On the characterisation of diffused light and optical elements in high concentrator photovoltaic modules
- Authors: Schultz, Ross Dane
- Date: 2015
- Subjects: Photovoltaic cells , Solar concentrators , Optical materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/5170 , vital:20817
- Description: High Concentrated Photovoltaics (H-CPV) promise a more efficient, higher power output than traditional photovoltaic modules. This is achieved by concentrating sunlight onto a small triple junction (CTJ) InGaP/InGaAs/Ge cell (ranging from 3.14 mm2 to 1 cm2) by using precision optical systems. These systems utilise non-imaging optics to concentrate and distribute the incident solar flux uniformly onto the CTJ device receiver to achieve maximum performance and power output from an H-CPV module. However, the performance of the device can be reduced due to the partial or complete absorption of a range of wavelengths present in the solar spectrum by the optical materials that are used for concentration. An investigation to determine the current density topographies of each subcell in a CTJ cell by multiple raster scans of an optical fibre receiver of a spectrometer in the plane of the aperture of the secondary’s optical element was conducted. Results showed that the physical properties of the optical elements’ material absorbed different amounts of the spectral content with respect to the subcell photosensitive wavelength regions. The facet properties of the primary optical Fresnel lens showed that the more rounded the Fresnel facets were, the lower the concentration of sunlight incident onto the CTJ cell. The increase in facet numbers showed an increase in scattering of the incident sunlight and chromatic aberrations. Chromatic aberration created by the refractive optics showed a variation in the amount of concentration on each individual subcell as well as the difference in intensity profiles across for the different subcells. Based on these results and the development of new multi-junction devices by industry, the performance of a four and six-junction device with the optical materials was investigated by simulations. The simulations showed that the careful integration of an additional subcell in a multi-junction device could rectify current mismatch between the subcells in the device. Based on the simulations, the best performing multi-junction cell was identified as the four-junction device that showed a cell and module efficiency under operation of 42.5 % and 35.5 %, respectively. Additionally, based on the performance results observed from the H-CPV module, the development of an HCPV module that would attempt to harness the incident tracked diffuse sunlight available to a concentrator photovoltaic (CPV) module for additional energy yield was undertaken. The part of the study comprised of measurements of the solar source, design of a prototype Hybrid High Concentrator Photovoltaic (HH-CPV) module. Results showed that power generation from the H-CPV system was highly dependent on the DNI levels and fluctuates greatly with variation in the DNI. The irradiance levels within the diffuse regions of the H-CPV module showed that the baseplate and vertical sides had an average irradiance range of 140-450 and 50-225 W.m-2, respectively. Irradiance topographic raster scans revealed that the baseplate and vertical sides had a relatively uniform intensity distribution and was identified as favourable sites for diffuse cell population. Simulations of various PV technologies showed the most suitable technology for the placement within the cavity of the HH-CPV module. The developed HH-CPV module was finalized with the utilization of CIS modules to harness the diffuse irradiance. During a 3 month power monitoring of the HH-CPV system, it was determined that the major power generation for the HH-CPV module come from the CPV component, while the CIS modules showed a minor power contribution. The total energy yield for the monitoring period was 45.99, 3.89 and 1.76 kW.h for the CPV, four-vertical sides and baseplate components, respectively. The increase in energy yield of the HH-CPV module when compared to the standard H-CPV module was determined to be 12.35 % for the monitoring period. The incorporation of the CIS modules into the H-CPV module to create the HH-CPV module did increase the energy yield of the module during high DNI conditions and did offset the almost zero power generation during low DNI conditions.
- Full Text:
- Date Issued: 2015
- Authors: Schultz, Ross Dane
- Date: 2015
- Subjects: Photovoltaic cells , Solar concentrators , Optical materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/5170 , vital:20817
- Description: High Concentrated Photovoltaics (H-CPV) promise a more efficient, higher power output than traditional photovoltaic modules. This is achieved by concentrating sunlight onto a small triple junction (CTJ) InGaP/InGaAs/Ge cell (ranging from 3.14 mm2 to 1 cm2) by using precision optical systems. These systems utilise non-imaging optics to concentrate and distribute the incident solar flux uniformly onto the CTJ device receiver to achieve maximum performance and power output from an H-CPV module. However, the performance of the device can be reduced due to the partial or complete absorption of a range of wavelengths present in the solar spectrum by the optical materials that are used for concentration. An investigation to determine the current density topographies of each subcell in a CTJ cell by multiple raster scans of an optical fibre receiver of a spectrometer in the plane of the aperture of the secondary’s optical element was conducted. Results showed that the physical properties of the optical elements’ material absorbed different amounts of the spectral content with respect to the subcell photosensitive wavelength regions. The facet properties of the primary optical Fresnel lens showed that the more rounded the Fresnel facets were, the lower the concentration of sunlight incident onto the CTJ cell. The increase in facet numbers showed an increase in scattering of the incident sunlight and chromatic aberrations. Chromatic aberration created by the refractive optics showed a variation in the amount of concentration on each individual subcell as well as the difference in intensity profiles across for the different subcells. Based on these results and the development of new multi-junction devices by industry, the performance of a four and six-junction device with the optical materials was investigated by simulations. The simulations showed that the careful integration of an additional subcell in a multi-junction device could rectify current mismatch between the subcells in the device. Based on the simulations, the best performing multi-junction cell was identified as the four-junction device that showed a cell and module efficiency under operation of 42.5 % and 35.5 %, respectively. Additionally, based on the performance results observed from the H-CPV module, the development of an HCPV module that would attempt to harness the incident tracked diffuse sunlight available to a concentrator photovoltaic (CPV) module for additional energy yield was undertaken. The part of the study comprised of measurements of the solar source, design of a prototype Hybrid High Concentrator Photovoltaic (HH-CPV) module. Results showed that power generation from the H-CPV system was highly dependent on the DNI levels and fluctuates greatly with variation in the DNI. The irradiance levels within the diffuse regions of the H-CPV module showed that the baseplate and vertical sides had an average irradiance range of 140-450 and 50-225 W.m-2, respectively. Irradiance topographic raster scans revealed that the baseplate and vertical sides had a relatively uniform intensity distribution and was identified as favourable sites for diffuse cell population. Simulations of various PV technologies showed the most suitable technology for the placement within the cavity of the HH-CPV module. The developed HH-CPV module was finalized with the utilization of CIS modules to harness the diffuse irradiance. During a 3 month power monitoring of the HH-CPV system, it was determined that the major power generation for the HH-CPV module come from the CPV component, while the CIS modules showed a minor power contribution. The total energy yield for the monitoring period was 45.99, 3.89 and 1.76 kW.h for the CPV, four-vertical sides and baseplate components, respectively. The increase in energy yield of the HH-CPV module when compared to the standard H-CPV module was determined to be 12.35 % for the monitoring period. The incorporation of the CIS modules into the H-CPV module to create the HH-CPV module did increase the energy yield of the module during high DNI conditions and did offset the almost zero power generation during low DNI conditions.
- Full Text:
- Date Issued: 2015
Synthesis, characterisation and antitumour activities of lanthanide complexes with hydrazones and carboxylic acid ligands
- Authors: Madanhire, Tatenda
- Date: 2020
- Subjects: Organic acids
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/48456 , vital:40878
- Description: The tridentate hydrazone ligands, (E)-N'-(2-hydroxybenzylidene)benzohydrazide (H2phen) and (E)-N'-(2-hydroxybenzylidene)nicotinohydrazide (H2Nic), were synthesised and complexed to Ln(III) acetates. The centrosymmetric, acetato-bridged dinuclear coordination compounds with the formulae, [La2(Hphen)2(OAc)4(H2O)2]·DMF·H2O (1), [Ln2(HNic)2(OAc)4(H2O)2]·DMF·H2O (Ln = La (2) and Nd (3)) and [Ln2(HNic)2(OAc)4(H2O)2]·DMF (Ln = Er (4) and Yb (5)) were isolated and characterised by elemental analyses, IR spectroscopy, UV-Vis spectroscopy, X-ray diffraction studies and SHAPE 2.1. The nine-coordinate complexes 1–3 crystallise in the triclinic space group P-1, with the metal centres having the distorted spherical capped square antiprism geometry (C4v), while the eight-coordinate Er(III) and Yb(III) complexes (monoclinic system, space group P21/c) display the geometry of distorted triangular dodecahedron (D2d). Geometry optimisation of the monoanionic forms of the hydrazone ligands (Hphen– and HNic– ) were performed using Density Functional Theory (DFT) with Becke’s three parameter hybrid method and correlation functional of Lee, Yang and Parr (B3LYP) with augcc-pVTZ basis set. Natural population analysis (NPA) and molecular electrostatic potential (MEP) maps indicated that the most preferred sites for electrophilic attack in the anionic ligands are the phenolate and carbonyl oxygens, and the azomethine nitrogens. The evaluation of the cytotoxic activity of the compounds on breast cancer (MCF-7), the endometrial carcinoma (HEC-1A) and the human monocytic (THP-1) cell lines using the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl tetrazolium bromide (MTT) assay revealed that the hydrazone ligands and complexes 1–4 are partially cytotoxic against MCF-7 cells, while the Schiff bases and complexes 3–5 significantly inhibit cell growth in HEC-1A cells. The complexation reactions of Ce(III), Nd(III), Gd(III) and Er(III) with the chelating/ bridging monoanionic ligand N-(2,6-dimethylphenyl)oxamate (Hpma– ) in basic media were performed in view of the potential applications of oxamate derivatives as cytotoxic agents. The coordination compounds were characterised by different Abstract T. Madanhire Nelson Mandela University xxvi physico-chemical techniques: elemental analysis, conductivity measurements, IR, 1 H NMR and UV-Vis-NIR spectroscopy. The anionic Hpma– was obtained through conversion of the proligand ethyl (2,6-dimethylphenylcarbamoyl)formate (Hdmp). The reactions afforded lanthanide(III)–oxamate coordination polymers of formulae: {[Ln(Hpma)3(MeOH)(H2O)]∙2MeOH}n (Ln = Ce (1) and Nd (2)), {[Gd2(Hpma)6(MeOH)4]∙6MeOH}n (3), {[Er2(Hpma)6(MeOH)(H2O)3]∙2MeOH}n (4) and [Ln2Na2(Hpma)8(EtOH)(H2O)6]n (Ln = Nd (5) and Gd (6)). The polymeric complexes feature Ln-Hpma moieties bridged by μ2-η 1 :η 1 :η 1 Hpma– , giving onedimensional zig-zag chains of the –Ln–O–C–O–Ln– type. Atomic charge analysis and the MEP map of the Hpma– moiety done using the DFT/B3LYP method were found to be consistent with the chelating and bridging modes of the anionic ligand through all the oxygen atoms. The evaluation of the cytotoxic activities of the metal salts, the proligand and the novel lanthanide complexes on MCF-7, HEC-1A and THP-1 cell lines revealed that only the rare-earth metal salts [Ce(NO3)3∙6H2O] and [Nd(NO3)3∙6H2O] showed modest cytotoxicity against MCF-7 and HEC-1A cells, respectively.
