Magister Scientiae - MSc / In this study we report on the effect of the deposition parameters on the morphology and structural properties of CNTs, synthesized by means of the hot-wire chemical vapour deposition technique. SEM, Raman and XRD results show that the optimum deposition conditions for the HWCVD synthesis of aligned MWCNTs, with diameters between 50 and 150 nm and lengths in the micrometer range are: Furnace temperature of 500 ºC, deposition pressure between 150 and 200 Torr, methane/hydrogen dilution of 0.67 and a substrateto- filament distance of 10 cm. / South Africa

Analysis and results are presented from EXOSAT observations of Seyfert type active galactic nuclei (AGN). The sample chosen for study axe 48 hard X-ray selected Seyfert type AGN including all 29 of the emission line AGN in the Piccinotti sample making this the largest such survey to date. EXOSAT, its detectors and methods of data analysis axe detailed, with emphasis on background subtraction techniques. One of the most important new results from EXOSAT data is the discovery that rapid variability (factor 2 over a few thousand seconds) is common in AGN. No evidence is found in the sample sources for any characteristic timescales of variability. Combining EXOSAT LE and ME data allowed us to obtain broad band X-ray spectra over the range 0.1-10 keV. Spectra in the ∼ 2-10 keV range are found to be well described by a simple power-law. The distribution of spectral indices across the sample can be approximated by a Gaussian distribution of mean a = 0.70 and a = 0.17. The spectra are not all consistent with this mean at the 90% confidence level and there must some intrinsic spread in AGN slopes. This spread can be constrained to 0.14. EXOSAT has also revealed a significant number of sources with complex soft X-ray spectra. These include spectra with a second spectral component at soft X-ray energies and sources with ''leaky" absorbing columns. Evidence that soft excess components occur in at least 50% of Seyfert type AGN, together with detection of rapid variability in the soft component provides the strongest support to date for an accretion disc model for AGN.

M.Sc. / Aerosol samples were collected at stations using simple filter unit, loaded with a 4 7 mm diameter pore size Nuclepore membrane filter. The sampling duration was 24 hours for each sample, with the total of 11 samples: seven for Thohoyandou and four for Bethlehem. The samples were analyzed with energy dispersive X-ray fluorescence spectrometry for up to 20 elements. Comparison for elemental concentrations of the data showed that the samples fall into three clusters on average (major: Ca, Cl, Si. S, Fe and AI; intermediate: K, Ti, Pb, Brand Zn; minor: Mn, Cr, As, Sr, Ni and Cu), with the samples collected from Bethlehem having high concentrations in all clusters. High concentrations in the samples collected on Bethlehem were attributed to entrainement of dust particles during the dry winter period. The results also show that the elements are associated with anthropogenic emissions. Therefore, the sampling station at Thohoyandou is considered as a background station due to the low aerosol concentration. The aerosol concentration levels at Thohoyandou can be attributed to biogenic sources because of the large presence of large forest areas in the region and in the vicinity of the sampling location. The samples collected in both regions reveal highly enriched sulphur, chlorine, zinc and lead. It is clearly proved that these elements come from local soil. Chromium and copper were both slightly enriched in Thohoyandou, but the concentration data for these two elements are not available. However it is supposed that these elements come from local soil as well. In another aerosol analysis, passive (diffusive) samplers were used to measure concentration levels for sulphur dioxide and nitrogen dioxide. The measurement campaign was carried out from Soweto in Johannesburg and Bohlokong in Bethlehem with the campaign lasting for two months during the w~nter season. A very clear result derived for sulphur dioxide was the dominating source contribution from use of coal for heating and cooking in both areas. For nitrogen dioxide, it was found that contribution from traffic in highly populated areas and from industrial activities in the neighbourhood of the two areas was the source. The role played by wood burning, is also another additional source used for domestic heating and even cooking.

M.Sc. (Geology) / Refer to full text for abstract

Magister Scientiae - MSc / In this study, the capabilities of Neutron Radiography (NRad) and -Tomography (NTomo), as well as X-ray Radiography (XRad) to investigate chlorides and chlorides corrosion effects within steel reinforced laboratory concrete samples are practically explored. Capabilities of Scanning Electron Microscopy (SEM), Prompt Gamma Neutron Activation Analysis (PGNAA), Particle Induced X-ray Emission (PIXE), Small-Angle Neutron Scattering (SANS), Neutron Diffraction (NDIFF) and X-ray Diffraction (XDIFF) analytical techniques are also explored through review of literature.

