Student Number : 0107507J - PhD thesis - School of Chemistry - Faculty of Science / Periodic mesoporous organosilica (PMO) materials (consisting of ethane groups in the framework) and bifunctional periodic mesoporous organosilica materials (consisting of ethane groups in the framework and either glycidoxypropyl groups or aminopropyl groups in the channels) were synthesized by the sol-gel method under basic conditions. Ethanesilica materials were synthesized by condensation of 1,2-bistrimethoxysilylethane (BTME) and by co-condensation of BTME with tetraethylorthosilicate (TEOS). Bifunctional periodic mesoporous organosilica materials were synthesized by the co-condensation of BTME with either 3- glycidoxypropyltriethoxysilane (GPTS) or 3-aminopropyltriethoxysilane (APTS). Cetyltrimethylammonium bromide was used as the structure-directing template. Cobalt ion incorporated ethanesilica and modified ethanesilica materials were synthesized in situ by adding cobalt nitrate to the reaction mixture. Cobalt was also supported on ethanesilica materials and APTS-modified materials by using the incipient wetness impregnation method. Raman spectroscopy and diffuse reflectance infrared spectroscopy (DRIFTS) results confirmed the formation of organosilica materials and showed that the surfactant was removed by solvent extraction. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) showed that the ethane portion of the materials (originating from the bridging ethane group in BTME) only decomposed at temperatures > 400 oC. These techniques also showed that the surfactant is removed by solvent extraction. Cobalt ion incorporation was confirmed by Raman spectroscopy and UV-vis diffuse reflectance spectroscopy. Powder powder X-ray diffraction (XRD) and nitrogen adsorption data indicated that the mesophase and textural properties of the materials are dependent on the reaction conditions (i.e. ageing duration, ageing temperature, amount of silica precursor(s), amount of water and amount of base (NH4OH)). The periodicity of the materials was indicated by the presence of low angle diffraction peaks in powder X-ray diffraction patterns. Cubic and hexagonal mesophases were identified using powder X-ray diffraction. When solvent extraction is prolonged, the BET surface area and the pore volume increase, while the average pore diameter decreases. Materials with more dominant XRD structural features and larger d values, higher surface areas, lower pore volumes and average pore diameters are obtained when low ageing temperatures are used. For samples prepared from a mixture of BTME and TEOS at a given temperature, the surface area was found to increase with increasing amount of TEOS added. This trend was observed for materials with and without cobalt. Type IV isotherms, typical of mesoporous materials, were obtained for ethanesilica and modified ethanesilica materials prepared without cobalt. For cobalt incorporated periodic mesoporous ethanesilica materials, the XRD lattice parameter (d100) increased whereas surface area and pore volume decreased with increasing cobalt loading. Nitrogen gas adsorption on samples with varying ratios of BTME:GPTS or BTME:APTS revealed that increasing the amount of GPTS or APTS affects pore size, surface area and pore volume as well as shapes of the isotherms and hysteresis loops. The hysteresis loops of the Type IV isotherms obtained for GPTS-modified ethane silica materials (without cobalt) change from Type H3 to Type H4. There is a tendency for pore sizes to change from mesopore to micropore when the amount of GPTS is increased. Isotherms of cobalt incorporated GPTS-modified ethane silica materials changed from Type IV to Type I. The surface area, pore volume and pore diameter decreased with increasing loading of GPTS or APTS as well as after cobalt incorporation.

