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Thesis (Ph.D.)--McMaster University (Canada), 1993. / Source: Dissertation Abstracts International, Volume: 54-12, Section: B, page: 6220. Adviser: R. F. W. Bader.

M.Sc. / This study focused on the synthesis and evaluation of phosphine ligands with multiple functional ities. Polar ligands suitable for use in homogeneous catalysis in aqueous/organic systems were synthesised, as were ligands incorporating a boron atom in an intramolecular Lewis acid-Lewis base interaction with the phosphorus atom. A malonate moiety was readily incorporated into a phosphorus starting material, and derivatives were obtained by reduction of the ester groups. The polar diol products were reacted with 1,4-butanesultone which made them water soluble and thus ideal for biphasic catalysis. Wittig chemistry was employed to introduce alkenes of varying electronic nature into a phosphorus-containing aldehyde starting material. The catalysed hydroboration reaction making use of diboron reagents was used to introduce a boron functionality into the resulting a, n-unsaturated ester phosphine I igands. All of the ligands produced were tested in transition metal-catalysed reactions, namely the Heck reaction, the Suzuki reaction, the Stille reaction, the carboxymethylation reaction and the hydroformylation reaction. The polar and water soluble ligands all showed comparable or improved yields to the standard benchmark triphenylphosphine ligand in organic, biphasic and ionic liquid media. The electronic nature of the alkene ligands largely dictated the activities observed in the Heck, Suzuki and Stille reactions. The electron rich ligands showed improved activities in the Heck reaction, while the electron poor ligands showed improved activities in the Suzuki reaction. In contrast, the Stille reaction seemed to be more affected by the steric demands of the ligands rather than by electronic considerations. It was also found that the boron containing ligands showed an enhanced activity in comparison to the boron free unsaturated and saturated ester ligands. This enhancement was directly ascribable to the Lewis acidic boron atom. This study allowed the synthesis of a range of functionally varying phosphine ligands which where shown to influence transition metal-catalysed reactions based specifically on the functionality present.

As tintas intumescentes vêm se tornando uma ótima alternativa para a proteção do aço contra o fogo. No entanto, o aço estrutural é aplicado em diversos setores da indústria, incluindo plataformas offshore de petróleo e gás e refinarias petroquímicas. Estas estruturas de alto desempenho ficam expostas a ambientes agressivos, o que torna necessário o desenvolvimento de tintas capazes de proteger o aço. Neste trabalho, foram preparadas tintas intumescentes epóxi formuladas com pó de gengibre e com casca de café como fonte de carbono e com trifenil fosfato (TPP) e fosfato de zinco (FZn) como fonte de fósforo. O objetivo principal deste trabalho foi desenvolver um sistema intumescente contendo compostos vegetais eficiente na proteção contra o fogo e capaz de proteger o substrato metálico contra a corrosão em ambiente salino. A avaliação foi realizada através de ensaio de resistência ao fogo (antes e após imersão em NaCl 3,5%), análise termogravimétrica (TGA), espectroscopia no infravermelho (FTIR), viscosidade Brookfield, aderência, ensaio estático de imersão, microscopia óptica (MO), microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), pirólise acoplada à cromatografia gasosa e à espectrometria de massas (Py-GC/MS), espectroscopia de impedância eletroquímica (EIE), metalografia e microdureza Vickers. Os compostos vegetais apresentaram potencial de aplicação como fonte de carbono em sistemas intumescentes, enquanto que o FZn foi eficiente substituindo o TPP como fonte de fósforo. O sistema contendo gengibre e TPP apresentou os melhores resultados gerais, mantendo o fenômeno de intumescência após imersão em solução salina e apresentando a melhor proteção contra a corrosão dentre as amostras de tinta intumescente. Por fim, o revestimento contendo TPP apresentou propriedades anticorrosivas superiores ao FZn na aplicação em sistemas intumescentes. / The intumescent coating have become a great alternative for the protection of steel against fire. However, structural steel is applied in several industry sectors, including offshore oil and gas platforms and petrochemical refineries. These high performance structures are exposed to aggressive environments, which makes it necessary to develop coatings capable of protecting steel. In this work, epoxy intumescent coatings formulated with ginger powder and coffee husk as carbon source and with triphenyl phosphate (TPP) and zinc phosphate (ZnP) as phosphorus source were prepared. The main objective of this work was to develop an intumescent system containing vegetable compounds efficient in fire protection and able to protect the metal substrate against corrosion in saline environment. The evaluation was performed by fire resistance test (before and after immersion in NaCl 3.5%), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR), Brookfield viscosity, adhesion tests, static immersion test, optical microscopy (OM), Scanning electron microscopy (SEM), X-ray diffraction (XRD), pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC / MS), electrochemical impedance spectroscopy (EIS), metallography and Vickers microhardness. Vegetable compounds presented potential as a carbon source in intumescent systems, while ZnP was efficient replacing TPP as a source of phosphorus. The system containing ginger and TPP presented the best overall results, maintaining the intumescence phenomenon after immersion in saline solution and presenting the best protection against corrosion among the intumescent coating samples. Finally, the coating containing TPP presented anticorrosive properties superior to FZn in the application in intumescent systems.

