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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Anionic-oxy cope rearrangement of vinylsulfides and enol ethers

Woodland, Christopher Andrew January 2003 (has links)
No description available.
2

Sequence-Controlled Copolymers from Tailored Pendant-Transformable Divinyl Monomers: Precise Control of Cyclopolymerization and Creation of Sequence-Oriented Properties / 側鎖変換性ジビニルモノマーからの配列制御共重合体の合成:環化重合の精密制御と配列特異的物性の創出

Xu, Xiaoyan 25 September 2023 (has links)
京都大学 / 新制・課程博士 / 博士(工学) / 甲第24905号 / 工博第5185号 / 新制||工||1990(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 大内 誠, 教授 田中 一生, 教授 大北 英生 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM
3

Estudo da adsorção de horseradish peroxidase (HRP) sobre superfícies planas e de sua atividade catalítica / Study on the adsorption of horseradish peroxidase (HRP) onto flat surfaces and its catalytic activity

Naves, Alliny Ferreira 10 July 2008 (has links)
Este trabalho está dividido em duas partes: (i) estudo da adsorção da enzima horseradish peroxidase (HRP) sobre substratos planos (lâminas de Si/SiO2, filmes ASP/Si/SiO2, filmes CABads/Si/SiO2, filmes CABspin/Si/SiO2 e filmes CMCABspin/Si/SiO2) seguida de testes da atividade enzimática da HRP imobilizada sobre estes substratos e (ii) obtenção de oligômeros divinílicos mediada pela HRP. Na primeira parte, a imobilização da HRP sobre substratos planos foi estudada através de elipsometria, microscopia de força atômica (AFM) e medidas de ângulo de contato. As isotermas de adsorção da HRP sobre Si/SiO2, APS/Si/SiO2 e CABads/Si/SiO2 apresentaram um aumento contínuo da quantidade de material adsorvido ΓHRP em função da concentração da solução de enzima até atingir um patamar de adsorção no qual verificou-se a formação de uma monocamada de HRP adsorvida. Nestes casos, o processo de adsorção da HRP pode ser descrito pelo modelo de adsorção aleatória (RSA). Para filmes HRP/CABspin/Si/SiO2 e HRP/CMCABspin/Si/SiO2 observou-se adsorção cooperativa de moléculas de HRP e formação de multicamadas. A adsorção da HRP sobre Si/SiO2, filmes APS, CABads e CMCABspin é um processo irreversível. Ao contrário, HRP adsorve reversivelmente sobre filmes CABspin, fato evidenciado pelo decréscimo de ~30% na espessura dos filmes de enzima. A atividade catalítica dos filmes de HRP imobilizados sobre substratos planos foi verificada na reação de oxidação do ABTS. Os testes de atividade catalítica mostraram que os substratos com a HRP adsorvida podem ser reutilizados 3 vezes sem dessorção ou perda da atividade catalítica da enzima, com exceção dos filmes HRP/CABspin/Si/SiO2 que se tornam inativos após a primeira catálise. A condição de máxima atividade catalítica de HRP imobilizada foi correlacionada com grau de cobertura de ~55%. O emprego do monômero etileno glicol dimetacrilato (EGDMA) em reações de polimerização catalisadas por filmes HRP/Si/SiO2 ou pela HRP livre em solução à temperatura ambiente revelou a formação de partículas cristalinas com geometria poligonal. Com objetivo de compreender a formação das estruturas cristalinas, a segunda parte do trabalho focou a formação de oligômeros de EGDMA e trietileno glicol dimetacrilato (TEGDMA) em meio aquoso catalisada pela HRP na presença H2O2 a temperatura ambiente. Os oligômeros de EGDMA e/ou TEGDMA foram caracterizados por gravimetria, cromatografia de permeação em gel, espectroscopia vibracional na região do infravermelho e espectroscopia 1H RMN. A auto-associação dos oligômeros originou partículas cristalinas com ângulos retos, como evidenciado pelas imagens de