MSc (Chemistry), Faculty of Science, University of the Witwatersrand, 2002

O cobalto é um dos principais componentes das ligas metálicas fundidas amplamente utilizadas na odontologia. Ele é considerado o constituinte de 45 a 70% de inúmeros trabalhos protéticos. Há evidência de elementos metálicos causarem toxicidade sistêmica e local. Este trabalho teve como objetivo, avaliar os efeitos do cobalto no epitélio juncional, epitélio adamantino, epitélio da gengiva inserida e ligamento periodontal do 1° molar superior do rato, durante a lactação. Para tal, foram utilizados ratos com 1 dia de vida pós-natal, cujas mães receberam 300mg de cloreto de cobalto por litro de água destilada no bebedouro (grupo tratado -T) e ratos cujas mães não receberam CoCl2 (grupo controle - C), durante toda a lactação. Ao final de 21dias, os filhotes foram sacrificados com sobredosagem anestésica. As cabeças foram separadas e fixadas em solução de alfac (álcool 80%- 85ml, formalina 10ml e ácido acético 5ml) incluídas em parafina e os cortes frontais seriados foram corados com hematoxilina e eosina. Os cortes foram focalizados ao microscópio de luz (100X), munido de uma câmara clara. Os núcleos das células dos tecidos estudados foram projetados sobre o papel com aumento final de 1000X e 50 núcleos de cada estrutura foram contornados com lápis preto para posterior medição do diâmetros maior (D) e menor (d). Uma vez determinados os diâmetros, foram estimados os seguintes parâmetros cariométricos: diâmetro geométrico médio, relação entre D/d, perímetro, área, volume, relação entre volume e área, excentricidade, coeficiente de forma e índice de contorno. Neste trabalho também foi utilizada uma grade impressa sobre papel. As imagens obtidas foram desenhadas sobre a grade. A grade pode ser usada tanto para contar pontos sobre uma determinada estrutura histológica bem como para contar intersecções entre duas estruturas contíguas, bastando para isso, no primeiro caso, considerar o número de pontos que caem sobre a estrutura em estudo, ou, no segundo caso, o número de vezes em que as superfícies vizinhas cortam a linha curva. Com a finalidade de se avaliar o volume citoplasmático, o volume celular, a relação núcleo/citoplasma, a densidade numérica celular, a relação superfície externa/camada basal, a espessura das camadas epiteliais e a densidade de superfície, foi utilizada ora a contagem de pontos ora o número de intersecções e aplicados às equações estereológicas apropriadas para cada uma dessas variáveis. Todos os dados colhidos foram submetidos à estatística não paramétrica - Teste de Wilcoxon-Mann-Whitney. Os núcleos dos tecidos estudados mostraram valores diminuídos, após cariometria, para os diâmetros maior, menor e médio; volume, área, perímetro e relação volume/área. Estereologicamente foi possível observar, no epitélio juncional, epitélio adamantino e no epitélio da gengiva inserida, células menos volumosas com citoplasma mais escasso levando a um maior número de células por mm3 de tecido. O ligamento periodontal também se apresentou desorganizado e com fibras de menor tamanho. Neste estudo, o cobalto ocasionou um quadro de hipotrofia epitelial, indicando uma ação direta nos epitélios juncional e adamantino, epitélio da gengiva inserida bem como no ligamento periodontal. / Cobalt is one of the main components of cast metal alloys broadly used in dentistry. It is the constituent of 45 to 70% of numerous prosthetic works. There is evidence that metal elements cause systemic and local toxicity. The purpose of the present study is to evaluate cobalt effects on the junctional epithelium, adamantine epithelium, inserted gum epithelium, and periodontal ligament of the superior first molar in rats, during lactation. To do this, 1-day old rats were used, whose mothers received 300mg of cobalt chloride per liter of distilled in the drinker (treated group T) and rats whose mothers did not receive CoCl2 (control group C), during lactation. After 21 days, the rat pups were killed with an anesthetic overdose. The heads were separated and fixed in an alfac solution (80% alcohol-85ml, formaline-10ml, and acetic acid-5ml), embedded in paraffin and stained with hematoxylin and eosin. The cuts were viewed under a light microscope (100X) with a clear chamber. The nucleus of the studied tissue cells were projected on paper with a final increase of 100X. Fifty nuclei from each structure were outlined with a black pencil so that the greater (D) and smaller (d) diameters could be measured. After determining the diameters, the following cariometric parameters were established: mean geometric diameter, D/d relation, perimeter, area, volume, volume/area relation, eccentricity, form coefficient, and contour index. This study also used a grid printed on paper. The images obtained were drawn over the grid, which was used to count points over a certain histological structure as well as to count intersections between two contiguous structures. All that was needed, in the first case, was to consider the number of points located over the studied structure, or, in the second case, the number of times that neighboring surfaces cut the curve line. With the aim to evaluate the cytoplasmic volume, cellular volume, cytoplasm/nucleus relation, cellular numeric density, external surface/basal layer relation, the thickness of epithelial layers, and surface density, point counting was used at times and, at others, the number of intersections was considered and applied to the appropriate stereological equations for each variable. All the collected data were subjected to non-parametric statistics Wilcoxon-Mann-Whitney Test. The nuclei of the studied tissues showed reduced values after cariometry for: greater, smaller, and mean diameter; volume; area; perimeter; and volume/area relation. Stereologically, it was observed, in the junctional epithelium, adamantine epithelium, and in the inserted gum epithelium, cells with less volume and with scarce cytoplasm, which caused a greater number of cells per mm3 of tissue. The periodontal ligament was also disorganized and with smaller fibers. In this study, cobalt caused epithelial hypertrophy symptoms, indicating a direct action on the junctional and adamantine epithelium, inserted gum epithelium, as well as on the periodontal ligament.