Cheung Chung Hong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 126-137). / Abstracts in English and Chinese. / ABSTRACT (English version) --- p.iii / ABSTRACT (Chinese version) --- p.vi / ACKNOWLEDGMENTS --- p.viii / TABLE OF CONTENTS --- p.ix / LIST OF FIGURES --- p.xiii / LIST OF TABLES --- p.xvii / Chapter CHAPTER ONE: --- INTRODUCTION --- p.1 / Chapter 1.1 --- Molecular Structure Determination --- p.1 / Chapter 1.2 --- Methods for Structure Determination --- p.1 / Chapter 1.2.1 --- Infrared (IR) Spectroscopy --- p.1 / Chapter 1.2.2 --- Electron Microscopy (EM) --- p.2 / Chapter 1.2.3 --- X-ray Diffraction (XRD) --- p.2 / Chapter 1.2.4 --- Nuclear Magnetic Resonance (NMR) Spectroscopy --- p.3 / Chapter 1.3 --- Solid State NMR Spectroscopy 一 Chemical Shielding Tensor --- p.4 / Chapter 1.4 --- Scope of This Thesis --- p.6 / Chapter CHAPTER TWO: --- PRINCIPLE AND THEORY --- p.7 / Chapter 2.1 --- Introduction --- p.7 / Chapter 2.2 --- Chemical Shielding Tensor (CST) --- p.7 / Chapter 2.2.1 --- Basis of Nuclear Magnetic Resonance --- p.7 / Chapter 2.2.2 --- Theoretical Description of CST --- p.8 / Chapter 2.3 --- CST Calculation --- p.11 / Chapter 2.3.1 --- Ramsey's Theory --- p.11 / Chapter 2.3.2 --- Gauge-including Atomic Orbitals (GIAO) Method --- p.13 / Chapter 2.4 --- Density Functional Theory (DFT) --- p.14 / Chapter 2.4.1 --- KS Theorem --- p.14 / Chapter 2.4.2 --- B3LYP - Hybrid DFT Functional --- p.16 / Chapter 2.5 --- Molecular Mechanic (MM) --- p.16 / Chapter 2.5.1 --- Basis Principle 一 Ball and Spring Model --- p.16 / Chapter 2.5.2 --- MM+ --- p.18 / Chapter 2.5.2.1 --- Bond Stretching --- p.18 / Chapter 2.5.2.2 --- Bond Bending --- p.19 / Chapter 2.5.2.3 --- Torsional Motion --- p.19 / Chapter 2.5.2.4 --- van der Waals Interaction --- p.19 / Chapter 2.5.2.5 --- Electrostatic Interaction --- p.20 / Chapter 2.5.2.6 --- Stretching-bending Interaction --- p.21 / Chapter 2.6 --- Isodesmic Reaction --- p.21 / Chapter CHAPTER THREE: --- METHODOLOGY AND EVALUATION --- p.23 / Chapter 3.1 --- Introduction --- p.23 / Chapter 3.2 --- Computational Method --- p.24 / Chapter 3.2.1 --- Evaluation of Different NMR Computation Level --- p.24 / Chapter 3.2.2 --- Computational Error 一 Round Off Error --- p.32 / Chapter 3.3 --- Local Structure Determination and Evaluation --- p.34 / Chapter 3.3.1 --- Methodology --- p.34 / Chapter 3.3.2 --- Definition of Local Structure --- p.37 / Chapter 3.3.3 --- Models used