to alpha-urea glycosides, is decribed. This two-step procedure begins with a highly selective nickel-catalyzed conversion of alpha-glycosyl trichloroacetimidate to alpha-trichloroacetamide. The alpha-selectivity in the reaction is controlled with a cationic nickel(II) catalyst, Ni(dppe)(OTf)2. Mechanistic studies have identified a coordination of the nickel catalyst with equatorial C2-ether group of the glycosyl trichloroacetimidate to be paramount for achieving an á-selective transformation. A cross-over experiment has indicated that the reaction does not proceed in an exclusively-intramolecular fashion. The alpha-trichloroacetamide products are directly converted into alpha-urea glycosides by reacting them with a variety of nucleophilic amines in presence of cesium carbonate. Only alpha-urea products are observed, as the reaction retains stereochemical integrity at the anomeric center during the urea-forming step.

Abstract This thesis describes efforts made on the development of an existing catalytic incinerator. The development work, called process characterization, consists of four general parts. These are the development of measurement methodology, the studying of construction materials, the selection of suitable catalysts and the testing of the effects of process operation conditions. The two application areas for catalytic incineration considered in this thesis are solvent emission abatement (VOC, volatile organic compounds) and chip bin emission abatement (SVOC, sulphur-containing volatile organic compounds). As a baseline, the process characterization is started with the development of measurement methodology. In general, the methodology will decrease costs and simplify the carrying out of the actual measurements and thereby make the measurement time more effective. In the methodology it is proposed that continuous total concentration measurement should be used in connection with qualitative sampling to obtain reliable measurement data. The selection of suitable construction materials for the application is very important. As shown in this thesis, the end conversions in solvent emission abatement may even be improved through the selection of the proper construction materials. In chip bin emission abatement, the problem arises from corrosive oxidation products that set limits on the construction materials used as well as on oxidation conditions. Catalyst selection is based on the following catalytic properties: activity, selectivity and durability. These catalytic properties are studied either at the laboratory or on an industrial scale. The catalytic materials tested are Pt, Pd, Pt-Pd, Cu-Mn oxides, MnO2-MgO, CuxMg(1-x)Cr2O4 and CuxCr2O4. The most important selection criteria in solvent emission abatement are proposed to be activity and selectivity. In the case of chip bin-SVOC-abatement, these are selectivity and durability. Based on these criteria, catalysts containing Cu-Mn oxides and Pt were demonstrated to be the best catalysts in VOC oxidation, and catalyst containing MnO2-MgO was shown to be best catalyst in SVOC oxidation. A study on the effect of process operation parameters (temperature, concentration and gas hourly space velocity (GHSV)) and moisture was carried out with the aid of factorial design. In VOC (n-butyl acetate) oxidation, the most influential process parameter was GHSV, which decreased the end conversion when it was increased. In SVOC (DMDS) oxidation, the effect of temperature was most significant. The end conversions increased as the temperature increased. Moisture slightly decreased the formation of by-products in n-butyl acetate oxidation. In DMDS oxidation, moisture slightly increased the end conversions at a lower temperature level (300°C). At the end of the thesis, these process parameters are also discussed from the standpoint of the catalysts' activity, selectivity and durability. Finally, proposals for process improvements are suggested.

A minor enantiomer recycling one-pot process usingω-functionalized prochiral aldehydes as starting materials and two reinforcing catalysts has been reported. The desired aldehyde for these process studies was 5-bromo-1-pentanal. In a two-phase solvent system, enzyme-catalyzed hydrolysis of the minor enantiomer regenerates continuously the prochiral starting material and Lewis acid catalysed addition of acetyl cyanide provides the O-acetylated cyanohydrins. The minor enantiomer recycling process has been studied and improved for 5-bromo-1-pentanal to receive high enantiomeric excess and yield of the expected O-acetylated cyanohydrin.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18997号 / 工博第4039号 / 新制||工||1622(附属図書館) / 31948 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 辻 康之, 教授 大江 浩一, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19239号 / 工博第4074号 / 新制||工||1628(附属図書館) / 32238 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 村上 正浩, 教授 吉田 潤一, 教授 松田 建児 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM