Thèse--Université de Bâle. / Curriculum vitae. "Abbréviations": p. [4].

Thesis (PH. D.)--University of Michigan, 1912. / Also issued in print.

Part one of this thesis concerns the polymerizability of some α,β-unsaturated monaldehydes and also relates the synthesis of some new polyaldehydes which have not been reported in the literature. Part two concerns the polymerization of glyoxal, the simplest dialdehyde, and the structure elucidation of this new polymer.

Wong, Chun Pong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 130-146). / Abstract also in Chinese. / Thesis Assessment Committee --- p.i / Declaration --- p.ii / Acknowledgements --- p.iii / 摘要 --- p.iv / Abstract --- p.vi / List of Abbreviations --- p.viii / List of Figures --- p.xii / List of Tables --- p.xiv / Content --- p.xv / Chapter Chapter 1 --- General Introduction --- p.1 / Chapter 1.1 --- Classification of aldehyde dehydrogenase --- p.1 / Chapter 1.2 --- Structure and catalytic mechanism of aldehyde dehydrogenase --- p.4 / Chapter 1.3 --- Multiple functions of aldehyde dehydrogenase --- p.11 / Chapter 1.4 --- Background of antiquitin --- p.13 / Chapter 1.5 --- Aim of study --- p.24 / Chapter Chapter 2 --- Structural Analysis of Human Antiquitin --- p.26 / Chapter 2.1 --- Introduction --- p.26 / Chapter 2.2 --- Materials and Methods --- p.30 / Chapter 2.2.1 --- Subcloning and expression of human antiquitin and its mutants --- p.30 / Chapter 2.2.2 --- Purification of human antiquitin and its mutants --- p.31 / Chapter 2.2.3 --- Kinetic properties of human antiquitin and its mutants --- p.32 / Chapter 2.2.4 --- Inhibitor studies of human antiquitin --- p.33 / Chapter 2.2.5 --- X-ray crystallography of human antiquitin ternary complex --- p.34 / Chapter 2.3 --- Results --- p.36 / Chapter 2.3.1 --- "Subcloning, expression and purification of human antiquitin and its mutants" --- p.36 / Chapter 2.3.2 --- Kinetic properties of human antiquitin and its mutants --- p.41 / Chapter 2.3.3 --- Inhibitor studies of human antiquitin --- p.44 / Chapter 2.3.4 --- X-ray crystallography of human antiquitin ternary complex --- p.47 / Chapter 2.4 --- Discussion --- p.56 / Chapter 2.4.1 --- Substrate specificity of recombinant human antiquitin --- p.56 / Chapter 2.4.2 --- Pyridoxine-dependent seizures and mutations in human antiquitin gene --- p.63 / Chapter 2.4.3 --- X-ray crystallography of human antiquitin ternary complex --- p.76 / Chapter Chapter 3 --- Functional Analysis of Human Antiquitin --- p.79 / Chapter 3.1 --- Introduction --- p.79 / Chapter 3.2 --- Materials and Methods --- p.83 / Chapter 3.2.1 --- Cell culture --- p.83 / Chapter 3.2.2 --- Transfection of HEK293 cells with siRNA --- p.83 / Chapter 3.2.3 --- Total protein extraction --- p.84 / Chapter 3.2.4 --- Total RNA extraction --- p.85 / Chapter 3.2.5 --- Real-time PCR assay --- p.86 / Chapter 3.2.6 --- Stress responsiveness of transfected HEK293 cells --- p.87 / Chapter 3.2.7 --- Cell growth analysis of transfected HEK293 cells --- p.87 / Chapter 3.2.8 --- Cell cycle profile analysis of transfected HEK293 cells --- p.88 / Chapter 3.2.9 --- Programmed cell death analysis of transfected HEK293 cells --- p.89 / Chapter 3.2.10 --- Confocal immunofluorescence microscopic analysis of transfected HEK293 cells --- p.89 / Chapter 3.2.11 --- Subcellular fractionation of transfected HEK293 cells --- p.90 / Chapter 3.2.12 --- Western blot analysis of transfected HEK293 cells --- p.90 / Chapter 3.3 --- Results --- p.93 / Chapter 3.3.1 --- Condition optimization for siRNA transfection in HEK293 cells --- p.93 / Chapter 3.3.2 --- Knock down of human antiquitin at protein and mRNA levels in HEK293 cells --- p.93 / Chapter 3.3.3 --- Stress responsiveness of transfected HEK293 cells --- p.99 / Chapter 3.3.4 --- Cell growth in transfected HEK293 cells --- p.102 / Chapter 3.3.5 --- Cell cycle profile analysis of transfected HEK293 cells --- p.107 / Chapter 3.3.6 --- Western blot analysis of cell cycle regulatory proteins of transfected HEK293 cells --- p.107 / Chapter 3.3.7 --- Programmed cell death analysis of transfected HEK293 cells --- p.111 / Chapter 3.3.8 --- Confocal immunofluorescence microscopic analysis of transfected HEK293 cells --- p.113 / Chapter 3.3.9 --- Subcellular fractionation of transfected HEK293 cells --- p.116 / Chapter 3.4 --- Discussion --- p.118 / Chapter 3.4.1 --- Lack of response of human antiquitin towards hyperosmotic stress --- p.118 / Chapter 3.4.2 --- Involvement of human antiquitin in cell growth --- p.119 / Chapter 3.4.3 --- Subcellular localization of human antiquitin --- p.124 / Chapter 3.4.4 --- Study of physiological function of human antiquitin using siRNA technique --- p.125 / Chapter Chapter 4 --- Future Prospects --- p.128 / References --- p.130