- Full Text:
- Date Issued: 2020
- Authors: Madanhire, Tatenda
- Date: 2020
- Subjects: Organic acids
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/48456 , vital:40878
- Description: The tridentate hydrazone ligands, (E)-N'-(2-hydroxybenzylidene)benzohydrazide (H2phen) and (E)-N'-(2-hydroxybenzylidene)nicotinohydrazide (H2Nic), were synthesised and complexed to Ln(III) acetates. The centrosymmetric, acetato-bridged dinuclear coordination compounds with the formulae, [La2(Hphen)2(OAc)4(H2O)2]·DMF·H2O (1), [Ln2(HNic)2(OAc)4(H2O)2]·DMF·H2O (Ln = La (2) and Nd (3)) and [Ln2(HNic)2(OAc)4(H2O)2]·DMF (Ln = Er (4) and Yb (5)) were isolated and characterised by elemental analyses, IR spectroscopy, UV-Vis spectroscopy, X-ray diffraction studies and SHAPE 2.1. The nine-coordinate complexes 1–3 crystallise in the triclinic space group P-1, with the metal centres having the distorted spherical capped square antiprism geometry (C4v), while the eight-coordinate Er(III) and Yb(III) complexes (monoclinic system, space group P21/c) display the geometry of distorted triangular dodecahedron (D2d). Geometry optimisation of the monoanionic forms of the hydrazone ligands (Hphen– and HNic– ) were performed using Density Functional Theory (DFT) with Becke’s three parameter hybrid method and correlation functional of Lee, Yang and Parr (B3LYP) with augcc-pVTZ basis set. Natural population analysis (NPA) and molecular electrostatic potential (MEP) maps indicated that the most preferred sites for electrophilic attack in the anionic ligands are the phenolate and carbonyl oxygens, and the azomethine nitrogens. The evaluation of the cytotoxic activity of the compounds on breast cancer (MCF-7), the endometrial carcinoma (HEC-1A) and the human monocytic (THP-1) cell lines using the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl tetrazolium bromide (MTT) assay revealed that the hydrazone ligands and complexes 1–4 are partially cytotoxic against MCF-7 cells, while the Schiff bases and complexes 3–5 significantly inhibit cell growth in HEC-1A cells. The complexation reactions of Ce(III), Nd(III), Gd(III) and Er(III) with the chelating/ bridging monoanionic ligand N-(2,6-dimethylphenyl)oxamate (Hpma– ) in basic media were performed in view of the potential applications of oxamate derivatives as cytotoxic agents. The coordination compounds were characterised by different Abstract T. Madanhire Nelson Mandela University xxvi physico-chemical techniques: elemental analysis, conductivity measurements, IR, 1 H NMR and UV-Vis-NIR spectroscopy. The anionic Hpma– was obtained through conversion of the proligand ethyl (2,6-dimethylphenylcarbamoyl)formate (Hdmp). The reactions afforded lanthanide(III)–oxamate coordination polymers of formulae: {[Ln(Hpma)3(MeOH)(H2O)]∙2MeOH}n (Ln = Ce (1) and Nd (2)), {[Gd2(Hpma)6(MeOH)4]∙6MeOH}n (3), {[Er2(Hpma)6(MeOH)(H2O)3]∙2MeOH}n (4) and [Ln2Na2(Hpma)8(EtOH)(H2O)6]n (Ln = Nd (5) and Gd (6)). The polymeric complexes feature Ln-Hpma moieties bridged by μ2-η 1 :η 1 :η 1 Hpma– , giving onedimensional zig-zag chains of the –Ln–O–C–O–Ln– type. Atomic charge analysis and the MEP map of the Hpma– moiety done using the DFT/B3LYP method were found to be consistent with the chelating and bridging modes of the anionic ligand through all the oxygen atoms. The evaluation of the cytotoxic activities of the metal salts, the proligand and the novel lanthanide complexes on MCF-7, HEC-1A and THP-1 cell lines revealed that only the rare-earth metal salts [Ce(NO3)3∙6H2O] and [Nd(NO3)3∙6H2O] showed modest cytotoxicity against MCF-7 and HEC-1A cells, respectively.
- Full Text:
- Date Issued: 2020
The survival of micro -enteprises in Kampala, Uganda :a substainable livelihoods approach
- Authors: Twinorugyendo,Penninah
- Date: 2016
- Subjects: Microfinance -- Uganda -- Kampala New Business Enterprises -- Uganda -- Kampala -- Finance , Small business -- Uganda -- Kampala
- Language: English
- Type: Thesis , Doctoral , PHD
- Identifier: http://hdl.handle.net/10948/45333 , vital:38571
- Description: This purpose of this thesis was to explain the resilience of certain micro-enterprises (MEs) in Kampala, Uganda – by focusing on their vulnerability, the assets that they brought to bear on the situation, the role of non-governmental organizations and government institutions in supporting MEs, and the strategies used by ME owners, themselves. As such, it adopts the Sustainable-Livelihoods approach – an approach that has not been used in Kampala before. Thus, it makes a valuable contribution to the field. Designed as a qualitative study, it used in-depth interviews and focus-group discussions. The major findings on vulnerability were linked to: the rising cost of materials; unfair licensing; the struggle to win tenders; local and foreign competition; and the disruption of utilities. The assets used to sustain the welfare of the MEs included: making use of a range of skill-acquisition strategies; leveraging networks; and pooling resources. Financial assets used by MEs revolved around informal savings and credit schemes; but the support given to the MEs through government agencies and NGOs was difficult to assess. Several important strategies were used by ME owners. One of these involved linking with formal construction companies. In addition, temporary workshops constructed out of wood-and-iron, were common. This increased mobility and allowed the re-use of materials. Furthermore, MEs manufactured their own tools, developed new marketing techniques, and diversified their income-generating activities. The significance of this study is two-pronged. It demonstrates that the resilience of MEs does depend on their own positive qualities, but also on an increasingly business-friendly national and international economic environment.
- Full Text:
- Date Issued: 2016
- Authors: Twinorugyendo,Penninah
- Date: 2016
- Subjects: Microfinance -- Uganda -- Kampala New Business Enterprises -- Uganda -- Kampala -- Finance , Small business -- Uganda -- Kampala
- Language: English
- Type: Thesis , Doctoral , PHD
- Identifier: http://hdl.handle.net/10948/45333 , vital:38571
- Description: This purpose of this thesis was to explain the resilience of certain micro-enterprises (MEs) in Kampala, Uganda – by focusing on their vulnerability, the assets that they brought to bear on the situation, the role of non-governmental organizations and government institutions in supporting MEs, and the strategies used by ME owners, themselves. As such, it adopts the Sustainable-Livelihoods approach – an approach that has not been used in Kampala before. Thus, it makes a valuable contribution to the field. Designed as a qualitative study, it used in-depth interviews and focus-group discussions. The major findings on vulnerability were linked to: the rising cost of materials; unfair licensing; the struggle to win tenders; local and foreign competition; and the disruption of utilities. The assets used to sustain the welfare of the MEs included: making use of a range of skill-acquisition strategies; leveraging networks; and pooling resources. Financial assets used by MEs revolved around informal savings and credit schemes; but the support given to the MEs through government agencies and NGOs was difficult to assess. Several important strategies were used by ME owners. One of these involved linking with formal construction companies. In addition, temporary workshops constructed out of wood-and-iron, were common. This increased mobility and allowed the re-use of materials. Furthermore, MEs manufactured their own tools, developed new marketing techniques, and diversified their income-generating activities. The significance of this study is two-pronged. It demonstrates that the resilience of MEs does depend on their own positive qualities, but also on an increasingly business-friendly national and international economic environment.
- Full Text:
- Date Issued: 2016
An evaluation and comparison of the plasticiser effects of p -Menthane-3,8-diol-citronellal acetal plasticiser with triethyl citrate and bis(2-ethylhexyl) terephthalate on ethylcellulose films.
- Authors: Marx, Johannes Scheepers
- Date: 2019
- Subjects: Plasticisers
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/44629 , vital:38164
- Description: In recent years, much attention has been focused on research to replace petroleumbased commodity plastics, in a cost-effective manner, with biodegradable materials offering competitive mechanical properties. The use of natural and/or biodegradable plasticisers, with low toxicity and good compatibility with several plastics, resins, rubber and elastomers in substitution of conventional plasticisers, such as phthalates and other synthetic plasticisers attract the market along with the increasing worldwide trend towards the use of bio-polymers. The main research objective entailed the behaviour of the novel bio-plasticiser PMDcitronellal acetal (PMD-CA) and its comparison with other commercial bio-plasticiser, triethyl citrate (TEC) and a non-phthalate plasticiser bis(2-ethylhexyl) terephthalate (DOTP), on ethylcellulose (EC) films to evaluate whether it would be feasible to replace them with PMD-CA. The films were produced by a casting technique and were characterised by mechanical properties, thermoanalysis, Scanning Electron Microscopy, disintegration and Fourier-Transform Infrared (FT-IR) spectroscopy. The addition of any of the three plasticisers to EC film increased the flexibility of the films. The plasticisers PMD-CA and DOTP added to EC formed tougher films as compared to EC films containing TEC shown by the high % elongation at break, strain and displacement. Statistically, it was proved that PMD-CA and DOTP had a more significant effect on % elongation of EC films than TEC, postulated to be due to their similar molecular size and structure. Thermoanalytical studies conducted revealed that the thermal degradation process of EC films proceeded in three basic stages, namely dehydration, depolymerisation and pyrolytic decomposition. Thermoanalytical analysis showed that unplasticised EC films had a higher glass transition value compared to the films containing any of the plasticisers and that PMD-CA and DOTP are more effective plasticisers compared to TEC due to their lower glass transition temperatures. The presence of plasticisers in the polymer matrix did change the surface morphology of polymer films. The addition of hydroxypropyl methylcellulose (HPMC) to EC PMD-CA and EC DOTP films caused more significant globule-like bubbles which were not uniform in size on the surface of these films. Observations were made that the type of plasticiser coating with or without pore former influenced the disintegration properties of films. HPMC, as pore former, played a significant role in the drug release system matrix. EC PMD-CA and EC DOTP polymeric films controlled the disintegration of the films in the acidic and weakly acidic medium. EC and EC TEC films had less significant control on the disintegration rate of the acidic and weakly acidic disintegration media. FT-IR characterisation of the films revealed comparable peaks observed in all the polymer-plasticiser combinations and therefore it was concluded that chemical interactions did not exist between the polymers and plasticisers. Added excipients (plasticisers and pore formers) were found to be compatible with EC films. It was concluded within the scope of this research that EC films plasticised with PMDCA, DOTP or TEC outperformed film properties of those compared to unplasticised EC film. The plasticising properties of the novel bio-plasticiser PMD-CA are similar compared to DOTP, and superior to triethyl citrate and could therefore be considered as an effective bioplasticiser for enteric coating formulations in the pharmaceutical industry.