Magister Pharmaceuticae - MPharm / In this study, new solid supramolecular derivatised forms of bis(adamantine-1-aminium) carbonate (ADTCO3) were prepared. ADTCO3 is a derivative of amantadine used for Parkinson’s disease and has antiviral properties against influenza-A, dengue fever and pharmacological activity towards Parkinson’s disease. The new forms prepared were polymorphic and co-crystal forms of ADTCO3. Polymorphism is a phenomenon where the ability of a substance to exist in two or more crystalline forms occurs when crystallised under different conditions and co-crystallization is the process of formation of multicomponent crystals of a drug substance. New solid forms often display different mechanical, physicochemical and thermal properties that can remarkably influence the bioavailability, hygroscopicity and stability of active pharmaceutical ingredients (APIs). For the formation of polymorphs of ADTCO3, techniques such as dry grinding, solvent-drop grinding, co-precipitation, sublimation and vapour diffusion were applied. For the development of co-crystals and/or complex formation, ADTCO3 was treated in combination with ten selected co-formers viz; benzoic acid, 4-hydroxybenzoic acid, cinnamic acid, 4-hydroxycinnamic acid, succinic acid, tartaric acid, salicylic acid, L-glutamic acid, citric acid monohydrate and L-glutaric acid using similar techniques as applied in the polymorphism study. The first four co-formers were selected for their potential biological activity and the latter six were selected for their generally regarded as safe (GRAS) status. All products were isolated and characterized using different analytical techniques to assess the thermal behaviour of the products by hot stage microscopy (HSM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). FTIR spectroscopy and proton-nuclear magnetic resonance (1HNMR) were used to identify and determine the purity of the parent compounds and the modified forms. X-ray powder diffraction was used to determine the formation of a new phase and single crystal X-ray diffraction was applied at the initial stages to identify ADTCO3 by its unit cell parameters. Furthermore, the Cambridge Structural Database (CSD) and other resources were used to generate information on the molecular structures of all elucidated parent compounds, their polymorphs and reported co-crystals. Four different polymorphic forms of ADTCO3 were identified (viz. ADTCO3 Forms I to IV) and sixteen co-crystals (viz. ADTCO3BA1 to ADTCO3BA5, ADTCO3HBA, ADTCO3CIN, ADTCO3HCIN, ADTCO3SUC, ADTCO3LTTA, ADTCO3SA, ADTCO3CA, ADTCO3GLA, ADTCO3GA) were synthesised. Of the sixteen co-crystals 5 were identified as ADTCO3BA “salt” co-crystal polymorphic forms and 2 as ADTCO3SUC co-crystal polymorphic forms. Two solvated “salt” co-crystal forms were also identified, namely; ADTCO3GLA and ADTCO3LTTA. ADTCO3GLA had a mass loss of 10.3% (n = 2.4) and ADTCO3LTTA had a mass loss of 5.25% (n = 0.86). Finally, the rest of the co-crystals ADTCO3HBA, ADTCO3CIN, ADTCO3HCIN, ADTCO3SA, ADTCO3CA and ADTCO3GA all crystallised as “salt” co-crystals.

No description available.

Histone H3 lysine 4 (H3K4) methylation is an evolutionarily conserved mark commonly associated with transcription activation in eukaryotes. In mammals, this post-translational modification is deposited by the KMT2 family of H3K4 methyltransferases. Biochemical studies have shown that the enzymatic activity of the KMT2 enzymes is regulated by a core complex of four evolutionarily conserved proteins: WDR5, RbBP5, ASH2L and DPY30, collectively known as WRAD, which are all important for global H3K4 methylation. However, how these proteins interact and regulate the activity of the KMT2 enzymes is not well investigated. During my PhD, I have used structural and biochemical approaches to determine the interactions underlying formation of the core complex and regulation of KMT2 enzymatic activity. My research have shown that 1) WDR5 uses two peptide-binding clefts on opposite sides of its β-propeller domain to bridge the KMT2 enzymes to the regulatory subunit RbBP5, 2) the WDR5 peptidyl-arginine-binding cleft exhibits plasticity to accommodate the binding of all KMT2 enzymes and 3) RbBP5 S350 phosphorylation stimulates formation of the RbBP5-ASH2L complex and H3K4 methylation by the mammalian KMT2 enzymes. Collectively, these studies have provided the structural basis for understanding the important interactions governing KMT2 complex assembly and activity.