Estudos sobre a formação dos complexos de metais, seus equilíbrios e, também, o aproveitamento analítico desses diferentes sistemas constituem uma tradicional linha de pesquisa em Química. Mais especificamente, as espécies formadas entre os vários pseudo-haletos e outros ligantes, com muitos cátions dos metais de transição, vêm sendo sistematicamente investigadas em nossos laboratórios de Química Analítica. Nesta linha, o emprego do íon tiocianato como ligante tem se destacado dentre os métodos analíticos para a determinação de cobalto, cuja procura tem sido crescente à medida que o homem, ao longo de sua evolução, descobre e produz novos materiais contendo esse metal. Desta forma, tendo em vista algumas características típicas do sistema Co(II)/SCN-, tal como sua intensa coloração, objetivou-se, nesta oportunidade, explorá-lo espectrofotometricamente com maior profundidade. Conseqüentemente, diversos parâmetros envolvidos na complexação dos íons cobalto (II) pelo tiocianato, tais como: a acidez do meio, a concentração disponível de ligante e a presença de solventes orgânicos no sistema, tiveram seus efeitos avaliados individualmente. Com os resultados destes estudos, estabeleceram-se as condições experimentais otimizadas para a montagem do método analítico, visando a determinação de íons cobalto(II). São elas: C (HClO4) =0,050 mol L-1 C (SCN-)=0,203 mol L-1 C(THF)=60% (v/v) Através de estudos espectrofotométricos preliminares, observou-se que o sistema apresenta dois máximos de absorção nestas condições experimentais: 316 e 622 nm, sendo esta última banda, aquela normalmente utilizada neste tipo de trabalho. Estudos de calibração nos dois comprimentos de onda indicaram que as leituras obedecem fielmente à lei de Beer em ambos os casos, porém com sensibilidade significativamente maior na região ultravioleta (E(316nm)= 1,20 x 104 e E(622nm)= 1,95 x 103 L mol-1 cm-1). Outros estudos sobre estabilidade, repetibilidade (precisão) e de possíveis interferentes também foram realizados, sendo os resultados bastante satisfatórios para fins analíticos. Observou-se interferência das espécies: I-, Al3+, IO3-, Mn2+, NO2-, BrO3-, S2O32-, Hg2+, Cd2+, quando presentes em concentrações cem vezes superiores à de cobalto(II). Entretanto, tal efeito desaparece quando estes íons acham-se em concentrações dez vezes maior do que a do metal de interesse. Aplicações analíticas do método proposto foram testadas em um produto farmacêutico (vitamina B12) e em uma liga odontológica, com resultados plenamente satisfatórios, já que os erros percentuais obtidos ficaram dentro da faixa aceitável (< 5%). A técnica de espectroscopia de absorção atômica foi utilizada paralelamente nestas análises, para efeito comparativo, na qual a determinação de cobalto mostrou-se possível na liga odontológica, mas inadequada para o fármaco (erro da ordem de 20%), nas condições de abertura realizadas. A comparação dos resultados mostra a potencialidade do método proposto, tendo em conta a simplicidade, exatidão e custo das aparelhagens. Finalizando, a possível influência do níquel (presente naturalmente em diversas amostras reais) na determinação de cobalto foi avaliada sob as condições experimentais estabelecidas para o método espectrofotométrico proposto. Observou-se que este “contaminante" natural exibe um pico de absorção em 245 nm e, através dos estudos, confirmou-se a aditividade das absorbâncias dos respectivos complexos (Co e Ni). Testou-se a possibilidade de determinação espectrofotométrica simultânea destes dois metais, através de leituras nos respectivos máximos (245 e 316 nm), empregando-se um sistema algébrico com duas equações simples, cujos resultados foram plenamente