Le sujet de la thèse a été orienté vers trois axes majeurs : l'étude de la photochimie des aldéhydes et de leur capacité à photoamorcer une polymérisation radicalaire, l'étude des aldéhydes en tant qu'amorceurs thermiques, avec l'étude des interactions entre des aldéhydes et des sels métalliques ou des sels d'iodonium et le développement industriel de formulations (ex: peinture) réticulables via les systèmes photochimique et/ou thermique développé avec des aldéhydes.Les aldéhydes sont des photoamorceurs efficaces sous irradiation UV-B. De nombreux aldéhydes, notamment les aromatiques, sont meilleurs sous air grâce au cycle de photo-oxydation. Le mécanisme général de la réaction a été déterminé au cours de cette thèse. Les aldéhydes sont également capables de sensibiliser les sels d'iodonium par transfert d'électron et/ou d'énergie et/ou par FRPCP, et ainsi d'amorcer une polymérisation cationique. Tout au long de la thèse, de nombreuses applications industrielles ont vu le jour grâce à la recherche réalisée sur les aldéhydes et le système d'amorçage photo/thermique. Des applications ont également été adaptées au nouveau système afin d'augmenter les performances du système amorceur précédent et d'en diminuer le coût. / The subject of this PhD was directed towards three major areas: the study of the photochemistry of aldehydes and their ability to photoinitiate radical polymerization, the study of aldehydes as thermal initiators, with the study of interactions between aldehydes and metal salts or iodonium salts and industrial development of formulations (eg painting) curable via photochemical and/or thermal systems developedwith aldehydes.The aldehydes are effective photoinitiators under UV-B irradiation. Many aldehydes, including aromatic, are better in air through the cycle of photo-oxidation. The general mechanism of the reaction was determined in this thesis. The aldehydes are also able to sensitize the iodonium salts by electron transfer and/or energy and/or FRPCP, thereby initiating a cationic polymerization. Throughout the PhD, many industrial applications have been developed through research conducted on the aldehydes and on the photo/thermal initiating system. Applications were also adapted to the new system to increase performance of the previous initiator system and decrease cost.

