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A dissertation submitted to the faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfilment of the requirements for the degree of Master of Science in Engineering – Chemical Engineering Johannesburg, 2017 / In this research, the C, H and O bond equivalent diagram was used to design processes for DME synthesis using natural gas as a feed. This research proposes alternative ways of producing DME using natural gas (a cleaner gas) compared to the traditional routes. The different feed combinations were assessed for the production of syngas. The crucial step is the H2:CO ratio in each feed which determines the DME synthesis process route and yield. The syngas process was developed under equilibrium and non-equilibrium conditions (assuming 100% methane conversion). The region of operation on the ternary bond diagram was limited by mass and energy balance and carbon deposition boundaries. The feed composition was as follows, (1) Feed 1: methane, steam and oxygen (2) Feed 2: methane, oxygen and carbon dioxide (3) Feed 3: methane, oxygen, carbon dioxide and water. Feed (2) had the highest DME yield. The most optimal reaction route produced DME via the JFE reaction route (H2:CO =1). The yield of DME was 0.67 moles of DME per mole methane processed under non-equilibrium conditions. The proposed route does not emit CO2, excess CO2 is recycled back to the reforming reactor. Under equilibrium, the yield of DME was 0.25 mole DME per mole methane processed. The results indicate that a combination of partial oxidation and dry reforming produces a syngas composition which results in a high DME yield compared to (1) and (3). / MT2017

Mycobacterium vaccae JOB5 and Graphium sp. were studied to evaluate their ability to cometabolize methyl tert-butyl ether (MTBE) and its metabolites after growth on two different alkanes, propane and iso-pentane. Both cultures were capable of cometabolizing MTBE and the metabolites, tert-butyl formate (TBF) and tert-butyl alcohol (TBA). MTBE, TBF, and TBA did not support growth of either microbe. Higher degradation rates were obtained in the bacterial system when the cultures were grown on iso-pentane. Nonlinear least squares regression and direct linear plot methods were used to estimate kinetic coefficients and provided comparable results. The enzymes from Mycobacterium vaccae JOB5 and Graphium sp. that promote the cometabolism of MTBE and its metabolites exhibited similar kinetics and substrate inhibition. The presence of the substrate decreased the degradation rate of MTBE and TBA suggesting competitive inhibition and preference for the substrate. Blockage experiment with acetylene suggested the presence of an alkane monooxygenase for the metabolism of MTBE and TBA, and a hydrolytic enzyme for the degradation of TBF. The presence of a hydrolase enzyme was supported by the fact that TBF was degraded to TBA under either aerobic or anaerobic conditions and was not inhibited by the presence of acetylene, propane, or isopentane. Measured rates of abiotic hydrolysis of TBF were significantly less than biodegradation rates. Acetylene acted as a reversible inhibitor for both cultures when tested in the presence of the growth media and as an inactivator when tested in the presence of a phosphate solution for the bacterial system. Growth-batch reactor experiments were conducted to compare the degradation of iso-pentane and MTBE with the predicted degradation rates based upon kinetic constants determined from single and dual-compound experiments. Experimental data was modeled with Monod kinetics and STELLA�� software. Reasonable predictions of reactor performance were achieved when Monod maximum utilization rates were increased compared to single and dual-compound experiments. / Graduation date: 2002

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This Thesis investigates the effect of membrane-active agents, such as synthetic ether lipids (SEL), local anaesthetics and polyunsaturated fatty acids (PUFAs) on human leukaemia cells. The two cell lines used were human acute myeloblastic leukaemia (HL60) cells and human myelogenous leukaemia (K562) cells. SEL, local anaesthetics and PUFAs were found to be cytotoxic to both cell lines at certain concentrations. The SEL ET-18-OCH(_3) was found to be cytotoxic to both cell lines but the HL60 cells were found to be the more sensitive cell line. HL60 cells were found to be so sensitive to the action of the local anaesthetic dibucaine that a subtoxic concentration that killed ≤10% was not determined. However, in K562 cells the combination of a subtoxic dibucaine concentration together with a range of ET-I8-OCH(_3) concentrations increased the cytotoxicity over that of ether lipid alone. PUFAs were shown to incorporate into plasma membrane phospholipids at concentrations as low as 1 μM after an incubation of 48 hours. PUFAs were shown to be cytotoxic, but the addition of vitamin E reduced the cytotoxicity of arachidonic acid, eicosapentaenoic acid and docosahexaenoic acid in HL60 cells, and of docosahexaenoic acid in K562 cells. This implied that lipid peroxidation was involved in PUFA cytotoxicity. This was, however, not confirmed. PUFA in combination with ET-I8-OCH3 resulted in a slight decrease in cytotoxicity. PUFA combined with dibucaine did not alter cytotoxicity. Cells were also treated with a combination of PUFA and 1-β-D- arabinofliranosylcytosine (ara-C), which is an agent known to induce cell differentiation. Onset of differentiation was determined by following haemoglobin accumulation in K562 cells. PUFA on their own were found to promote accumulation of haemoglobin. The greatest accumulation of haemoglobin was observed with K562 cells treated with PUFA and ara-C.

The derivatives of boradiazaindacene (BODIPY) are highly fluorescent dyes which have quantum yields near 1.0. These dyes that have exceptional spectral and photophysical stability as compared to other fluorescent groups are used for several different applications. The fluorescent sensor molecules for the detection of cations with PET (photoinduced-electron transfer) mechanism in general have been obtained by the differentiation of the BODIPY core. The extension of conjugation over the pyrrole ring shifts the absorption and emission at longer wavelength. Moreover, it is seen that red emission occurs from an ICT (intramolecular-charge transfer) state. iii In this study, we designed and synthesized an unsymetrically substituted BODIPY dye series, carrying a cation-sensitive phenylazacrown ether group conjugated to the core, and investigated the ion sensing properties of these compounds. Both aza-crown derivatives displayed selectivity towards Ca(II).