- Full Text:
- Date Issued: 2019
- Authors: Marx, Johannes Scheepers
- Date: 2019
- Subjects: Plasticisers
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/44629 , vital:38164
- Description: In recent years, much attention has been focused on research to replace petroleumbased commodity plastics, in a cost-effective manner, with biodegradable materials offering competitive mechanical properties. The use of natural and/or biodegradable plasticisers, with low toxicity and good compatibility with several plastics, resins, rubber and elastomers in substitution of conventional plasticisers, such as phthalates and other synthetic plasticisers attract the market along with the increasing worldwide trend towards the use of bio-polymers. The main research objective entailed the behaviour of the novel bio-plasticiser PMDcitronellal acetal (PMD-CA) and its comparison with other commercial bio-plasticiser, triethyl citrate (TEC) and a non-phthalate plasticiser bis(2-ethylhexyl) terephthalate (DOTP), on ethylcellulose (EC) films to evaluate whether it would be feasible to replace them with PMD-CA. The films were produced by a casting technique and were characterised by mechanical properties, thermoanalysis, Scanning Electron Microscopy, disintegration and Fourier-Transform Infrared (FT-IR) spectroscopy. The addition of any of the three plasticisers to EC film increased the flexibility of the films. The plasticisers PMD-CA and DOTP added to EC formed tougher films as compared to EC films containing TEC shown by the high % elongation at break, strain and displacement. Statistically, it was proved that PMD-CA and DOTP had a more significant effect on % elongation of EC films than TEC, postulated to be due to their similar molecular size and structure. Thermoanalytical studies conducted revealed that the thermal degradation process of EC films proceeded in three basic stages, namely dehydration, depolymerisation and pyrolytic decomposition. Thermoanalytical analysis showed that unplasticised EC films had a higher glass transition value compared to the films containing any of the plasticisers and that PMD-CA and DOTP are more effective plasticisers compared to TEC due to their lower glass transition temperatures. The presence of plasticisers in the polymer matrix did change the surface morphology of polymer films. The addition of hydroxypropyl methylcellulose (HPMC) to EC PMD-CA and EC DOTP films caused more significant globule-like bubbles which were not uniform in size on the surface of these films. Observations were made that the type of plasticiser coating with or without pore former influenced the disintegration properties of films. HPMC, as pore former, played a significant role in the drug release system matrix. EC PMD-CA and EC DOTP polymeric films controlled the disintegration of the films in the acidic and weakly acidic medium. EC and EC TEC films had less significant control on the disintegration rate of the acidic and weakly acidic disintegration media. FT-IR characterisation of the films revealed comparable peaks observed in all the polymer-plasticiser combinations and therefore it was concluded that chemical interactions did not exist between the polymers and plasticisers. Added excipients (plasticisers and pore formers) were found to be compatible with EC films. It was concluded within the scope of this research that EC films plasticised with PMDCA, DOTP or TEC outperformed film properties of those compared to unplasticised EC film. The plasticising properties of the novel bio-plasticiser PMD-CA are similar compared to DOTP, and superior to triethyl citrate and could therefore be considered as an effective bioplasticiser for enteric coating formulations in the pharmaceutical industry.
- Full Text:
- Date Issued: 2019
Enhanced visualisation techniques to support access to personal information across multiple devices
- Authors: Beets, Simone Yvonne
- Date: 2014
- Subjects: Information visualisation , Database management , Web services , Personal information management
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10500 , http://hdl.handle.net/10948/d1021136
- Description: The increasing number of devices owned by a single user makes it increasingly difficult to access, organise and visualise personal information (PI), i.e. documents and media, across these devices. The primary method that is currently used to organise and visualise PI is the hierarchical folder structure, which is a familiar and widely used means to manage PI. However, this hierarchy does not effectively support personal information management (PIM) across multiple devices. Current solutions, such as the Personal Information Dashboard and Stuff I’ve Seen, do not support PIM across multiple devices. Alternative PIM tools, such as Dropbox and TeamViewer, attempt to provide a means of accessing PI across multiple devices, but these solutions also suffer from several limitations. The aim of this research was to investigate to what extent enhanced information visualisation (IV) techniques could be used to support accessing PI across multiple devices. An interview study was conducted to identify how PI is currently managed across multiple devices. This interview study further motivated the need for a tool to support visualising PI across multiple devices and identified requirements for such an IV tool. Several suitable IV techniques were selected and enhanced to support PIM across multiple devices. These techniques comprised an Overview using a nested circles layout, a Tag Cloud and a Partition Layout, which used a novel set-based technique. A prototype, called MyPSI, was designed and implemented incorporating these enhanced IV techniques. The requirements and design of the MyPSI prototype were validated using a conceptual walkthrough. The design of the MyPSI prototype was initially implemented for a desktop or laptop device with mouse-based interaction. A sample personal space of information (PSI) was used to evaluate the prototype in a controlled user study. The user study was used to identify any usability problems with the MyPSI prototype. The results were highly positive and the participants agreed that such a tool could be useful in future. No major problems were identified with the prototype. The MyPSI prototype was then implemented on a mobile device, specifically an Android tablet device, using a similar design, but supporting touch-based interaction. Users were allowed to upload their own PSI using Dropbox, which was visualised by the MyPSI prototype. A field study was conducted following the Multi-dimensional In-depth Long-term Case Studies approach specifically designed for IV evaluation. The field study was conducted over a two-week period, evaluating both the desktop and mobile versions of the MyPSI prototype. Both versions received positive results, but the desktop version was slightly preferred over the mobile version, mainly due to familiarity and problems experienced with the mobile implementation. Design recommendations were derived to inform future designs of IV tools to support accessing PI across multiple devices. This research has shown that IV techniques can be enhanced to effectively support accessing PI across multiple devices. Future work will involve customising the MyPSI prototype for mobile phones and supporting additional platforms.
- Full Text:
- Date Issued: 2014
- Authors: Beets, Simone Yvonne
- Date: 2014
- Subjects: Information visualisation , Database management , Web services , Personal information management
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10500 , http://hdl.handle.net/10948/d1021136
- Description: The increasing number of devices owned by a single user makes it increasingly difficult to access, organise and visualise personal information (PI), i.e. documents and media, across these devices. The primary method that is currently used to organise and visualise PI is the hierarchical folder structure, which is a familiar and widely used means to manage PI. However, this hierarchy does not effectively support personal information management (PIM) across multiple devices. Current solutions, such as the Personal Information Dashboard and Stuff I’ve Seen, do not support PIM across multiple devices. Alternative PIM tools, such as Dropbox and TeamViewer, attempt to provide a means of accessing PI across multiple devices, but these solutions also suffer from several limitations. The aim of this research was to investigate to what extent enhanced information visualisation (IV) techniques could be used to support accessing PI across multiple devices. An interview study was conducted to identify how PI is currently managed across multiple devices. This interview study further motivated the need for a tool to support visualising PI across multiple devices and identified requirements for such an IV tool. Several suitable IV techniques were selected and enhanced to support PIM across multiple devices. These techniques comprised an Overview using a nested circles layout, a Tag Cloud and a Partition Layout, which used a novel set-based technique. A prototype, called MyPSI, was designed and implemented incorporating these enhanced IV techniques. The requirements and design of the MyPSI prototype were validated using a conceptual walkthrough. The design of the MyPSI prototype was initially implemented for a desktop or laptop device with mouse-based interaction. A sample personal space of information (PSI) was used to evaluate the prototype in a controlled user study. The user study was used to identify any usability problems with the MyPSI prototype. The results were highly positive and the participants agreed that such a tool could be useful in future. No major problems were identified with the prototype. The MyPSI prototype was then implemented on a mobile device, specifically an Android tablet device, using a similar design, but supporting touch-based interaction. Users were allowed to upload their own PSI using Dropbox, which was visualised by the MyPSI prototype. A field study was conducted following the Multi-dimensional In-depth Long-term Case Studies approach specifically designed for IV evaluation. The field study was conducted over a two-week period, evaluating both the desktop and mobile versions of the MyPSI prototype. Both versions received positive results, but the desktop version was slightly preferred over the mobile version, mainly due to familiarity and problems experienced with the mobile implementation. Design recommendations were derived to inform future designs of IV tools to support accessing PI across multiple devices. This research has shown that IV techniques can be enhanced to effectively support accessing PI across multiple devices. Future work will involve customising the MyPSI prototype for mobile phones and supporting additional platforms.
- Full Text:
- Date Issued: 2014
On the mocvd growth of ZnO
- Authors: Pagni, Olivier Demeno
- Date: 2004
- Subjects: Zinc oxide thin films , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11075 , http://hdl.handle.net/10948/382 , Zinc oxide thin films , Metal organic chemical vapor deposition
- Description: Zinc oxide (ZnO) is a II-VI semiconductor material that offers tremendous potential as a light emitter in the blue-to-UV range. It has a wurtzite structure, and a direct band gap that can be tuned from 3.0 to 4.0 eV by alloying with Cd or Mg, respectively. In this work, ZnO thin films were grown by metalorganic chemical vapor deposition (MOCVD) on n-Si 2 ° off (100), amorphous glass, n-GaAs (100), and c-plane sapphire substrates. Diethyl zinc (DEZn) and tert-butanol (TBOH) were chosen as precursors. For the first time, Second Harmonic Generation Imaging was applied to the mapping of ZnO epilayers. The images obtained highlighted the polycrystalline character of the thin films, and provided insight as to the growth mode of ZnO on Si. The influence of substrate temperature on the structural properties of the epilayers was investigated by X-ray diffraction and optical microscopy. Grain sizes as high as 54 nm were measured. The optimum temperature range for this system proved to be 450 – 500 °C. The influence of the VI:II ratio during growth on the optical properties of the epilayers was studied by UV-vis-near IR spectroscopy. The lowest Urbach tail E0 parameter was measured for material grown at a VI:II ratio of 18:1. The films’ free electron concentration was shown to decrease by over two orders of magnitude, from 1019 to 1017 cm-3, as the VI:II ratio increased from 10 to 60:1. This decrease in carrier concentration with rising VI:II ratio was paralleled to the surge at 12 K of a photoluminescence (PL) emission band characteristic of p-type ZnO. The band gap energies extracted from room temperature transmission spectra ranged between 3.35 and 3.38 eV, in agreement with the value of 3.35 eV measured by room temperature PL. Moreover, variable temperature PL spectra were recorded between 12 and 298 K on ZnO grown on Si. The 12 K spectrum was dominated by a donor-bound exciton (D°X) at 3.36 eV, while the 298 K scan displayed strong free exciton emission (FX) at 3.29 eV. The width of the D°X band proved to be as narrow as 7 meV. The intensity ratio between the room temperature near-band edge emission and the defect-related green band was as high as 28:1, highlighting the optical quality of the layers deposited in this work. The electrical properties of the thin films were studied by Hall measurements (van der Pauw configuration), and a maximum room temperature mobility of 11 cm2/Vs was recorded. Furthermore, a palladium (Pd) Schottky barrier diode on ZnO was fabricated. The barrier height and ideality factor were calculated from current–voltage measurements to be 0.83 eV and 1.6, respectively. The capacitance–voltage curve of the diode yielded a carrier concentration in the depletion region of 8·1017 cm-3. This study has shown that the optical and electrical properties of ZnO depend strongly on the growth conditions employed. A suitable choice of growth parameters can yield high quality ZnO that may be used for various devices. Keywords: Hall, MOCVD, optical spectroscopy, photoluminescence, Schottky barrier diode, SH Imaging, X-ray diffraction, ZnO.