in Local Structure Determination --- p.37 / Chapter 3.3.3.1 --- Model without CST Modification (Mod-1) --- p.38 / Chapter 3.3.3.2 --- Models with CST Modification --- p.39 / Chapter 3.3.3.2.1 --- Model Using Correction Factors (Mod-2) --- p.39 / Chapter 3.3.3.2.2 --- Model Using Linear Equation (Mod-3) --- p.40 / Chapter 3.3.4 --- Evaluation - Me2P(S)C(OH)R1R2 --- p.41 / Chapter 3.4 --- Determination of Possible Conformation in Powder and Evaluation --- p.53 / Chapter 3.4.1 --- Introduction --- p.53 / Chapter 3.4.2 --- Methodology --- p.54 / Chapter 3.4.2.1 --- Preparation of Calibration Curve --- p.54 / Chapter 3.4.2.2 --- Determination of Possible Conformation Contributing to the Observed CST --- p.57 / Chapter 3.4.3 --- Evaluation --- p.59 / Chapter 3.5 --- Discussion --- p.72 / Chapter 3.5.1 --- Factors Affecting CST --- p.72 / Chapter 3.5.1.1 --- Inter-molecular Interaction --- p.72 / Chapter 3.5.1.1.1 --- O-H----S --- p.73 / Chapter 3.5.1.1.2 --- C-H----S --- p.78 / Chapter 3.5.1.1.3 --- van der Waals Forces --- p.80 / Chapter 3.5.1.2 --- Conformation --- p.81 / Chapter 3.5.2 --- Effect of Experimental Error on the Calculated Structure --- p.82 / Chapter 3.6 --- Summary --- p.84 / Chapter CHAPTER FOUR: --- APPLICATIONS --- p.86 / Chapter 4.1 --- Introduction --- p.86 / Chapter 4.2 --- Tetramethyldiphoshine Disulfide (TMPS) --- p.86 / Chapter 4.2.1 --- Local Structure --- p.87 / Chapter 4.2.2 --- Conformation --- p.92 / Chapter 4.3 --- "Carbon Compounds : 1,3,5-Trimethoxybenzene (1,3,5-TMB) and 1,4-Dimethoxybenzene (1,4-DMB)" --- p.97 / Chapter 4.3.1 --- Local Structure --- p.98 / Chapter 4.3.2 --- Conformation --- p.103 / Chapter 4.4 --- Conclusion --- p.110 / Chapter CHAPTER FIVE: --- CONCLUSIONS --- p.111 / APPENDIX --- p.114 / REFERENCES --- p.126

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A direct injection nebulizer (DIN) was constructed in our laboratory and was evaluated as an interface between a liquid chromatography column and an inductively coupled plasma-atomic emission spectrometer (ICP-AES). Optimum operating conditions, detection limits and reproducibility of the DIN closely matched literature data for a somewhat different commercial device. In addition, when using the DIN for sample introduction, the ICP detection exhibited uniform response towards phosphorous compounds of different volatilities. / Department of Chemistry

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.