Chan, King Lun Michel. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 111-121). / Abstracts in English and Chinese. / THESIS ASSESSMENT COMMITTEE --- p.i / ACKNOWLEDGEMENTS --- p.ii / 摘要 --- p.iv / ABSTRACT --- p.v / LIST OF ABBREVIATIONS --- p.xi / Chapter CHAPTER 1 --- INTRODUCTION / Chapter 1.1 --- Aldehyde Dehydrogenase Superfamily / Chapter 1.1.1 --- Classification and Substrate Specificities of Aldehyde Dehydrogenases --- p.1 / Chapter 1.1.2 --- Multiple Functions of Aldehyde Dehydrogenases and their Roles in Metabolism --- p.4 / Chapter 1.1.3 --- Structural Organization of Aldehyde Dehydrogenases in view of their Catalytic Mechanism --- p.7 / Chapter 1.2 --- Antiquitin / Chapter 1.2.1 --- Discovery and Plant Antiquitins --- p.15 / Chapter 1.2.2 --- Animal Antiquitins --- p.17 / Chapter 1.2.3 --- Human Antiquitin Gene Mutations and Pyridoxine-dependent Seizures --- p.19 / Chapter 1.2.4 --- Previous Findings on Seabream Antiquitin --- p.20 / Chapter 1.3 --- Aims of Study --- p.22 / Chapter CHAPTER 2 --- MATERIALS AND METHODS / Chapter 2.1 --- Materials / Chapter 2.1.1 --- "Subcloning, Expression and Purification of Human Antiquitin" --- p.24 / Chapter 2.1.2 --- Characterization of Human Antiquitin --- p.25 / Chapter 2.1.3 --- "Crystallization of Human Antiquitin, Diffraction Data Collection and Structure Determination" --- p.26 / Chapter 2.1.4 --- Mutational Studies of Human Antiquitin --- p.26 / Chapter 2.2 --- Methods / Chapter 2.2.1 --- "Subcloning, Expression and Purification of Human Antiquitin" / Chapter 2.2.1.1 --- Subcloning of the Full-length Human Antiquitin cDNA --- p.27 / Chapter 2.2.1.2 --- Bacterial Expression of Recombinant Human Antiquitin --- p.29 / Chapter 2.2.1.3 --- Purification of Human Antiquitin --- p.30 / Chapter 2.2.2 --- Characterization of Human Antiquitin / Chapter 2.2.2.1 --- Sodium Dodecyl Sulfate Polyacrylamide Gel Electrophoresis --- p.31 / Chapter 2.2.2.2 --- Size-exclusion Chromatography - Multi-angle Light Scattering --- p.32 / Chapter 2.2.2.3 --- Isoelectric Focusing --- p.33 / Chapter 2.2.2.4 --- pH-rate Profile --- p.33 / Chapter 2.2.2.5 --- Stability Studies --- p.34 / Chapter 2.2.2.6 --- Substrate Specificity Study --- p.35 / Chapter 2.2.3 --- "Crystallization of Human Antiquitin, Diffraction Data Collection and Structure Determination" / Chapter 2.2.3.1 --- Crystallization of Human Antiquitin --- p.36 / Chapter 2.2.3.2 --- Diffraction Data Collection and Model Building --- p.37 / Chapter 2.2.4 --- Mutational Studies of Human Antiquitin / Chapter 2.2.4.1 --- Preparation of Mutant Plasmids --- p.39 / Chapter 2.2.4.2 --- "Expression, Purification and Kinetics Studies of Mutants" --- p.39 / Chapter CHAPTER 3 --- RESULTS / Chapter 3.1 --- "Subcloning, Expression and Purification of Human Antiquitin" --- p.43 / Chapter 3.2 --- Characterization of Human Antiquitin --- p.49 / Chapter 3.3 --- "Crystallization of Human Antiquitin, Diffraction Data Collection and Structure Determination" / Chapter 3.3.1 --- "Crystallization, Data Collection and Refinement" --- p.59 / Chapter 3.3.2 --- Human Antiquitin Structure --- p.63 / Chapter 3.4 --- Mutational Studies of Human Antiquitin --- p.75 / Chapter CHAPTER 4 --- DISCUSSION / Chapter 4.1 --- Characterization and Substrate Specificity of Recombinant Human Antiquitin --- p.83 / Chapter 4.2 --- Crystallization and Crystal Structure of Human Antiquitin / Chapter 4.2.1 --- Crystallization --- p.86 / Chapter 4.2.2 --- Overall structure --- p.86 / Chapter 4.2.3 --- Cofactor binding --- p.88 / Chapter 4.2.4 --- Substrate Binding and Catalysis --- p.91 / Chapter 4.3 --- Mutations in Human Antiquitin Gene and their Relationship with Pyridoxine-dependent Seizures --- p.95 / Chapter 4.4 --- Comparison of Antiquitin Gene and Other Aldehyde Dehydrogenases --- p.104 / Chapter CHAPTER 5 --- FUTURE PROSPECTS --- p.106 / LIST OF REFERENCES --- p.111 / APPENDIX --- p.122

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Unprotected N-H aziridine aldehydes are surprisingly stable compounds which can undergo reactions in the absence of protecting groups. In total, three different transformations were explored during my Master’s thesis. The conversions include the dissociation of the aziridine aldehydes, which exist as dimers, and their subsequent re-dimerization in various solvents. The development of mixed aziridine aldehyde adducts and their attempted modifications will also be discussed. Finally, the discovery of N-H aziridine compounds containing a 1,3-dicarbonyl functionality will be discussed, as will their attempted transformations.