- Full Text:
- Date Issued: 2004
- Authors: Pagni, Olivier Demeno
- Date: 2004
- Subjects: Zinc oxide thin films , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11075 , http://hdl.handle.net/10948/382 , Zinc oxide thin films , Metal organic chemical vapor deposition
- Description: Zinc oxide (ZnO) is a II-VI semiconductor material that offers tremendous potential as a light emitter in the blue-to-UV range. It has a wurtzite structure, and a direct band gap that can be tuned from 3.0 to 4.0 eV by alloying with Cd or Mg, respectively. In this work, ZnO thin films were grown by metalorganic chemical vapor deposition (MOCVD) on n-Si 2 ° off (100), amorphous glass, n-GaAs (100), and c-plane sapphire substrates. Diethyl zinc (DEZn) and tert-butanol (TBOH) were chosen as precursors. For the first time, Second Harmonic Generation Imaging was applied to the mapping of ZnO epilayers. The images obtained highlighted the polycrystalline character of the thin films, and provided insight as to the growth mode of ZnO on Si. The influence of substrate temperature on the structural properties of the epilayers was investigated by X-ray diffraction and optical microscopy. Grain sizes as high as 54 nm were measured. The optimum temperature range for this system proved to be 450 – 500 °C. The influence of the VI:II ratio during growth on the optical properties of the epilayers was studied by UV-vis-near IR spectroscopy. The lowest Urbach tail E0 parameter was measured for material grown at a VI:II ratio of 18:1. The films’ free electron concentration was shown to decrease by over two orders of magnitude, from 1019 to 1017 cm-3, as the VI:II ratio increased from 10 to 60:1. This decrease in carrier concentration with rising VI:II ratio was paralleled to the surge at 12 K of a photoluminescence (PL) emission band characteristic of p-type ZnO. The band gap energies extracted from room temperature transmission spectra ranged between 3.35 and 3.38 eV, in agreement with the value of 3.35 eV measured by room temperature PL. Moreover, variable temperature PL spectra were recorded between 12 and 298 K on ZnO grown on Si. The 12 K spectrum was dominated by a donor-bound exciton (D°X) at 3.36 eV, while the 298 K scan displayed strong free exciton emission (FX) at 3.29 eV. The width of the D°X band proved to be as narrow as 7 meV. The intensity ratio between the room temperature near-band edge emission and the defect-related green band was as high as 28:1, highlighting the optical quality of the layers deposited in this work. The electrical properties of the thin films were studied by Hall measurements (van der Pauw configuration), and a maximum room temperature mobility of 11 cm2/Vs was recorded. Furthermore, a palladium (Pd) Schottky barrier diode on ZnO was fabricated. The barrier height and ideality factor were calculated from current–voltage measurements to be 0.83 eV and 1.6, respectively. The capacitance–voltage curve of the diode yielded a carrier concentration in the depletion region of 8·1017 cm-3. This study has shown that the optical and electrical properties of ZnO depend strongly on the growth conditions employed. A suitable choice of growth parameters can yield high quality ZnO that may be used for various devices. Keywords: Hall, MOCVD, optical spectroscopy, photoluminescence, Schottky barrier diode, SH Imaging, X-ray diffraction, ZnO.
- Full Text:
- Date Issued: 2004
Characterization of WC-VC-Co and WC-VC-TiC-Co hardmetals
- Authors: Hashe, Nobom Gretta
- Date: 2007
- Subjects: Carbides , Hard materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10533 , http://hdl.handle.net/10948/522 , http://hdl.handle.net/10948/d1011723 , Carbides , Hard materials
- Description: This thesis contains the results of a study focused on cubic carbide and carbonitride grain growth retardation in hardmetals. Large additions of VC, or VC and TiC, or (W,V)C were made to the WC-Co hardmetal, which was then sintered in vacuum or nitrogen. The effectiveness of Ti as the grain growth inhibitor, and the influence of nitrogen sintering on grain coarsening were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffractrometry (XRD) and atom probe field ion microscope (APFIM). Analysis of vacuum-sintered WC-VC-Co revealed that the cubic carbide grains have a core-rim structure. Ti was found to be a core-rim inhibitor in vacuum-sintered WCVC- TiC-Co. The average cubic carbide grain size distribution for the vacuumsintered materials was narrowed in the Ti-containing hardmetal. The nitrogen-sintered WC-VC-TiC-Co consisted of two phases of cubic carbonitride, one with high Ti-content and the other with high (W,V)-content. The surface region of the nitrogen-sintered WC-VC-TiC-Co was covered with a cubic carbonitride phase. Similar phenomena was observed in nitrogen-sintered WC-VC-Co where two types of carbonitrides were found, those with high V-content and the others with low Vcontent. A gradient zone, consisting of fine WC grains in a Co-rich binder and free from cubic carbonitride grains, was created in the surface region. The nitrogensintered materials consisted of a narrow grain size distribution. The use of (W,V)C as a starting powder affected the mechanical properties of the material with the WC-(W,V)C-Co material being the hardest of those produced in this study. Addition of (W,V)C powder to WC-Co was shown to be the most effective way to limit the cubic carbide grain size during sintering and produce a hard material. The cubic carbide grain size in the material produced this way was the smallest of all studied.
- Full Text:
- Date Issued: 2007
- Authors: Hashe, Nobom Gretta
- Date: 2007
- Subjects: Carbides , Hard materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10533 , http://hdl.handle.net/10948/522 , http://hdl.handle.net/10948/d1011723 , Carbides , Hard materials
- Description: This thesis contains the results of a study focused on cubic carbide and carbonitride grain growth retardation in hardmetals. Large additions of VC, or VC and TiC, or (W,V)C were made to the WC-Co hardmetal, which was then sintered in vacuum or nitrogen. The effectiveness of Ti as the grain growth inhibitor, and the influence of nitrogen sintering on grain coarsening were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffractrometry (XRD) and atom probe field ion microscope (APFIM). Analysis of vacuum-sintered WC-VC-Co revealed that the cubic carbide grains have a core-rim structure. Ti was found to be a core-rim inhibitor in vacuum-sintered WCVC- TiC-Co. The average cubic carbide grain size distribution for the vacuumsintered materials was narrowed in the Ti-containing hardmetal. The nitrogen-sintered WC-VC-TiC-Co consisted of two phases of cubic carbonitride, one with high Ti-content and the other with high (W,V)-content. The surface region of the nitrogen-sintered WC-VC-TiC-Co was covered with a cubic carbonitride phase. Similar phenomena was observed in nitrogen-sintered WC-VC-Co where two types of carbonitrides were found, those with high V-content and the others with low Vcontent. A gradient zone, consisting of fine WC grains in a Co-rich binder and free from cubic carbonitride grains, was created in the surface region. The nitrogensintered materials consisted of a narrow grain size distribution. The use of (W,V)C as a starting powder affected the mechanical properties of the material with the WC-(W,V)C-Co material being the hardest of those produced in this study. Addition of (W,V)C powder to WC-Co was shown to be the most effective way to limit the cubic carbide grain size during sintering and produce a hard material. The cubic carbide grain size in the material produced this way was the smallest of all studied.
- Full Text:
- Date Issued: 2007
Advances in platinum-amine chemotherapeutic agents : their chemistry and applicationc
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
Ruthenium and palladium assisted silver transport in silicon carbide
- Authors: O'Connell, Jacques Herman
- Date: 2012
- Subjects: Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10404 , http://hdl.handle.net/10948/d1010960 , Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Full Text:
- Date Issued: 2012
- Authors: O'Connell, Jacques Herman
- Date: 2012
- Subjects: Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10404 , http://hdl.handle.net/10948/d1010960 , Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Full Text:
- Date Issued: 2012
Surface modifications of InAs: effect of chemical processing on electronic structure and photoluminescent properties
- Eassa, Nahswa Abo Alhassan Eassa
- Authors: Eassa, Nahswa Abo Alhassan Eassa
- Date: 2012
- Subjects: Indium arsenide , Chemical processes , Photoluminescence
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8714 , vital:26423
- Description: In this thesis, the effects of various chemical treatments on the surface modification of bulk InAs are investigated. The study focuses on the chemical processes that occur upon the exposure of the surface to sulphur-, chlorine- and bromine-containing solutions and oxygen, and the resulting changes to the electronic structure of the surface, as deduced from photoluminescence (PL) measurements, X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), Raman scattering and scanning electron microscopy (SEM). Three processing treatments were evaluated: i) treatment with sulphur-based solutions (Na2S:9H2O, (NH4)2S + S, [(NH4)2S / (NH4)2SO4] + S); ii) etching in halogen-based solutions (bromine-methanol and HCl: H2O); and iii) thermal oxidation. A significant overall enhancement in PL response was observed after chemical treatment or thermal oxidation, which is associated with a reduction in surface band bending. These changes correlate with the removal of the native oxide, in addition to the formation of well-ordered layers of In-S (or In-As)O as a passivating layer, indicating that electronic passivation occurs at the surface. The passivating effect on sulphide treated surfaces is unstable, however, with an increase in band bending, due to reoxidation, observed over periods of a few days. The lowest re-oxidation rate was observed for ([(NH4)2S / (NH4)2SO4] + S). Etching in HCl:H2O and Br-methanol solutions of appropriate concentrations and for moderate times (1 min) resulted in smooth and defect-free InAs surfaces. Etching completely removed the native oxides from the surface and enhanced the PL response. The adsorption of bromine and chlorine onto the InAs surface led to the formation of As-Brx , In-Brx, As-Clx and In-Clxcompounds (x = 1, 2, 3), as inferred from changes in the In 3d3/2; 5/2 and As 3d core level binding energies. The etch rate was found to decrease because of strong anisotropic effects. The improvements in surface properties were reversed, however, if the concentrations of the etchants increased or the etch time was too long. In the worst cases, pit formation and inverted pyramids with {111} side facets were observed. Surface treatments or thermal oxidisation significantly enhanced the PL intensity relative to that of the as-received samples. This was due to a reduction in the surface state density upon de-oxidation, or in some cases, to the formation of a well ordered oxide layer on the surface. The overall increase in PL intensity after treatment is ascribed to a reduction in band bending near the surface. This allows several welldefined peaks not observed or reported previously for bulk InAs (with a carrier concentration n~2x1016 cm-3), to be studied. A combination of PL and XPS measurements before and after the various treatments was used to identify the chemical nature of the impurities giving rise to bound exciton recombination in InAs (111).