satisfatórios. As faixas úteis de trabalho, em termos de concentrações de cobalto e níquel foram, respectivamente: 0,94 a 4,04 mg L-1 e 28,7 a 123,7 mg L-1, respectivamente. / Studies about the formation of metallic complexes, their equilibria and also the analytical utilization of these different systems represent a traditional research line in Chemistry. More specifically, the species formed among the various pseudohalides and other ligands, with several cations of transition metals, have been systematically investigated in our Laboratories. The use of the thiocyanate ion as ligand has been intensive from among the analytical methods for cobalt(II) determination, of which interest has increased more recently, according to the man discovers and production of new materials containing this metal. Due some typical characteristics of the system Co(II)/SCN-, such as its colored complexes, the principal purpose of this study was to explore it more carefully by visible-ultraviolet spectrophotometry. Consequently, several parameters involved in the cobalt(II)/thiocyanate complexes formation, such as acidity level, concentration of free ligand, and the percentage of organic solvents in the system, had their respective effects evaluated individually. Through the results of these diverse studies, appropriate experimental conditions were established for the analytical methods, for the determination of the cobalt(II) ion. They are: C (HClO4)=0.050 mol L-1 C (SCN-)=0.203 mol L-1 C(THF)=60% (v/v) Preliminary spectrophotometry studies showed two absorption maxima (peaks) under these optimized experimental conditions: 316 and 622 nm, being this last visible band normally applied for this type of work (determination). Calibration studies at these two wavelengths showed that the Beer’s Law is obeyed in both cases, but a higher sensitivity was obtained in the ultraviolet region ( E(316nm)= 1.20 x 104 e E(622nm)= 1.95 x 103 L mol-1 cm-1). Other studies about stability, precision, accuracy and possible interferences were also performed, showing satisfactory results for the analytical purposes. It was observed some interference of the following species: I-, Al3+, IO3-, Mn2+, NO2-, BrO3-, S2O32-, Hg2+ and Cd2+, when present in concentrations one hundred times higher than the cobalt(II). However, this effect disappears when these ions are presented on concentration just ten times higher. Analytical applications of the proposed method were tested for a pharmaceutical product (B12 vitamin) and for an odontological alloy, with large success, since the percentage of error was within the tolerance range (<5%). Atomic absorption spectroscopy was also used in this analysis for comparision, in which the cobalt determination was possible for the alloy but inadequate for the pharmaceutical product (error about 20%). Comparison of the results shows the potentiality of this alternative spectrophotometric method, taking in account its simplicity, accuracy and equipments prices. Finally, the influence of nickel (naturally present in several real samples) on the spectrophotometric cobalt determination was evaluated, under the optimized experimental conditions. It was observed that this natural “contaminating" exhibits an absorption peak at 245 nm. Other confirmatory studies show the additivities of the respective absorbances (nickel and cobalt/thiocyanate complexes), allowing the simultaneous spectrophotometric determination of these these metals, using a matematical system with two equations (peaks 245 and 316 nm). This attempt was well satisfactory and the useful concentration ranges for cobalt and nickel were, respectively, 0.94 to 4.04 mg L-1 and 28.7 to 123.7 mg L-1.

