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京都大学 / 新制・課程博士 / 博士(地域研究) / 甲第24117号 / 地博第306号 / 新制||地||119(附属図書館) / 京都大学大学院アジア・アフリカ地域研究研究科東南アジア地域研究専攻 / (主査)教授 古澤 拓郎, 准教授 坂本 龍太, 准教授 小坂 康之 / 学位規則第4条第1項該当 / Doctor of Area Studies / Kyoto University / DGAM

Feedback-based learning is a process in which decisions are made based on the previous feedback. This learning process is influenced by acute stress. However, different laboratory stressors elicit different physiological response patterns, which may influence feedback processing differently. Moreover, individual differences in stress reactivity may be associated with reward sensitivity. Therefore, the present study investigated the effects of psychosocial and physical stress on feedback-based learning. The relationship between stress reactivity and reward sensitivity was also examined. Ninety-two college-aged subjects were assigned into the mental arithmetic (MA) task or the cold pressor task (CPT) group. All subjects performed a feedback-based learning task prior to and after the stressor. Cardiovascular reactions, stress experiences, and learning outcomes were recorded during tasks. Trait differences in behavioral inhibition and activation (BIS/BAS) were also measured. Results indicated different patterns of cardiovascular reactions to the MA and CPT. Learning outcomes were differentially influenced by the MA and CPT. Moreover, subjective stress scores were negatively correlated with the learning rate in the pre-stress learning task. Additionally, BAS Drive subscale score was related to the processing of positive feedback. The results suggested that physical and psychosocial stress influence learning through distinct neural mechanisms and psychological processes. Motivational processes underlie the relationship between stress reactivity and reward sensitivity. This study extended research on stress and learning, and the findings have applied implications in various areas. / Ph. D.

5 Title: Methylene-bis(phosphonate) Derivatives for Modification of Biomolecules Author: Tomáš David Department: Department of Inorganic Chemistry, Faculty of Science Supervisor: RNDr. Vojtěch Kubíček, Ph.D. Supervisor's e-mail address: vvvojta@seznam.cz Abstract The aim of this work was to prepare derivatives of methylen-bis(phosphonic) acid. Thirty compounds (from which 29 are new) were prepared with moderate or good yields. All compounds were fully characterized by NMR and MS. Four new crystal structures were obtained by RTG monocrystal analysis. Derivative containing 4-nitrobenzyl group in the side chain was used for study of bis(phosphonates) adsorption parametres to hydroxyapatite (with quantification by UV-Vis spectroscopy). Several derivatives containing characteristic functi- onal groups (-NH2, -COOH, -NCS) were prepared. These compound are suitable for further derivatization, mainly for conjugation with more complex structures through amide bond or thiourea bridge. Conjugates of building blocks with fluorescent probe (fluorescein and dansyl) were prepared for potencial optical imaging. Further modification of one of the dansyl derivative afforded trifunctional molecule - contating bis(phosphonate) as a vector for a bone tissue, a fluorescent probe for a possible fluorescent imaging and a free...

L’objectif de cette thèse a été de développer des matériaux catalytiques contenant des complexes Ru(NHC), à partir de matériaux hybrides organique-inorganique contenant des fonctions imidazolium parfaitement distribuées dans une matrice de silice. La passivation de surface de ces matériaux, suivie de la formation du NHC et d’une réaction avec [RuCl2(p-cymene)]2 a permis d’obtenir des espèces de surface bien définies de formule générale RuCl2(NHC)(L), où L est un ligand para-cymene (p-cymene) ou un ligand THF, selon les conditions de réaction, et peut être remplacé par PMe3. Ces catalyseurs ont ensuite été testés dans la réaction d’hydrogénation du CO2 en présence d’amines pour donner des formamides. Les systèmes mono-NHC se sont avérés très actifs en présence de ligands PMe3, mais la lixiviation du métal a été observée, mettant en évidence la faible stabilité de la liaison Ru-NHC dans les conditions de réaction. Cependant, des systèmes dinucléaires Ru(bis-NHC) ont été développés, et ils ont montré une meilleure activité et stabilité que les systèmes mono-NHC dans l’hydrogénation du CO2, en présence de PMe3 comme ligand. Cela a permis d’utiliser des températures de réaction bien plus élevées (200°C) et d’obtenir des catalyseurs hétérogènes avec des performances s’approchant du meilleur catalyseur homogène, Cl2Ru(dppe)2. / The goal of this PhD was to elaborate supported Ru-NHC catalytic materials based on hybrid organic-inorganic materials having imidazolium units perfectly distributed within a silica matrix. Passivation of these imidazolium materials followed by formation of NHC-carbene and reaction with [RuCl2(p-cymene)]2 provided these well-defined surface sites of general structures RuCl2(NHC)(L), where L was para-cymene (p-cymene) or THF depending on the reaction conditions, which could be further replaced by PMe3. These systems were then tested in the hydrogenation of CO2 in presence of amine to give formamides. The mono-NHC systems were highly active only in the presence of PMe3 ligands, but suffered from Ru leaching, evidencing the low stability of the NHC-Ru bond under the reaction conditions. On the other hand, dinuclear bis-NHC Ru systems were also developed, and they displayed much improved activity and stability in the hydrogenation of CO2 in the presence of PMe3 compared to the mono-NHC systems. This allowed the use of much higher reaction temperatures (200 °C) and provided heterogeneous catalysts with performances close to those obtained with the best homogeneous catalysts, Cl2Ru(dppe)2.