- Full Text:
- Date Issued: 2012
- Authors: Eassa, Nahswa Abo Alhassan Eassa
- Date: 2012
- Subjects: Indium arsenide , Chemical processes , Photoluminescence
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8714 , vital:26423
- Description: In this thesis, the effects of various chemical treatments on the surface modification of bulk InAs are investigated. The study focuses on the chemical processes that occur upon the exposure of the surface to sulphur-, chlorine- and bromine-containing solutions and oxygen, and the resulting changes to the electronic structure of the surface, as deduced from photoluminescence (PL) measurements, X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), Raman scattering and scanning electron microscopy (SEM). Three processing treatments were evaluated: i) treatment with sulphur-based solutions (Na2S:9H2O, (NH4)2S + S, [(NH4)2S / (NH4)2SO4] + S); ii) etching in halogen-based solutions (bromine-methanol and HCl: H2O); and iii) thermal oxidation. A significant overall enhancement in PL response was observed after chemical treatment or thermal oxidation, which is associated with a reduction in surface band bending. These changes correlate with the removal of the native oxide, in addition to the formation of well-ordered layers of In-S (or In-As)O as a passivating layer, indicating that electronic passivation occurs at the surface. The passivating effect on sulphide treated surfaces is unstable, however, with an increase in band bending, due to reoxidation, observed over periods of a few days. The lowest re-oxidation rate was observed for ([(NH4)2S / (NH4)2SO4] + S). Etching in HCl:H2O and Br-methanol solutions of appropriate concentrations and for moderate times (1 min) resulted in smooth and defect-free InAs surfaces. Etching completely removed the native oxides from the surface and enhanced the PL response. The adsorption of bromine and chlorine onto the InAs surface led to the formation of As-Brx , In-Brx, As-Clx and In-Clxcompounds (x = 1, 2, 3), as inferred from changes in the In 3d3/2; 5/2 and As 3d core level binding energies. The etch rate was found to decrease because of strong anisotropic effects. The improvements in surface properties were reversed, however, if the concentrations of the etchants increased or the etch time was too long. In the worst cases, pit formation and inverted pyramids with {111} side facets were observed. Surface treatments or thermal oxidisation significantly enhanced the PL intensity relative to that of the as-received samples. This was due to a reduction in the surface state density upon de-oxidation, or in some cases, to the formation of a well ordered oxide layer on the surface. The overall increase in PL intensity after treatment is ascribed to a reduction in band bending near the surface. This allows several welldefined peaks not observed or reported previously for bulk InAs (with a carrier concentration n~2x1016 cm-3), to be studied. A combination of PL and XPS measurements before and after the various treatments was used to identify the chemical nature of the impurities giving rise to bound exciton recombination in InAs (111).
- Full Text:
- Date Issued: 2012
Ocean dynamics of the shelf and bays of the eastern Agulhas bank: a process-oriented numerical modelling study
- Authors: Bailey, Dylan Francis
- Date: 2020
- Subjects: Oceanography -- Research , Marine biology , Marine meteorology , Hydrography
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49038 , vital:41595
- Description: There is a general need for a broader base of information on the finer detail of ocean processes in the Eastern Agulhas Bank region. In this thesis, the Regional Ocean Modelling System (ROMS) was applied to resolve high resolution (~1km) bay and shelf scale ocean processes along the south eastern coastline of South Africa using an offline multi-nested approach. Experimental and reference ocean model runs were used with in situ instrument mooring data to investigate how currents and temperature in the bays and the adjacent shelf are affected by the bathymetry, Agulhas Current (AC), regional winds, and coastal trapped waves (CTW). Focus was given to temperature, circulation, and coastal trapped waves, given the abundance of hourly in situ mooring data for these variables, making them suitable for comparison with the ocean model. SST variability trends were seasonally and spatially predictable, being greatest in the summer months and smallest in the winter months. A region of high SST variability extended from Port Alfred toward the south-west, indicating entrainment of nearshore upwelled water and instabilities in the inshore front of the AC. Shelf bottom temperature variability had a more spatially diverse seasonal trend, with coastal variability the highest (lowest) and offshore variability the lowest (highest) during the summer (winter) months. A distinct asymmetry in mean seasonal shelf bottom temperatures evident to the south of Algoa Bay and St Francis Bay was shown to be dependent on the profile of the shelf margin in relation to the inshore front of the AC using an experimental model run. Bay-scale anti-cyclonic circulation patterns dominate the bays throughout the year, with regions of strong mean surface currents occurring south of Cape Recife and Cape St Francis. General circulation patterns over the shelf are strongly governed by regional wind regimes, with the strongest flows being south-westward occurring during north-easterly wind events. Shelf bottom flows typically follow the expected Ekman-veering response, apart from near coastal flows that are topographically steered. A region of consistently strong south-westward shelf bottom flow extends from the east of Port Alfred to the shelf margin south of Bird Island. This flow is predominantly driven by the AC, although its velocity is strongly governed by regional winds. Circulation patterns during powerful eastward moving wind systems are strongly governed by the passage of associated CTW. Comparisons with an experimental model run where surface winds were removed revealed that the shelf wave was responsible for 61% of water volume displacement during a CTW event, and that the coastal shear turbulence caused by this displacement has a direct effect on the mixed layer depth. The links made between the complex shelf and bay ocean processes indicate that subtle changes to the ocean state will have far reaching effects on the regional ocean environment and its biota. Given the challenges of climate change, this is of paramount importance if we are to quantify these effects and mitigate their impacts, particularly with respect to the socio-economic dependency of those who rely on the ocean for its living resources.
- Full Text:
- Date Issued: 2020
- Authors: Bailey, Dylan Francis
- Date: 2020
- Subjects: Oceanography -- Research , Marine biology , Marine meteorology , Hydrography
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49038 , vital:41595
- Description: There is a general need for a broader base of information on the finer detail of ocean processes in the Eastern Agulhas Bank region. In this thesis, the Regional Ocean Modelling System (ROMS) was applied to resolve high resolution (~1km) bay and shelf scale ocean processes along the south eastern coastline of South Africa using an offline multi-nested approach. Experimental and reference ocean model runs were used with in situ instrument mooring data to investigate how currents and temperature in the bays and the adjacent shelf are affected by the bathymetry, Agulhas Current (AC), regional winds, and coastal trapped waves (CTW). Focus was given to temperature, circulation, and coastal trapped waves, given the abundance of hourly in situ mooring data for these variables, making them suitable for comparison with the ocean model. SST variability trends were seasonally and spatially predictable, being greatest in the summer months and smallest in the winter months. A region of high SST variability extended from Port Alfred toward the south-west, indicating entrainment of nearshore upwelled water and instabilities in the inshore front of the AC. Shelf bottom temperature variability had a more spatially diverse seasonal trend, with coastal variability the highest (lowest) and offshore variability the lowest (highest) during the summer (winter) months. A distinct asymmetry in mean seasonal shelf bottom temperatures evident to the south of Algoa Bay and St Francis Bay was shown to be dependent on the profile of the shelf margin in relation to the inshore front of the AC using an experimental model run. Bay-scale anti-cyclonic circulation patterns dominate the bays throughout the year, with regions of strong mean surface currents occurring south of Cape Recife and Cape St Francis. General circulation patterns over the shelf are strongly governed by regional wind regimes, with the strongest flows being south-westward occurring during north-easterly wind events. Shelf bottom flows typically follow the expected Ekman-veering response, apart from near coastal flows that are topographically steered. A region of consistently strong south-westward shelf bottom flow extends from the east of Port Alfred to the shelf margin south of Bird Island. This flow is predominantly driven by the AC, although its velocity is strongly governed by regional winds. Circulation patterns during powerful eastward moving wind systems are strongly governed by the passage of associated CTW. Comparisons with an experimental model run where surface winds were removed revealed that the shelf wave was responsible for 61% of water volume displacement during a CTW event, and that the coastal shear turbulence caused by this displacement has a direct effect on the mixed layer depth. The links made between the complex shelf and bay ocean processes indicate that subtle changes to the ocean state will have far reaching effects on the regional ocean environment and its biota. Given the challenges of climate change, this is of paramount importance if we are to quantify these effects and mitigate their impacts, particularly with respect to the socio-economic dependency of those who rely on the ocean for its living resources.
- Full Text:
- Date Issued: 2020
Rhenium complexes with multidentate benzazoles and related N,X-donor (X = N, O, S) ligands
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
The kinetics and associated equilibria of high oxidation state osmium complexes
- Authors: McFadzean, Belinda Julie
- Date: 2007
- Subjects: Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10371 , http://hdl.handle.net/10948/732 , Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Description: The reduction of osmium tetroxide by a series of alcohols was studied spectrophotometrically. The reaction was observed to occur in two steps, unlike previously reported studies on this reaction. The identities of both reactants and products were established via a range of techniques. Equilibrium and kinetic data were gathered and reaction models were evaluated using equilibrium and kinetic modelling software. The following complexation reaction model emerged that simulates both the equilibrium and kinetic data. Os(VIII) + RCH2OHOs(VI) + RCHO2 Os(VIII) + Os(VI)k+2k1Complexk-2 Conditional rate constants and equilibrium constants were generated. Rate constants for the alcohol reactions were correlated with the Taft σ* constant. The ρ* value obtained (-1.4) is consistent with a hydride transfer mechanism coupled with synchronous removal of the hydroxyl proton. The identity of the osmium(VIII)-osmium(VI) complex has been suggested. Thermodynamic parameters were also reported. The rate constants for benzyl alcohol and 2-chloroethanol deviated from those predicted by the Taft plot. An explanation of enhanced resonance effects is offered for benzyl alcohol and an alternative reaction mechanism, involving proton abstraction, is offered for 2-chloroethanol. The reaction of the oxidation products of alcohols, namely ketones, with osmium tetroxide produced rate constants that were, perhaps surprisingly, far larger than those of the alcohols. A reaction mechanism for the oxidation of the ketones is suggested, which involves the enolate ion as the reactive starting reagent.
- Full Text:
- Date Issued: 2007
- Authors: McFadzean, Belinda Julie
- Date: 2007
- Subjects: Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10371 , http://hdl.handle.net/10948/732 , Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Description: The reduction of osmium tetroxide by a series of alcohols was studied spectrophotometrically. The reaction was observed to occur in two steps, unlike previously reported studies on this reaction. The identities of both reactants and products were established via a range of techniques. Equilibrium and kinetic data were gathered and reaction models were evaluated using equilibrium and kinetic modelling software. The following complexation reaction model emerged that simulates both the equilibrium and kinetic data. Os(VIII) + RCH2OHOs(VI) + RCHO2 Os(VIII) + Os(VI)k+2k1Complexk-2 Conditional rate constants and equilibrium constants were generated. Rate constants for the alcohol reactions were correlated with the Taft σ* constant. The ρ* value obtained (-1.4) is consistent with a hydride transfer mechanism coupled with synchronous removal of the hydroxyl proton. The identity of the osmium(VIII)-osmium(VI) complex has been suggested. Thermodynamic parameters were also reported. The rate constants for benzyl alcohol and 2-chloroethanol deviated from those predicted by the Taft plot. An explanation of enhanced resonance effects is offered for benzyl alcohol and an alternative reaction mechanism, involving proton abstraction, is offered for 2-chloroethanol. The reaction of the oxidation products of alcohols, namely ketones, with osmium tetroxide produced rate constants that were, perhaps surprisingly, far larger than those of the alcohols. A reaction mechanism for the oxidation of the ketones is suggested, which involves the enolate ion as the reactive starting reagent.