No presente trabalho, foram estudados catalisadores de Co10%SiO2, com adições de La2O3 e CeO2, para a reação de reforma a vapor do etanol (RVE), visando aumentar a atividade catalítica e reduzir a formação de carbono sobre o catalisador. O teor mássico de cobalto utilizado foi de 10%, enquanto que os teores de La e Ce seguiram as seguintes proporções em 10%CoLa2%Ce50%-xSi50%, onde X = 2%, 4% e 6%. Os suportes foram preparados pelos métodos de co-precipitação e impregnação a fim de avaliar o efeito do método de preparação sobre o comportamento catalítico, e a fase ativa foi incorporada através do método da impregnação. Todos os catalisadores obtidos foram submetidos à análise de Espectroscopia Dispersiva em Emissão de Raios X (EDX), Difratometria de Raios X (DRX), Redução à Temperatura Programada (RTP) e Área Superficial Específica pelo método BET. Os catalisadores preparados pelo método de co-precipitação do suporte também foram analisados por Difratometria de Raios X- H2 \"in Situ\". Em seguida os catalisadores foram aplicados na reação RVE, e dentre os catalisadores estudados o que apresentou a maior seletividade para o H2 em cada método foi selecionado para a realização de estudos referentes á variação do teor em massa da fase ativa (10% e 20%) e a variação da temperatura de reação. O desempenho destes catalisadores foi comparado com o obtido para os catalisadores sem aditivo no suporte. Após os testes catalíticos, o coque formado foi quantificado por Análise Elementar e caracterizado por Microscopia Eletrônica de Varredura (MEV) e Difratometria de Raios X. Ao analisar os resultados de DRX e RTP observou-se a formação da fase Co3O4 para todos os catalisadores. E para os catalisadores mistos Co/La-Ce-Si, cujos suportes foram co-precipitados e impregnados, identificou-se, através do DRX, a formação da solução sólida entre o óxido de cério e o óxido lantânio. Nos ensaios reacionais foi observado que os catalisadores com maiores teores de La3+, para ambos os métodos de preparação, foram mais seletivos para H2, e que a temperatura influenciou no desempenho catalítico da reação. Ao analisar o carbono após a RVE, somente os catalisadores suportados em La2O3 puro, para ambos os métodos, apresentaram a espécie La2O2CO3 identificada através da DRX, que minimiza a formação do coque, e através da analise por MEV do catalisador após a reação, verificou-se que o coque formado foi filamentoso, permitindo a exposição do cobalto metálico por um maior período de tempo. / This research reports studies with Co/SiO2 catalysts modified with La2O3 and CeO2 by steam reforming of ethanol (SRE) in order to increase the catalytic activity and reduce the carbon formation on the catalyst. The amount of Co used was 10%, already of La and Ce were 10% CoLaxCe50-xSi50, where X = 2%, 4% and 6%. The supports were prepared according co-precipitation and impregnation methods in order to evaluate the effect on the catalytic performance. The active phase was incorporated by impregnation method. All were characterized by Energy Dispersive X Ray Spectroscopy (EDX), X Ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and Specific Surface Area (BET) and those prepared by co-precipitation were also analyzed by X Ray Diffraction in Situ. Thereafter, the catalysts were applied in the SRE and the highest selectivity against H2 in each method was selected for studies of variation of the mass content of active phase (10% and 20%) and temperature reaction. The performance was compared with catalysts without additive in the holder. After tests, the coke formed was determined by Elemental Analysis and characterized by Scanning Electron Microscopy (SEM) and XRD. From the XRD and TPR results was possible identify the presence of Co3O4 phase in all catalysts. In the mixed catalyst (Co/Ce-La-Si) was identified, by XRD, the formation of solid solutions between the cerium and lanthanum. Was observed that the catalyst with higher concentrations of La3+, in both methods of preparation, were more selective against H2, furthermore the temperature affected the performance of the catalysis. After characterization and quantification of the produced carbon during SRE, only catalysts supported in pure La2O3, for both methods, showed the formation of La2O2CO3, which minimizes coke formation and was identified by XRD. Through of SEM analysis of the catalyst after the reaction, it was found that coke formed a filamentous-like structure, allowing the exposure of the metallic cobalt for a longer period of time with the support.