microscopia eletrônica de varredura. As medidas de calorimetria exploratória diferencial e difração de raio-x confIrmaram a cristalinidade das amostras. Os oligômeros de EGDMA, TEGDMA e EGDMA-co-TEGDMA sintetizados na presença do sistema HRP-H2O2 apresentaram grupos vinila pendentes, boa solubilidade em clorofórmio e ponto de fusão bem definido, evidenciando pouca reticulação ou ciclização e mostrando que as propriedades catalíticas da HRP propiciam um ambiente reacional apropriado para produzir materiais poliméricos com novas características. / This work is divided into two parts: (i) study on the adsorption of the enzyme horseradish peroxidase (HRP) onto flat substrates (silicon wafers, ASP/Si/SiO2 films, CABads/Si/SiO2 films, CABspin/Si/SiO2 films, and CMCABspin/Si/SiO2 films) followed by enzymatic catalytic tests of HRP immobilized onto these substrates, and (ii) formation of divinyl-based oligomers mediated by HRP. In the first part, the HRP immobilization onto flat substrates was investigated by means of ellipsometry, atomic force microscopy (AFM), and contact angle measurements. Adsorption isotherms of HRP onto silicon wafers, APS/Si/SiO2, and CABads/Si/SiO2 presented the continuous increase of HRP adsorbed amount ΓHRP as a function of enzyme solution concentration until an adsorption plateau, which evidenced monolayer formation. In these cases, the HRP adsorption process can be described by the random sequential adsorption model (RSA). For HRP/CABspin/Si/SiO2 and HRP/CMCABspin/Si/SiO2 cooperative adsorption of HRP molecules and multilayer formation were evidenced. The HRP adsorption onto silicon wafers, APS, CABads, and CMCABspin films is an irreversible process. Contrarily, HRP adsorbed reversibly onto CABspin films, since desorption of ~30% could be detected. The catalytic activity of HRP films immobilized onto flat substrates was verified by oxidation reaction of ABTS. Catalytic tests showed that substrates with adsorbed HRP can be reused three times without desorption or catalytic activity lost, except for HRP/CABspin/Si/SiO2 films, which became inactive after first use. The emulsion polymerization of ethylene glycol dimethacrylate (EGDMA) in mediated by HRP/Si/SiO2 films or by free HRP at room temperature revealed the formation of crystalline particles with polygonal geometry. In order to understand the formation of such crystalline structures, the second part of this thesis focused on EGDMA and/or triethylene glycol dimethacrylate (TEGDMA) oligomers formation in aqueous medium catalyzed by HRP in the presence of H2O2 at room temperature. EGDMA and/or TEGDMA oligomers were characterized by means of gravimetry, gel permeation chromatography, infrared vibrational spectroscopy and 1H NMR spectroscopy. Self-assembling of oligomers led to right-angled crystalline particles, as evidenced by scanning electron microscopy images. Differential scanning calorimetry and X-ray diffractometry measurements ratified the samples crystallinity. EGDMA, TEGDMA and EGDMA-co-TEGDMA oligomers synthesized in the presence of HRP-H2O2 system presented pendant vinyl groups along the chains, good solubility in chloroform, and well defined melting point. These features evidenced few crosslinking or cyclization and revealed that the catalytic properties of HRP provide an appropriate environrnent for production of materials with new characteristics.
4

Estudo da adsorção de horseradish peroxidase (HRP) sobre superfícies planas e de sua atividade catalítica / Study on the adsorption of horseradish peroxidase (HRP) onto flat surfaces and its catalytic activity