- Full Text:
- Date Issued: 2007
Population ecology of Indo-Pacific bottlenose dolphins along the south-east coast of South Africa
- Vargas-Fonseca, O. Alejandra
- Authors: Vargas-Fonseca, O. Alejandra
- Date: 2018
- Subjects: Bottlenose dolphin -- South Africa -- Western Cape , Bottlenose dolphin -- Ecology -- South Africa -- Western Cape Adaptation (Biology) Population biology -- Research
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/36090 , vital:33890
- Description: In this study, the genetic population structure of the Indo-Pacific bottlenose dolphin (Tursiops aduncus) was assessed across the Agulhas and Natal Bioregions of South Africa. At the same time, the abundance, distribution and habitat use of T. aduncus was investigated using boat-based surveys along 145 km of coastline from Goukamma Marine Protected Area (MPA) to Tsitsikamma MPA along the south-east coast of South Africa (Agulhas Bioregion). Tursiops aduncus habitat preferences were assessed based on locations of sightings and recorded behaviour, and compared with those of the sympatric Indian Ocean humpback dolphins (Sousa plumbea). Strong patterns of differentiation between two sub-populations of T. aduncus were identified using double digest Restriction Site Associated DNA sequencing (ddRADseq). Pairwise FST were significant (p < 0.05) between individuals from the Agulhas and Natal Bioregions and yielded values of 0.033 for all the loci. Resource requirements, specialization and differences in habitat use possibly provided sufficient isolation allowing differentiation between sub-populations of the two ecologically distinct bioregions, despite the lack of any prominent boundary to gene flow. The two identified sub-populations should each be managed as a distinct conservation unit. The abundance estimate of T. aduncus for the study area according to an open population model (POPAN) was 2,295 individuals (95% CI: 1,157 - 4,553). Although closed models were considered inappropriate, such a model was applied for the Plettenberg Bay part of the study area in isolation, to allow for comparison with a previous estimate. The comparison showed a 72.3% decrease in abundance between the two periods: from 6,997 (95% CI: 5,230 - 9,492) in 2002 - 2003 to 1,940 (95% CI: 1,448 - 2,600) in 2014 - 2016. The mean group size also declined from 120 (range: 1 - 500) to 26 (range: 1 - 100). The results highlight the importance of assessing abundance changes at other sites to inform the revision of T. aduncus conservation status in South Africa. Tursiops aduncus were encountered throughout the area. The lowest encounter rate was along rocky and exposed shorelines. These areas were, however, associated with relatively larger group sizes and greater likelihood of travelling behaviour, whereas sandy bottomed areas, where encounter rates were highest (e.g. parts of Plettenberg Bay and the Goukamma MPA), were more likely to be associated with other behaviours (e.g. foraging, socialising). There was a relatively low association of encounters with MPAs, possibly due to the fact that two of the three MPAs in the area (Tsitsikamma and Robberg) were characterised by non-preferred habitat, namely rocky shorelines. Comparison with Sousa plumbea showed similarity in habitat preferences between the species, though S. plumbea also showed an affinity for estuarine habitats. Two areas that were highly utilised by both species were located along Goukamma MPA and the north-east section in Plettenberg Bay including the Keurbooms Estuary. The latter is unprotected and a management measure could be to create a controlled-use zone to reduce disturbance to dolphins there.
- Full Text:
- Date Issued: 2018
- Authors: Vargas-Fonseca, O. Alejandra
- Date: 2018
- Subjects: Bottlenose dolphin -- South Africa -- Western Cape , Bottlenose dolphin -- Ecology -- South Africa -- Western Cape Adaptation (Biology) Population biology -- Research
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/36090 , vital:33890
- Description: In this study, the genetic population structure of the Indo-Pacific bottlenose dolphin (Tursiops aduncus) was assessed across the Agulhas and Natal Bioregions of South Africa. At the same time, the abundance, distribution and habitat use of T. aduncus was investigated using boat-based surveys along 145 km of coastline from Goukamma Marine Protected Area (MPA) to Tsitsikamma MPA along the south-east coast of South Africa (Agulhas Bioregion). Tursiops aduncus habitat preferences were assessed based on locations of sightings and recorded behaviour, and compared with those of the sympatric Indian Ocean humpback dolphins (Sousa plumbea). Strong patterns of differentiation between two sub-populations of T. aduncus were identified using double digest Restriction Site Associated DNA sequencing (ddRADseq). Pairwise FST were significant (p < 0.05) between individuals from the Agulhas and Natal Bioregions and yielded values of 0.033 for all the loci. Resource requirements, specialization and differences in habitat use possibly provided sufficient isolation allowing differentiation between sub-populations of the two ecologically distinct bioregions, despite the lack of any prominent boundary to gene flow. The two identified sub-populations should each be managed as a distinct conservation unit. The abundance estimate of T. aduncus for the study area according to an open population model (POPAN) was 2,295 individuals (95% CI: 1,157 - 4,553). Although closed models were considered inappropriate, such a model was applied for the Plettenberg Bay part of the study area in isolation, to allow for comparison with a previous estimate. The comparison showed a 72.3% decrease in abundance between the two periods: from 6,997 (95% CI: 5,230 - 9,492) in 2002 - 2003 to 1,940 (95% CI: 1,448 - 2,600) in 2014 - 2016. The mean group size also declined from 120 (range: 1 - 500) to 26 (range: 1 - 100). The results highlight the importance of assessing abundance changes at other sites to inform the revision of T. aduncus conservation status in South Africa. Tursiops aduncus were encountered throughout the area. The lowest encounter rate was along rocky and exposed shorelines. These areas were, however, associated with relatively larger group sizes and greater likelihood of travelling behaviour, whereas sandy bottomed areas, where encounter rates were highest (e.g. parts of Plettenberg Bay and the Goukamma MPA), were more likely to be associated with other behaviours (e.g. foraging, socialising). There was a relatively low association of encounters with MPAs, possibly due to the fact that two of the three MPAs in the area (Tsitsikamma and Robberg) were characterised by non-preferred habitat, namely rocky shorelines. Comparison with Sousa plumbea showed similarity in habitat preferences between the species, though S. plumbea also showed an affinity for estuarine habitats. Two areas that were highly utilised by both species were located along Goukamma MPA and the north-east section in Plettenberg Bay including the Keurbooms Estuary. The latter is unprotected and a management measure could be to create a controlled-use zone to reduce disturbance to dolphins there.
- Full Text:
- Date Issued: 2018
Monitoring carbon stocks in the sub-tropical thicket biome using remote sensing and GIS techniques : the case of the Great Fish River Nature Reserve and its environs, Eastern Cape province, South Africa
- Authors: Nyamugama, Adolph
- Date: 2013
- Subjects: Fragmented landscapes -- South Africa -- Eastern Cape -- Remote sensing , Environmental degradation -- South Africa -- Eastern Cape , Remote sensing , Geographic information systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10672 , http://hdl.handle.net/10948/d1020303
- Description: The subtropical thicket biome in the Eastern Cape Province of South Africa has been heavily degraded and transformed due overutilization during the last century. The highly degraded and transformed areas exhibit a significant loss of above ground carbon stocks (AGC) and loss of SOC content. Information about land use /cover change and fragmentation dynamics is a prerequisite for measuring carbon stock changes. The main aim of this study is to assess the trends of land use/cover change, fragmentation dynamics, model the temporal changes of AGC stocks in the Great Fish River Nature Reserve and its environs from 1972 to 2010, quantify and map the spatial distribution of SOC concentrations in the partial subtropical thicket cover in the Great Fish River Nature Reserve and environs (communal rangelands). Multi-temporal analyses based on 1972 Landsat MSS, 1982 and 1992 Landsat TM, 2002 Landsat ETM and 2010 SPOT 5 High Resolution images were used for land use/cover change detection and fragmentation analysis. Object oriented post-classification comparison was applied for land use/cover change detection analysis. Fragmentation dynamics analysis was carried out by computing and analyzing landscape metrics in land use/cover classes. Landscape fragmentation analyses revealed that thicket vegetation has increasingly become fragmented, characterized by smaller less linked patches of intact thicket cover. Landscape metrics for intact thicket and degraded thicket classes reflected fragmentation, as illustrated by the increase in the Number of Patches (NP), Patch Density (PD), Landscape Shape Index (LSI), and a decrease in Mean Patch Size (MPS). The use of remote sensing techniques and landscape metrics was vital for the understanding of the dynamics of land use/cover change and fragmentation. Baseline land use/cover maps produced for 1972, 1982, 1992 2002 and 2010 and fragmentation analyses were then used for analyzing carbon stock changes in the study area. To model the temporal changes of AGC stocks in the Great Fish River Nature Reserve and its environs from 1972 to 2010, a method based on the integration of RS and GIS was employed for the estimation of AGC stocks in a time series. A non-linear regression model was developed using NDVI values generated from SPOT 5 HRG satellite imagery of 2010 as the independent variable and AGC stock estimates from field plots as the dependent variable. The regression model was used to estimate AGC stocks for the entire study area on the 2010 SPOT 5 HRG and also extrapolated to the 1972 Landsat MSS, 1982 and 1992 Landsat TM, and 2002 Landsat ETM. The AGC stocks for the period 1972 -1982, 1982-1992, 1992-200) and 2002-2010 were compared by means of change detection analysis. The comparison of AGC stocks was carried out at subtropical thicket class level. The results showed a decline of AGC stocks in all the classes from 1972 to 2010. Degraded and transformed thicket classes had the highest AGC stock losses. The decline of AGC stocks was attributed to thicket transformation and degradation which were caused by anthropogenic activities. To map and quantify SOC concentration in partial (fractional) thicket vegetation cover, the spectral reflectance of both thicket vegetation and bare-soils was measured in situ. Soil samples were collected from the sampling sites and transported to the laboratory for spectral reflectance and SOC measurements. Thicket vegetation and bare soil reflectance were measured using spectroscopy both in situ and under laboratory conditions. Their respective endmembers were extracted from ASTER imagery using the Pixel Purity Index (PPI). The endmembers were validated with in situ and laboratory thicket and bare-soil reflectance signatures. The spectral unmixing technique was applied to ASTER imagery to discriminate pure pixels of thicket vegetation and bare-soils; a residual spectral image was produced. The Residual Spectral Unmixing (RSU) procedure was applied to the residual spectral image to produce an RSU soil spectrum image. Partial Least Squares Regression (PSLR) model was developed using spectral signatures of a residual soil spectrum image as the independent variable and SOC concentration measured from soil samples as the dependent variable. The PSLR prediction model was used to predict SOC concentration on the RSU soil spectral image. The predicted SOC concentration was then validated with SOC concentration measured from the field plots. A Strong correlation (R2 = 0.82) was obtained between the predicted SOC concentration and the SOC concentration measured from field samples. The PSLR was then used to generate a map of SOC concentration for the Great Fish River Nature Reserve and its environs. Areas with very low SOC concentrations were found in the degraded communal villages, as opposed to the higher SOC values in the protected area. The results confirmed that RS techniques are key to estimating and mapping the spatial distribution of SOC concentration in partial subtropical thicket vegetation. Partial thicket vegetation has a huge influence on the soil spectra; it can influence the prediction of SOC concentration. The use of the RSU approach eliminates partial thicket vegetation cover from bare soil spectra. The residual soil spectrum image contains enough information for the mapping of SOC concentration. The technique has the potential to augment the applicability of airborne imaging spectroscopy for soil studies in the sub-tropical thicket biome and similar environments.