by Ho Kai Wing Kevin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 94-98). / ABSTRACT --- p.iv / ACKNOWLEDGEMENTS --- p.vi / Chapter CHAPTER ONE: --- INTRODUCTION --- p.1 / Chapter 1.1 --- Basic Co-NMR Theory --- p.1 / Chapter 1.2 --- Method Employed --- p.5 / Chapter 1.2.1 --- Solvent Dependent Studies on Cobalt(III) complexes using 59Co NMR Spectroscopy --- p.5 / Chapter 1.2.2 --- Relationship between δiso and NQCC of Cobalt(III) Complexes in Solid --- p.7 / Chapter 1.3 --- Donor Acceptor Interactions --- p.8 / Chapter 1.4 --- Objectives of this Thesis --- p.10 / Chapter CHAPTER TWO: --- EXPERIMENTAL --- p.11 / Chapter 2.1 --- Synthesis --- p.11 / Chapter 2.2 --- NMR Measurements --- p.13 / Chapter 2.2.1 --- 59Co NMR Measurements --- p.13 / Chapter 2.2.2 --- 13c NMR Measurements (T1 Measurements) --- p.14 / Chapter 2.3 --- Viscosity Measurements --- p.15 / Chapter 2.4 --- UV-Vis Spectral Measurements --- p.15 / Chapter CHAPTER THREE --- 59Co NMR STUDY OF MAGNETIC COBALT(III) COMPLEXES --- p.16 / Chapter 3.1 --- Solvent-Dependent Studies of Cobalt(III) Complexes --- p.16 / Chapter 3.1.1 --- "Study of [Co(en)3]Cl3 and cis, trans-[Co(en)2(N3)2]NO3" --- p.17 / Chapter 3.1.2 --- Study of trans- [Co(en)2(NH3)2]Cl3 and trans- [Co(en)2(N02)2]NO3 --- p.29 / Chapter 3.1.3 --- "Study of trans- Na[Co(acac)2 (N02)2],trans- [Co(acac)2(N02)(NH3)] and trans-[Co(acac)2(NH3)2]I" --- p.36 / Chapter 3.1.4 --- Summary --- p.48 / Chapter 3.2 --- "Simultaneous Determination of CSA, ic, and NQCC of Cobalt(III) complexes in Different Solvents" --- p.49 / Chapter 3.2.1 --- Method --- p.49 / Chapter 3.2.2 --- "Study of trans- Na[Co(acac)2(N02)2],trans- [Co(acac)2(N02)(NH3)] and trans-[Co(acac)2(NH3)2]I and trans-[Co(acac)2(MeNH2)2]I" --- p.52 / Chapter 3.2.3 --- Study of trans- [Co(en)2(N〇2)2]N03 and trans- [Co(en)2(NCS)2]NCS --- p.58 / Chapter 3.2.4 --- Study of trans- [Co(en)2(NH3)2]Cl3 and trans- [Co(en)2(N3)2]NO3 --- p.63 / Chapter 3.2.5 --- Summary --- p.68 / Chapter 3.3 --- Resolution of the d-d Electronic Transition Energies in Cobalt Complexes and its Application to the Donor-Acceptor Interactionsin Cobalt Complexes - Application of Equation 3.3.1 --- p.70 / Chapter 3.3.1 --- Method --- p.70 / Chapter 3.3.2 --- "Study of trans- [Co(en)2(N02)2]N03,trans- [Co(en)2(NCS)2]NCS, trans- [Co(en)2(N3)2]N03 and trans- [Co(en)2(NH3)2]Cl3" --- p.72 / Chapter 3.3.3 --- "Study of trans- Na[Co(acac)2(NO2)2],trans- [Co(acac)2(N02)(NH3)] and trans-[Co(acac)2(NH3)2]I" --- p.86 / Chapter CHAPTER FOUR --- CONCLUSION AND FUTURE WORKS --- p.92 / REFERENCES --- p.94

by Chung Sai Cheong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1993. / Includes bibliographical references (leaves 94-99). / DESCRIPTIVE NOTE / ABSTRACT --- p.iii / ACKNOWLEDGEMENTS --- p.v / Chapter CHAPTER ONE: --- INTRODUCTION --- p.1 / Chapter CHAPTER TWO: --- EXPERIMENTAL --- p.6 / Chapter 2.1 --- Synthesis --- p.6 / Chapter 2.2 --- NMR Measurement --- p.6 / Chapter 2.2.1 --- Solid State 59Co NMR --- p.6 / Chapter 2.2.2 --- Solution NMR --- p.7 / Chapter 2.2.2.1 --- 59Co NMR Measurements --- p.7 / Chapter 2.2.2.2 --- 13C NMR Measurements --- p.8 / Chapter 2.3 --- UV-Vis Spectral Measurements --- p.9 / Chapter 2.4 --- Computer Simulation --- p.10 / Chapter CHAPTER THREE: --- QUANTITATIVE CORRELATION OF SHIELDING ANISOTROPY AND NQCC - APPLICATION TO SOLVATION STUDIES OF OCTAHEDRAL COBALT (III)COMPLEXES / Chapter 3.1 --- Introduction --- p.11 / Chapter 3.2 --- Theory --- p.15 / Chapter 3.3 --- Results and Discussion --- p.20 / Chapter 3.3.1 --- The 