Alliny Ferreira Naves 10 July 2008 (has links)
Este trabalho está dividido em duas partes: (i) estudo da adsorção da enzima horseradish peroxidase (HRP) sobre substratos planos (lâminas de Si/SiO2, filmes ASP/Si/SiO2, filmes CABads/Si/SiO2, filmes CABspin/Si/SiO2 e filmes CMCABspin/Si/SiO2) seguida de testes da atividade enzimática da HRP imobilizada sobre estes substratos e (ii) obtenção de oligômeros divinílicos mediada pela HRP. Na primeira parte, a imobilização da HRP sobre substratos planos foi estudada através de elipsometria, microscopia de força atômica (AFM) e medidas de ângulo de contato. As isotermas de adsorção da HRP sobre Si/SiO2, APS/Si/SiO2 e CABads/Si/SiO2 apresentaram um aumento contínuo da quantidade de material adsorvido ΓHRP em função da concentração da solução de enzima até atingir um patamar de adsorção no qual verificou-se a formação de uma monocamada de HRP adsorvida. Nestes casos, o processo de adsorção da HRP pode ser descrito pelo modelo de adsorção aleatória (RSA). Para filmes HRP/CABspin/Si/SiO2 e HRP/CMCABspin/Si/SiO2 observou-se adsorção cooperativa de moléculas de HRP e formação de multicamadas. A adsorção da HRP sobre Si/SiO2, filmes APS, CABads e CMCABspin é um processo irreversível. Ao contrário, HRP adsorve reversivelmente sobre filmes CABspin, fato evidenciado pelo decréscimo de ~30% na espessura dos filmes de enzima. A atividade catalítica dos filmes de HRP imobilizados sobre substratos planos foi verificada na reação de oxidação do ABTS. Os testes de atividade catalítica mostraram que os substratos com a HRP adsorvida podem ser reutilizados 3 vezes sem dessorção ou perda da atividade catalítica da enzima, com exceção dos filmes HRP/CABspin/Si/SiO2 que se tornam inativos após a primeira catálise. A condição de máxima atividade catalítica de HRP imobilizada foi correlacionada com grau de cobertura de ~55%. O emprego do monômero etileno glicol dimetacrilato (EGDMA) em reações de polimerização catalisadas por filmes HRP/Si/SiO2 ou pela HRP livre em solução à temperatura ambiente revelou a formação de partículas cristalinas com geometria poligonal. Com objetivo de compreender a formação das estruturas cristalinas, a segunda parte do trabalho focou a formação de oligômeros de EGDMA e trietileno glicol dimetacrilato (TEGDMA) em meio aquoso catalisada pela HRP na presença H2O2 a temperatura ambiente. Os oligômeros de EGDMA e/ou TEGDMA foram caracterizados por gravimetria, cromatografia de permeação em gel, espectroscopia vibracional na região do infravermelho e espectroscopia 1H RMN. A auto-associação dos oligômeros originou partículas cristalinas com ângulos retos, como evidenciado pelas imagens de microscopia eletrônica de varredura. As medidas de calorimetria exploratória diferencial e difração de raio-x confIrmaram a cristalinidade das amostras. Os oligômeros de EGDMA, TEGDMA e EGDMA-co-TEGDMA sintetizados na presença do sistema HRP-H2O2 apresentaram grupos vinila pendentes, boa solubilidade em clorofórmio e ponto de fusão bem definido, evidenciando pouca reticulação ou ciclização e mostrando que as propriedades catalíticas da HRP propiciam um ambiente reacional apropriado para produzir materiais poliméricos com novas características. / This work is divided into two parts: (i) study on the adsorption of the enzyme horseradish peroxidase (HRP) onto flat substrates (silicon wafers, ASP/Si/SiO2 films, CABads/Si/SiO2 films, CABspin/Si/SiO2 films, and CMCABspin/Si/SiO2 films) followed by enzymatic catalytic tests of HRP immobilized onto these substrates, and (ii) formation of divinyl-based oligomers mediated by HRP. In the first part, the HRP immobilization onto flat substrates was investigated by means of ellipsometry, atomic force microscopy (AFM), and contact angle measurements. Adsorption isotherms of HRP onto silicon wafers, APS/Si/SiO2, and CABads/Si/SiO2 presented the continuous increase of HRP adsorbed amount ΓHRP as a function of enzyme solution concentration until an adsorption plateau, which evidenced monolayer formation. In these cases, the HRP adsorption process can be described by the random sequential adsorption model (RSA). For HRP/CABspin/Si/SiO2 and HRP/CMCABspin/Si/SiO2 cooperative adsorption of HRP molecules and multilayer formation were evidenced. The HRP adsorption onto silicon wafers, APS, CABads, and CMCABspin films is an irreversible process. Contrarily, HRP adsorbed reversibly onto CABspin films, since desorption of ~30% could be detected. The catalytic activity of HRP films immobilized onto flat substrates was verified by oxidation reaction of ABTS. Catalytic tests showed that substrates with adsorbed HRP can be reused three times without desorption or catalytic activity lost, except for HRP/CABspin/Si/SiO2 films, which became inactive after first use. The emulsion polymerization of ethylene glycol dimethacrylate (EGDMA) in mediated by HRP/Si/SiO2 films or by free HRP at room temperature revealed the formation of crystalline particles with polygonal geometry. In order to understand the formation of such crystalline structures, the second part of this thesis focused on EGDMA and/or triethylene glycol dimethacrylate (TEGDMA) oligomers formation in aqueous medium catalyzed by HRP in the presence of H2O2 at room temperature. EGDMA and/or TEGDMA oligomers were characterized by means of gravimetry, gel permeation chromatography, infrared vibrational spectroscopy and 1H NMR spectroscopy. Self-assembling of oligomers led to right-angled crystalline particles, as evidenced by scanning electron microscopy images. Differential scanning calorimetry and X-ray diffractometry measurements ratified the samples crystallinity. EGDMA, TEGDMA and EGDMA-co-TEGDMA oligomers synthesized in the presence of HRP-H2O2 system presented pendant vinyl groups along the chains, good solubility in chloroform, and well defined melting point. These features evidenced few crosslinking or cyclization and revealed that the catalytic properties of HRP provide an appropriate environrnent for production of materials with new characteristics.
5