- Full Text:
- Date Issued: 2013
- Authors: Nyamugama, Adolph
- Date: 2013
- Subjects: Fragmented landscapes -- South Africa -- Eastern Cape -- Remote sensing , Environmental degradation -- South Africa -- Eastern Cape , Remote sensing , Geographic information systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10672 , http://hdl.handle.net/10948/d1020303
- Description: The subtropical thicket biome in the Eastern Cape Province of South Africa has been heavily degraded and transformed due overutilization during the last century. The highly degraded and transformed areas exhibit a significant loss of above ground carbon stocks (AGC) and loss of SOC content. Information about land use /cover change and fragmentation dynamics is a prerequisite for measuring carbon stock changes. The main aim of this study is to assess the trends of land use/cover change, fragmentation dynamics, model the temporal changes of AGC stocks in the Great Fish River Nature Reserve and its environs from 1972 to 2010, quantify and map the spatial distribution of SOC concentrations in the partial subtropical thicket cover in the Great Fish River Nature Reserve and environs (communal rangelands). Multi-temporal analyses based on 1972 Landsat MSS, 1982 and 1992 Landsat TM, 2002 Landsat ETM and 2010 SPOT 5 High Resolution images were used for land use/cover change detection and fragmentation analysis. Object oriented post-classification comparison was applied for land use/cover change detection analysis. Fragmentation dynamics analysis was carried out by computing and analyzing landscape metrics in land use/cover classes. Landscape fragmentation analyses revealed that thicket vegetation has increasingly become fragmented, characterized by smaller less linked patches of intact thicket cover. Landscape metrics for intact thicket and degraded thicket classes reflected fragmentation, as illustrated by the increase in the Number of Patches (NP), Patch Density (PD), Landscape Shape Index (LSI), and a decrease in Mean Patch Size (MPS). The use of remote sensing techniques and landscape metrics was vital for the understanding of the dynamics of land use/cover change and fragmentation. Baseline land use/cover maps produced for 1972, 1982, 1992 2002 and 2010 and fragmentation analyses were then used for analyzing carbon stock changes in the study area. To model the temporal changes of AGC stocks in the Great Fish River Nature Reserve and its environs from 1972 to 2010, a method based on the integration of RS and GIS was employed for the estimation of AGC stocks in a time series. A non-linear regression model was developed using NDVI values generated from SPOT 5 HRG satellite imagery of 2010 as the independent variable and AGC stock estimates from field plots as the dependent variable. The regression model was used to estimate AGC stocks for the entire study area on the 2010 SPOT 5 HRG and also extrapolated to the 1972 Landsat MSS, 1982 and 1992 Landsat TM, and 2002 Landsat ETM. The AGC stocks for the period 1972 -1982, 1982-1992, 1992-200) and 2002-2010 were compared by means of change detection analysis. The comparison of AGC stocks was carried out at subtropical thicket class level. The results showed a decline of AGC stocks in all the classes from 1972 to 2010. Degraded and transformed thicket classes had the highest AGC stock losses. The decline of AGC stocks was attributed to thicket transformation and degradation which were caused by anthropogenic activities. To map and quantify SOC concentration in partial (fractional) thicket vegetation cover, the spectral reflectance of both thicket vegetation and bare-soils was measured in situ. Soil samples were collected from the sampling sites and transported to the laboratory for spectral reflectance and SOC measurements. Thicket vegetation and bare soil reflectance were measured using spectroscopy both in situ and under laboratory conditions. Their respective endmembers were extracted from ASTER imagery using the Pixel Purity Index (PPI). The endmembers were validated with in situ and laboratory thicket and bare-soil reflectance signatures. The spectral unmixing technique was applied to ASTER imagery to discriminate pure pixels of thicket vegetation and bare-soils; a residual spectral image was produced. The Residual Spectral Unmixing (RSU) procedure was applied to the residual spectral image to produce an RSU soil spectrum image. Partial Least Squares Regression (PSLR) model was developed using spectral signatures of a residual soil spectrum image as the independent variable and SOC concentration measured from soil samples as the dependent variable. The PSLR prediction model was used to predict SOC concentration on the RSU soil spectral image. The predicted SOC concentration was then validated with SOC concentration measured from the field plots. A Strong correlation (R2 = 0.82) was obtained between the predicted SOC concentration and the SOC concentration measured from field samples. The PSLR was then used to generate a map of SOC concentration for the Great Fish River Nature Reserve and its environs. Areas with very low SOC concentrations were found in the degraded communal villages, as opposed to the higher SOC values in the protected area. The results confirmed that RS techniques are key to estimating and mapping the spatial distribution of SOC concentration in partial subtropical thicket vegetation. Partial thicket vegetation has a huge influence on the soil spectra; it can influence the prediction of SOC concentration. The use of the RSU approach eliminates partial thicket vegetation cover from bare soil spectra. The residual soil spectrum image contains enough information for the mapping of SOC concentration. The technique has the potential to augment the applicability of airborne imaging spectroscopy for soil studies in the sub-tropical thicket biome and similar environments.
- Full Text:
- Date Issued: 2013
An investigation of the binding capacities of recombinant domain mutants of the human Polymeric Immunoglobulin Receptor (pIgR)
- Authors: Prinsloo, Earl Adin Gerard
- Date: 2006
- Subjects: Immunoglobulins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10307 , http://hdl.handle.net/10948/403 , Immunoglobulins
- Description: The membrane bound glycoprotein, polymeric immunoglobulin receptor (pIgR) is the primary transport molecule of the polymeric immunoglobulins, dimeric IgA and pentameric IgM, across epithelial cells. This process, known as transcytosis, is essential in order to establish immunity at mucosal surfaces. Typically, pIgR binds to the polymeric immunoglobulin at the basolateral surface of the epithelial cell, via five homologous immunoglobulin-like domains of the ectodomain. Binding is covalent to IgA and non-covalent to IgM; the IgM binding varying among species. The pIgR-bound complex is released at the apical surface of the cell after cleavage of pIgR at Arg585, thereafter referred to as secretory component (SC). SC confers protective and immunologic functions to the polymeric immunoglobulin. Free SC, i.e. not complexed with polymeric immunoglobulins, is also known to be released into mucosal secretions; and binds to pathogenic bacteria and bacterial products. It is known that domain I of the ectodomain is the primary domain in the interaction with polymeric immunoglobulins, while domain V is involved in a covalent linkage with IgA. However, little is known of domains II-IV and their role in immunoglobulin binding, particularly to IgM. This study aimed to characterize the binding of recombinant human pIgR domain mutants to polymeric IgM using immunological, biophysical and cell based techniques; thereby allowing greater insight into the contribution of each of the five domains. The unique domain structure allowed for selective amplification of single and multiple domain mutants from cloned human PIGR ectodomain cDNA. Mutants were cloned and expressed in Esherichia coli BL21 (DE3) as inclusion bodies. Recombinant mutant proteins were refolded in vitro by equilibrium gradient dialysis and purified to homogeneity. Equilibrium binding data show significant contributions to specific binding as a factor of domain presence. Binding kinetics determined by biophysical surface plasmon resonance measurements show the interplay between association and dissociation rates as defined by individual domains. In vitro competitive binding studies using the human intestinal carcinoma, HT29, known to constitutively express pIgR, show that the constructed recombinant domain mutants outcompete native pIgR. The level of competition is shown to be dependant on the domains downstream of domain I. The data also confirm the biological activity of the first in vitro refolded recombinant human SC.
- Full Text:
- Date Issued: 2006
- Authors: Prinsloo, Earl Adin Gerard
- Date: 2006
- Subjects: Immunoglobulins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10307 , http://hdl.handle.net/10948/403 , Immunoglobulins
- Description: The membrane bound glycoprotein, polymeric immunoglobulin receptor (pIgR) is the primary transport molecule of the polymeric immunoglobulins, dimeric IgA and pentameric IgM, across epithelial cells. This process, known as transcytosis, is essential in order to establish immunity at mucosal surfaces. Typically, pIgR binds to the polymeric immunoglobulin at the basolateral surface of the epithelial cell, via five homologous immunoglobulin-like domains of the ectodomain. Binding is covalent to IgA and non-covalent to IgM; the IgM binding varying among species. The pIgR-bound complex is released at the apical surface of the cell after cleavage of pIgR at Arg585, thereafter referred to as secretory component (SC). SC confers protective and immunologic functions to the polymeric immunoglobulin. Free SC, i.e. not complexed with polymeric immunoglobulins, is also known to be released into mucosal secretions; and binds to pathogenic bacteria and bacterial products. It is known that domain I of the ectodomain is the primary domain in the interaction with polymeric immunoglobulins, while domain V is involved in a covalent linkage with IgA. However, little is known of domains II-IV and their role in immunoglobulin binding, particularly to IgM. This study aimed to characterize the binding of recombinant human pIgR domain mutants to polymeric IgM using immunological, biophysical and cell based techniques; thereby allowing greater insight into the contribution of each of the five domains. The unique domain structure allowed for selective amplification of single and multiple domain mutants from cloned human PIGR ectodomain cDNA. Mutants were cloned and expressed in Esherichia coli BL21 (DE3) as inclusion bodies. Recombinant mutant proteins were refolded in vitro by equilibrium gradient dialysis and purified to homogeneity. Equilibrium binding data show significant contributions to specific binding as a factor of domain presence. Binding kinetics determined by biophysical surface plasmon resonance measurements show the interplay between association and dissociation rates as defined by individual domains. In vitro competitive binding studies using the human intestinal carcinoma, HT29, known to constitutively express pIgR, show that the constructed recombinant domain mutants outcompete native pIgR. The level of competition is shown to be dependant on the domains downstream of domain I. The data also confirm the biological activity of the first in vitro refolded recombinant human SC.
- Full Text:
- Date Issued: 2006
The concentration of ten metals in the tissues of shark species Squalus megalops and Mustelus mustelus (Chondrichthyes) occuring along the Southeastern coast of South Africa
- Erasmus, Christina Petronella
- Authors: Erasmus, Christina Petronella
- Date: 2004
- Subjects: Sharks -- South Africa -- Effect of metals on. , Marine pollutio -- South Africa.
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11095 , http://hdl.handle.net/10948/d1019683
- Description: The southeastern coast of South Africa is deemed unpolluted and with the exception of a few localized areas, is believed to be pristine. This study aimed to (1) assess the concentration of metals in the water and sharks (Squalus megalops, Mustelus mustelus) from different sites along the southeastern coast, (2) determine the effects that metals have on each other and investigate the accumulation and storage of metals in different shark tissues, (3) determine the effects of length and sex on metal concentration and the presence of metallothioneins in the liver. Metal concentrations in water from seven sites along the southeastern coast revealed concentrations below the detection limit of the extraction method, except for iron at St. Francis Bay which was below the recommended levels as supplied by DWAF. Met al concentrations in S. megalops from the seven sites revealed significantly elevated levels in individuals from Algoa and St. Francis Bay when compared to the other 5 sites. This was observed for all metals except manganese, which had a higher concentration at Cape Agulhas. After comparing the metal levels in muscle tissue (S. megalops) with data from the Department of Health it was concluded that the sharks caught at Algoa and St. Francis Bay were unsuited for human consumption. Liver and vertebral tissues from both S. megalops and M. mustelus were deemed unsuited for human consumption but further research should be conducted especially on vertebral metal concentrations. Comparing the metal concentration in different tissue types of S. megalops and M. mustelus significant difference were observed and attributed to differences in the maturity (thus age) of the two species. Significant differences in the metal concentration of males and females for both the species were observed. A higher number of differences were however observed in M. mustelus than in S. megalops, most probably due to the differences in maturity. Length and weight vs. metal concentration regressions in the males and females of both species revealed more negative than positive trends. This was found to be in accordance with other studies from around the world. Using the life stages of S. megalops, significant differences in the average concentration of metals were observed between the life stages, with embryos usually having the highest concentration. The metal concentration series determined for S. megalops were similar to that which have been reported in the literature in that iron and zinc occupied the highest concentration positions while cadmium, copper and manganese occupied the last three. The spleen usually had the highest metal concentration except for aluminium in skin and arsenic in muscle tissue. Pearson correlation revealed significant negative correlations between cadmium and the mentioned metals suggesting that cadmium replaces essential metals such as manganese, iron and copper as. Negative correlations between essential metals were observed most probably due to the competition for binding positions on ligands. Positive correlations were observed between metals in sp ecific tissue types and may be indicative of synergistic effects, e.g. aluminium may result in the accumulation of other metals such as cadmium. Positive and negative correlations between a specific metal and different tissue types have also been observed and it appears that there are movement of metals between tissue types. Positive correlation for essential metals between yolk and other tissue have been observed, although no correlations for non-essential metals were observed. This could potentially indicate a mechanism that prevents the accumulation of nonessential metals in embryos. Though no metallothioneins were isolated form the liver, the presence of cadmium in other proteins indicate that that cadmium is substituted for essential metals, and as this may result in deleterious physiological effects, further studies should be conducted. In conclusion it can be said that although some of the results were expected there are still quite a few unanswered question and further studies should be conducted.