O objetivo deste estudo foi avaliar a influência de dois aditivos, propionaldehyde (propanal aldeído) e 2,3-butanedione (diquetona diacetil), nas propriedades de comonômeros, copolímeros e resinas compostas à base de Bis-GMA, quando diluído com TEGDMA, Bis-GMA propoxilado (CH3Bis-GMA) e Bis-GMA propoxilado fluorinado (CF3Bis-GMA). Comonômeros, copolímeros e compósitos experimentais foram preparados combinando Bis-GMA com TEGDMA, CH3Bis-GMA, CF3Bis-GMA e, aldeído (24 e/ou 32 mol%) e diquetona (24 e/ou 32 mol%). No caso dos compósitos, partículas híbridas silanizadas (bário aluminosilicato; 60 peso%) foram adicionadas aos comonômeros. Para a fotopolimerização, adicionou-se canforoquinona (0,2 peso%) e N,N-dimetil-p-toluidina (0,2 peso%). Os comonômeros e copolímeros experimentais tiveram as seguintes propriedades avaliadas: viscosidade, contração de polimerização, grau de conversão, ângulo de contato (em esmalte, dentina e vidro), temperatura de transição vítrea (DSC e equação de Fox), microdureza, alteração de rugosidade superficial e desgaste por abrasão. Os compósitos experimentais, tiveram avaliadas as seguintes propriedades: resistência flexural, módulo de elasticidade, tração diametral, módulo de resiliência, microdureza, alteração de rugosidade superficial e desgaste por abrasão. Os sistemas Bis-GMA/TEGDMA e Bis-GMA/CH3Bis-GMA tiveram suas propriedades significantemente alteradas pela incorporação de aditivos (propanal ou diquetona). Os aditivos (propanal/diquetona) não influenciaram de forma significante as propriedades do sistema Bis-GMA/CF3Bis-GMA. O efeito dos aditivos nas propriedades dos materiais analisados relaciona-se à sua abilidade em aumentar o grau de conversão de alguns sistemas resinosos / The purpose of this study was to evaluate the effect of two additives, propionaldehyde (aldehyde) and 2,3-butanedione (diketone), on the properties of Bis-GMA based comonomer, copolymer and composites when diluted with TEGDMA, propoxylated Bis- GMA (CH3Bis-GMA) and propoxylated fluorinated Bis-GMA (CF3Bis-GMA). Experimental comonomer/copolymer/composites were prepared combining Bis-GMA and TEGDMA, CH3Bis-GMA, CF3Bis-GMA, with aldehyde (24 and/or 32 mol%) and diketone (24 and/or 32 mol%). For composites, hybrid treated filler (barium aluminosilicate glass; 60 wt%) was added to monomer mixtures. Photopolymerization was effected by using camphorquinone (0.2 wt%) and N,N-dimethyl-p-toluidine (0.2 wt%). Experimental comonomer/copolymers viscosity, polymerization shrinkage, degree of conversion, contact angle (enamel, dentin and glass surfaces), glass transition temperature (DSC and Fox equation), microhardness, surface roughness changes and wear were evaluated. Experimental composites, flexural strength, modulus of elasticity, diametral tensile strength, modulus of resilience, microhardness, surface roughness changes and wear were also assessed. Bis-GMA/TEGDMA and Bis- GMA/CH3Bis-GMA systems had properties significantly influenced by incorporation of additives (either propanal or diketone). Additives (propanal/diketone) did not significantly influence on Bis-GMA/CF3Bis-GMA system properties. The effect of additives on the evaluated material properties is mainly attributed to their ability in improving some resin systems degree of conversion