59Co NMR Powder Spectrum of Diamagnetic Cobalt Complexes --- p.20 / Chapter 3.3.2 --- The Correlation of NQCC with Chemical Shift Anisotropy in the Solid State --- p.34 / Chapter 3.3.3 --- Application of Equation 3.16in Solution Studies --- p.39 / Chapter 3.3.3.1 --- The Chemical Shift --- p.39 / Chapter 3.3.3.2 --- The Effective Correlation Time --- p.48 / Chapter 3.3.3.3 --- The Nuclear Quadrupole Coupling Constant --- p.49 / Chapter 3.4 --- Summary --- p.51 / Chapter CHAPTER FOUR: --- 59Co AND 13C RELAXATION OF Co(acac)3 IN HYDROGEN BONDING (KALOMETHANE) SOLVENTS / Chapter 4.1 --- Introduction --- p.53 / Chapter 4.2 --- Results and Discussion --- p.57 / Chapter 4.2.1 --- The Static NMR Powder Spectrum Co(acac)3 --- p.57 / Chapter 4.2.2 --- Chemical shift --- p.60 / Chapter 4.2.3 --- Relaxation --- p.67 / Chapter 4.2.3.1 --- The 13C Relaxation --- p.67 / Chapter 4.2.3.2 --- The 59Co Relaxation --- p.71 / The Spin Rotation Interaction --- p.71 / The Temperature Behaviour of Relaxa- tion Rate --- p.72 / The Nuclear Quadru- pole Coupling Constant --- p.76 / The Correlation Time --- p.82 / Chapter 4.3 --- Summary --- p.90 / Chapter CHAPTER FIVE: --- CONCLUSION --- p.91 / REFERENCES --- p.94

by Andy Kwong Shun Tse. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaves 53-57). / ACKNOWLEDGMENTS --- p.i / ABBREVIATIONS --- p.ii / ABSTRACT --- p.iv / CONTENTS --- p.v / Chapter Part 1: --- Serendipitous Synthesis of Cobalt(III) and Rhodium (III) Porphyrin-phosphoryls / Chapter I. --- INTRODUCTION --- p.1 / Chapter II. --- RESULTS AND DISCUSSIONS --- p.6 / Chapter III. --- CONCLUSION --- p.28 / Chapter Part 2: --- Synthesis of Rhodium(III) Porphyrin-silyls / Chapter I. --- INTRODUCTION --- p.29 / Chapter II. --- RESULTS AND DISCUSSIONS --- p.32 / Chapter III. --- CONCLUSION --- p.41 / EXPERIMENTAL --- p.42 / REFERENCES --- p.53 / APPENDIX I-III --- p.58 / LIST OF SPECTRA --- p.61 / SPECTRA --- p.62

The reactions of cobalt halides with lithium dialkylamides have been investigated. The reaction with lithium diethylamide proved to be very unusual. This reaction was fully studied and the main products were shown to be lithium chloride, cobalt metal and bis(4-ethylimino-2-butene-2-ethylamino)Cob~lt(II). The latter product which was a volatile brown liquid was identified by its physical and . . chemical properties and the physical properties of derivatives prepared from the ligand after removal of the cobalt. Bis-(4-ethylimino-2-butene-2-ethylamino)cobalt(II) is a nitrogen analogue of the metal acetylacetonates and shows many similar properties. The ligand 4-ethylimino-2-ethylamino-2-butene • was shown, by the magnetic moment and electronic spectra of the tetrahedral cobalt compound, to produce a very high ligand field. A reaction mechanism has been proposed to explain the products 'of the reaction of cobalt chloride with lithium diethylamide. The reactions of other lithium dialkylamides with cobalt halides haye shown that dialkylamino compounds of cobalt(II) exist but are generally unstable thermally and very oxygen sensitive. The only stable (thermally) dialkylamino cobalt(II) compound prepared was bis-hexamethyldisilylamino cobalt(II). In solution this compound was shown· to be a linear two coordinate compound of cobalt(II). This unusual stereochemistry for cobalt(II) presents many theoretical problems before the magnetic and spectral properties ,are fully understood. It was found that the other dialkylamino cobalt(II) compounds produced were u!lstable.thermally decomposing above room temperature. The most stable compounds were formed when the dialkyl- group produced large steric hindrance. Two new alkolides were prepared from the dialkyamino cobalt(II) compounds. The magnetic and spectral properties of these compounds indicate that they are polymeric. possibly three coordinate compounds of cobalt.