Catalyse à l'or (I/III) : de la réactivité au catalyseur, en passant par l'analyse structurale / Gold (I/III) catalysis : from reactivity to catalyst, through structural analysis

Hoffmann, Marie 26 June 2015 (has links)
La catalyse organométallique est l’un des outils les plus puissants de la synthèse chimique, car elle permet de réaliser des transformations sélectives et spécifiques selon le catalyseur employé. Dans ce contexte, les sels et complexes d’or ont émergé il y a une quinzaine d’années et se sont révélés très utiles et attractifs pour la synthèse organique, faisant preuve de propriétés particulières de type acide de Lewis à la fois π (alcyno- alcènophilie) et σ (oxo- azaphile). L’objectif initial de cette thèse a été d'approfondir l’étude de la réactivité de l’or au travers la mise au point de nouvelles réactions catalysées par l’or(I/III). Si la majorité des réactions développées en catalyse à l’or concerne des processus de type π, nous avons dans un premier temps, souhaité évaluer son potentiel dans une réaction qui repose sur une activation purement σ, la cyclisation de Nazarov. Cette réaction a ensuite été étendue à un processus de type cascade, combinant activations π et σ. De plus, la formation d’un sous-produit inattendu au cours de cette étude a orienté nos recherches vers un nouveau processus catalytique, le réarrangement de γ–acyloxy alcynylcétones en furanes. Par la suite, nous nous sommes aussi intéressés au potentiel de l’or dans les réactions asymétriques, ce qui a conduit au développement d’un nouveau type de complexes d’or chiraux basés sur des ligands de type NHC-oxazoline. Enfin, nous nous sommes proposés d’utiliser la spectroscopie RMN J-résolue hétéronucléaire (une méthode simple mais peu exploitée), pour répondre à des problèmes d’attribution structurale. / Organometallic catalysis is one of the most powerful tools in chemical synthesis, because, depending on the catalyst, it allows for selective and specific transformations. Thus, the reactivity of gold salts and complexes was revamped around fifteen years ago. Nowadays, they are considered as powerful and very attractive for organic synthesis, showing both π (alcyno- alcènophilie) and σ (oxo- azaphile) Lewis acid properties.The first objective of this thesis was to study the reactivity of gold catalysts by the development of new reactions catalyzed by gold(I/III). If most of the developed reactions in gold catalysis is related to π activation, we proved its potential in a reaction dealing with σ activation, the Nazarov cyclization. This reaction was then extended to a cascade process, combining both π and σ Lewis acidities. Moreover, the obtainment of an unexpected by-product during the study directed our research towards a new gold catalytic reaction, the formation of furans from γ-acyloxyalkynyl ketones. Subsequently, we were also interested in the potential of gold in asymmetric reactions, which led to the development of new chiral gold complexs, based on NHC-oxazoline type ligands. Finally, we proposed to use the heteronuclear J-resolved NMR spectroscopy (a simple but scarce method), to answer some structural assignment problems.
6