The molecular and crystal structures of dibenzobarrelene and a number of its diester derivatives, and three dibenzosemibullvalenes have been determined by the use of X-ray crystallography. The objectives of the study were to investigate whether or not the di-π-methane photorearrangement could be carried out in the solid state, and how such solid state results would differ from results obtained in solution. In addition, we were interested in investigating the extent to which intermolecular steric effects would modulate or change the course of the photorearrangement in the solid state as compared to its solution pathway with the view of developing a structure-reactivity correlation for the reaction in the solid state. All the dibenzobarrelenes underwent the di-π-methane photorearrangement in the solid state to give the corresponding dibenzosemibullvalene photoproduct(s). In the symmetrical 11,12-diester derivatives of dibenzobarrelene, only one di-π-methane photoproduct could be identified for each of the reactants. The ethyl/ethyl and isopropyl/iso-propyl diester derivatives displayed polymorphism. An absolute asymmetric synthesis was performed on one of the dimorphs of the iso-propyl/iso-propyl derivative which crystallized in a chiral space group, and a quantitative enantiomeric excess yield was obtained. The molecular structures of all the compounds studied showed different degrees of conjugation of the ester carbonyl groups to the central vinyl bond. The unsymmetrical 11,12-diester derivatives yielded regioisomeric dibenzosemibullvalene photoproducts. Generally, the reactions in the solid state were found to be more regioselective than the same reactions in solution. The observed differences of the relative quantities of regioisomeric photoproducts in the solid state are interpreted on the basis of intermolecular steric effects. In appropriate systems, intermolecular steric effects may be used to predict successfully not only the major regioisomeric product of a di-π-methane photorearrangement in the solid state, but also the major enantiomeric product. One regioisomeric photoproduct is obtained for each 9,11 and 10,11-diester derivative. The photoproducts obtained from these unsymmetrical 9,11 and 10,11-diester derivatives of dibenzobarrelene show that electronic effects may be the dominant factor which governs the photochemical reaction pathway of this class of compounds in the solid state. Overall, intermolecular steric hindrance and electronic factors affect the solid state photochemical pathway of each compound to different extents. There appears to be an interplay of electronic and steric factors in determining the reaction pathway which leads to the major product in the solid state. The dominance of one factor (steric versus electronic) over the other in the determination of the most favorable photochemical pathway is dependent upon the conformations of the ester groups and their relative extents of conjugation to the central vinyl bond, and the relative intermolecular steric environments of the ester groups or substituents involved in the first step (vinyl-benzo bridging) of the photochemical reaction. / Science, Faculty of / Chemistry, Department of / Graduate

X-ray Computer Tomography (CT) is well suited to the inspection of Fibre-Reinforced-Plastic (FRP) composite materials. However, a range of limitations currently restrict its uptake. The aim of the present research was to develop advanced inspection procedures that overcome these limitations and increase the scope of composite structures that can be inspected by industrial cone beam CT. Region of Interest (ROI) CT inspection of FRP laminated panels was investigated and two data completion methods developed to overcome reconstruction errors caused by truncated projection data. These allow accurate, highly magnified regions to be reconstructed on objects that extend beyond the Field-of-View (FOV) of the detector. The first method extended the truncated projection data using a cosine signal tailing off to zero attenuation. This method removed the strong 'glowing' artefacts but an inherent error existed across the reconstructed ROI. This did not affect the defect detectability of the inspection but was viewed as problematic for applications requiring accurate density measurements. The second method used prior knowledge of the test object so that a model could be created to estimate the missing data. This technique removed errors associated with ROI reconstruction thus significantly improving the accuracy. Techniques for extending the FOV were developed and applied to the inspection of FRP wind turbine blades; over 1.5X larger than the conventional scanning FOV. Two data completion methods were developed requiring an asymmetrically positioned detector. The first was based on the cosine tailing technique and the second used fan beam ray redundancy properties to estimate the missing data. Both produced accurate reconstructions for the 'offset' projection data, demonstrating that it was possible to approximately double the FOV. The cosine tailing method was found to be the more reliable. A dual energy image CT technique was developed to extend the optimum dynamic range and improve defect detectability for multi-density objects. This was applied to FRP composite/Titanium lap joints showing improved detectability of both volumetric and planar defects within the low density FRP. The dual energy procedure was validated using statistical performance measures on a specially fabricated multi-density phantom. The results showed a significant improvement in the detail SNR when compared to conventional CT scans.