Adverse tissue reactions to hip prostheses containing CoCr alloys have been widely reported, particularly for implants utilising a metal-on-metal bearing surface or, more recently, a modular taper junction and have been termed Adverse Response to Metal Debris (ARMD). Histological assessments of synovial tissues from patients at revision operation often demonstrate an extensive accumulation of macrophages and abundant tissue necrosis or fibrosis. The inflammatory response starts with the recruitment of immune cells and requires the egress of macrophages from the inflamed site for resolution of the reaction. Metal particles have previously been shown to affect cell migration but the effects of cobalt and chromium on macrophages' motility remain largely unknown. In vitro and in vivo macrophage migration during exposure to cobalt and chromium ions and nanoparticles were examined in this thesis. Cobalt, but not chromium, was found to significantly reduced macrophage motility (>50%). This was found to involve an increase in both cell spreading and the formation of intracellular podosome-type adhesion structures, as well as enhanced cell adhesion to the extracellular matrix (ECM). The formation of podosomes was also associated with the production and activation of matrix metalloproteinase-9 (MMP9) and enhanced ECM degradation. These effects were driven by the down-regulation of RhoA signalling through the generation of reactive oxygen species (ROS). The effect of the Co2+ and Cr3+ metal ions on tissue remodelling and pseudotumour formation which can lead to pain, swelling, limited range of joint movement and extensive tissue lesions, was explored using a multiscale approach. Both 2D and 3D in vitro culture systems were deplored to examine the effects of these ions on human fibroblast activation and mechanobiology. It was observed that Co2+ induced a fibrotic response characterised by cytoskeletal remodelling and enhanced collagen matrix contraction. This was associated with an increase in cell stiffness (~45%) and contractile forces (~80%) measured by atomic force microscopy and traction force microscopy, respectively. These effects were also triggered by the generation of ROS. Moreover, this fibrotic response was enhanced in the presence of macrophages, which increased the prevalence of α-SMA positive fibroblasts and collagen synthesis. These events were verified in vivo by examining the synovial fibroblasts and tissues from hips of patients with metal-on-metal hip implants and patients undergoing primary hip replacement. The findings revealed that fibroblasts isolated from patients undergoing MoM revision THA were more biomechanically active than the control group. Moreover, synovial tissues from patients undergoing MoM revision THA displayed evidence of extensive tissue remodelling and fibrosis. These findings revealed that cobalt leads to adverse tissue reactions via inducing macrophage retention, fibroblast-mediated matrix remodelling and modulating the interplay between macrophage and fibroblast. These distinctive effects can help us understand the pathogenesis of ARMD and the cellular response to cobalt-based alloys, which will inform biocompatibility test protocols and future implant designs.