Fractionation of natural organic matter (NOM) in water using prepared porous silica based materials as size exclusion (SEC)/GEL permeation chromatography (GPC) stationary phases

Bopape, Dineo Anna 06 1900 (has links)
Natural organic matter (NOM) is a diverse blend of decomposed animal and plant material found in different natural water sources. Due to its large and complex structure, NOM is difficult to both remove and characterize in water. Therefore, there is a need to separate NOM into its components before it can be characterized. The aim of this project was to fractionate NOM through a novel size exclusion chromatography (SEC) composite (poly (styrene-divinyl benzene) (PS-DVB) and Polysilsesquioxane (PSQ)) packed column. Raw and final water samples from Mid-Vaal (MV), Olifantspoort (LO), Mtwalume (MT) and Preekstoel (P) were investigated. Poly (styrene-divinyl benzene) (PS-DVB) and polysilsesquioxane were both synthesized and optimized at various temperatures, compositions and time periods. An end-capping material such as hexamethyldisilizane (HMDS) was added on the PSQ to prevent active silanol groups on the polysilsesquioxane (PSQ) from reacting with active sites of NOM (our analyte). The E-PSQ (end-capped PSQ) and PS-DVB materials were packed in eight different SPE cartridges first, before the materials could be packed in the SEC column. This packing was done to check for the best mass composition of the E-PSQ and PS-DVB. From the obtained SPE results, both the EPSQ and PS-DVB were packed in one SEC/GPC column at a ratio of 1:1 in order to form the composite hybrid material. The packed SEC column was connected to an HPLC instrument and various column efficiency tests were evaluated. The results for the test of interactions with acidic compounds implied that the column can be used for the acidic analytes such as those forming NOM composition (humic acids, fulvic acids) and the column had minimum silanol groups. For hydrophobic interactions the stationary phase strength was different to that of the commercial columns and it could selectively elute molecules based on their different masses. The steric selectivity test showed that the stationary phase could separate and distinguish between molecules with similar hydrophobicity and structure but different shapes (o-terphenyl and triphenylene). The Hydrogen bonding capacity (HBC) test showed that the column had minimum silanol groups and the end-capping was successful on the E-PSQ. After fractionation of all the water samples, the MT raw showed NOM peaks around 1.8 mins, 3.4 mins and 5.3, and the final showed NOM peaks around 1.8 mins and 5.5 mins. The Mid-Vaal (MV) raw and final samples shows NOM peaks at around 1.8 mins and 6 mins. The Preekstoel (P) final water had one NOM peak at around 1.8 mins and raw samples had two NOM peaks around 1.8 mins and 6 mins. / Chemistry / M. Sc. (Chemistry)

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