- Full Text:
- Date Issued: 2004
- Authors: Erasmus, Christina Petronella
- Date: 2004
- Subjects: Sharks -- South Africa -- Effect of metals on. , Marine pollutio -- South Africa.
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11095 , http://hdl.handle.net/10948/d1019683
- Description: The southeastern coast of South Africa is deemed unpolluted and with the exception of a few localized areas, is believed to be pristine. This study aimed to (1) assess the concentration of metals in the water and sharks (Squalus megalops, Mustelus mustelus) from different sites along the southeastern coast, (2) determine the effects that metals have on each other and investigate the accumulation and storage of metals in different shark tissues, (3) determine the effects of length and sex on metal concentration and the presence of metallothioneins in the liver. Metal concentrations in water from seven sites along the southeastern coast revealed concentrations below the detection limit of the extraction method, except for iron at St. Francis Bay which was below the recommended levels as supplied by DWAF. Met al concentrations in S. megalops from the seven sites revealed significantly elevated levels in individuals from Algoa and St. Francis Bay when compared to the other 5 sites. This was observed for all metals except manganese, which had a higher concentration at Cape Agulhas. After comparing the metal levels in muscle tissue (S. megalops) with data from the Department of Health it was concluded that the sharks caught at Algoa and St. Francis Bay were unsuited for human consumption. Liver and vertebral tissues from both S. megalops and M. mustelus were deemed unsuited for human consumption but further research should be conducted especially on vertebral metal concentrations. Comparing the metal concentration in different tissue types of S. megalops and M. mustelus significant difference were observed and attributed to differences in the maturity (thus age) of the two species. Significant differences in the metal concentration of males and females for both the species were observed. A higher number of differences were however observed in M. mustelus than in S. megalops, most probably due to the differences in maturity. Length and weight vs. metal concentration regressions in the males and females of both species revealed more negative than positive trends. This was found to be in accordance with other studies from around the world. Using the life stages of S. megalops, significant differences in the average concentration of metals were observed between the life stages, with embryos usually having the highest concentration. The metal concentration series determined for S. megalops were similar to that which have been reported in the literature in that iron and zinc occupied the highest concentration positions while cadmium, copper and manganese occupied the last three. The spleen usually had the highest metal concentration except for aluminium in skin and arsenic in muscle tissue. Pearson correlation revealed significant negative correlations between cadmium and the mentioned metals suggesting that cadmium replaces essential metals such as manganese, iron and copper as. Negative correlations between essential metals were observed most probably due to the competition for binding positions on ligands. Positive correlations were observed between metals in sp ecific tissue types and may be indicative of synergistic effects, e.g. aluminium may result in the accumulation of other metals such as cadmium. Positive and negative correlations between a specific metal and different tissue types have also been observed and it appears that there are movement of metals between tissue types. Positive correlation for essential metals between yolk and other tissue have been observed, although no correlations for non-essential metals were observed. This could potentially indicate a mechanism that prevents the accumulation of nonessential metals in embryos. Though no metallothioneins were isolated form the liver, the presence of cadmium in other proteins indicate that that cadmium is substituted for essential metals, and as this may result in deleterious physiological effects, further studies should be conducted. In conclusion it can be said that although some of the results were expected there are still quite a few unanswered question and further studies should be conducted.
- Full Text:
- Date Issued: 2004
Sedimentology and sequence stratigraphy of the Congo and Kalahari basins of South Central Africa and their evolution during the formation and break-up of West Gondwana
- Authors: Linol, Bastien
- Date: 2013
- Subjects: Sedimentary basins -- Africa , Sedimentology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10655 , http://hdl.handle.net/10948/d1012148 , Sedimentary basins -- Africa , Sedimentology
- Description: The high elevated (ca. 1100 m) continental Kalahari Basin (KB) of southern Africa and the linked lower lying (ca. 400 m) Congo Basin (CB) of central Africa preserve in their interiors extensive sedimentary rock sequences and sediments that represent a unique record of the Phanerozoic geodynamic and climatic evolution of sub-Saharan Africa. In this thesis, field observations and new borehole data from the Democratic Republic of Congo (DRC) and Botswana are integrated with new paleontology and geochronology to present a substantially revised stratigraphy for the CB, and south-central Africa in general. This work also introduces a new multiphase model for the subsidence and uplift history of the CB, and improves correlations with the Cape-Karoo Basin (CKB) of South Africa and the Paraná Basin (PB) of south-east Brazil. Four deep boreholes, each between 2 and 4.5 km deep, drilled in the centre of the CB in the 1950’s and 1970’s are re-examined together with the colonial literature (in French) and available seismic data. This stratigraphic and basin analysis is complemented with new U-Pb dates of detrital zircons from core-samples of two of the boreholes (Samba and Dekese), as well as from samples collected during field work in the Kwango region of the south-west DRC. This work, for the first time, constrains the maximum ages and source provenances of the successions in the CB. Following the Pan African orogens (ca. 650-530 Ma), extensive sequences of red beds were deposited by regional paleocurrents to the south. These are now best preserved (1 km thick) along the West Congo, Oubanguides, and Lufilian Belts surrounding the CB. Overlying a hiatus that represents most of the early-Paleozoic, is a 1 to 3 km thick succession of easterly derived glacial, and then continental sequences of the Karoo Supergroup. This succession records the first main episode of subsidence [10-15 m/Ma], interrupted by a phase of uplift that is likely related to far-field intracontinental deformation within Gondwana supercontinent during the Variscan and Cape Fold orogenies (ca. 250-330 Ma) at its peripheries. Detrital zircons from the lower Karoo diamictites are dated at 1.85-2.05 Ga and 1.37- 1.42 Ga, and thus sourced from Paleoproterozoic (Eburnean) and mid-Mesoproterozoic (Kibaran type-I) basement rocks in Uganda and Tanzania. Zircons from all the other successions in the CB date predominantly at 950-1050 Ma and 500-800 Ma. These are derived from sediment recycling of late-Mesoproterozoic (Kibaran type-II) and late- Neoproterozoic (Pan African) sources in the Central African Republic (CAR) and Chad. A distinct unconformity across the Karoo Supergroup in the CB is overlain by 500- 1000 m Jurassic-Cretaceous sequences, here named the Congo Supergroup. During initial rapid subsidence [10-50 m/Ma], late-Jurassic (Kimmeridgian) shallow marine to continental sedimentation attests to a short transgression of proto-Indian Ocean waters into the northern CB (at 160 m above present day sea-level), succeeded by widespread deposition of aeolian dunes that extend from the southern CB to the PB in South America. The youngest zircons from these aeolian sediments in the CB date at 190 Ma and 240-290 Ma, and most likely indicate the influence of extensive silicic volcanic ash derived from the proto-Andes along the south-western margin of Gondwana. Two superimposed mid-Cretaceous (Albian-Cenomanian) lacustrine sequences in the central CB record a succeeding, slower [10-15 m/Ma], phase of basin subsidence during the opening of the South Atlantic (ca. 85-135 Ma). These Cretaceous sequences are in turn truncated by another regional peneplanation surface covered by Cenozoic (Eocene) silcretized sands and alluviums of the Kalahari Group, only 50-250 m thick in the centre of the CB. Southward, on top of the Kalahari Plateau in the central desert region of north-west Botswana, new boreholes intercepted laterally equivalent condensed lacustrine carbonates and calcretes (20-50 m thick) covered by sands. These terrestrial sequences are key archives of late-Mesozoic – Cenozoic paleo-climate changes, yet they remain stratigraphically unresolved. This new analysis of the Phanerozoic continental basins of south-central Africa and their equivalents in South America, opens a fresh continental-scale window into how West Gondwana break-up and concomitant epeirogenic uplifts of Kalahari (>2 km) and Congo (>200 m) are linked to interactions between the lithosphere and mantle geodynamics, and how these processes likely affected global climate changes.
- Full Text:
- Date Issued: 2013
- Authors: Linol, Bastien
- Date: 2013
- Subjects: Sedimentary basins -- Africa , Sedimentology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10655 , http://hdl.handle.net/10948/d1012148 , Sedimentary basins -- Africa , Sedimentology
- Description: The high elevated (ca. 1100 m) continental Kalahari Basin (KB) of southern Africa and the linked lower lying (ca. 400 m) Congo Basin (CB) of central Africa preserve in their interiors extensive sedimentary rock sequences and sediments that represent a unique record of the Phanerozoic geodynamic and climatic evolution of sub-Saharan Africa. In this thesis, field observations and new borehole data from the Democratic Republic of Congo (DRC) and Botswana are integrated with new paleontology and geochronology to present a substantially revised stratigraphy for the CB, and south-central Africa in general. This work also introduces a new multiphase model for the subsidence and uplift history of the CB, and improves correlations with the Cape-Karoo Basin (CKB) of South Africa and the Paraná Basin (PB) of south-east Brazil. Four deep boreholes, each between 2 and 4.5 km deep, drilled in the centre of the CB in the 1950’s and 1970’s are re-examined together with the colonial literature (in French) and available seismic data. This stratigraphic and basin analysis is complemented with new U-Pb dates of detrital zircons from core-samples of two of the boreholes (Samba and Dekese), as well as from samples collected during field work in the Kwango region of the south-west DRC. This work, for the first time, constrains the maximum ages and source provenances of the successions in the CB. Following the Pan African orogens (ca. 650-530 Ma), extensive sequences of red beds were deposited by regional paleocurrents to the south. These are now best preserved (1 km thick) along the West Congo, Oubanguides, and Lufilian Belts surrounding the CB. Overlying a hiatus that represents most of the early-Paleozoic, is a 1 to 3 km thick succession of easterly derived glacial, and then continental sequences of the Karoo Supergroup. This succession records the first main episode of subsidence [10-15 m/Ma], interrupted by a phase of uplift that is likely related to far-field intracontinental deformation within Gondwana supercontinent during the Variscan and Cape Fold orogenies (ca. 250-330 Ma) at its peripheries. Detrital zircons from the lower Karoo diamictites are dated at 1.85-2.05 Ga and 1.37- 1.42 Ga, and thus sourced from Paleoproterozoic (Eburnean) and mid-Mesoproterozoic (Kibaran type-I) basement rocks in Uganda and Tanzania. Zircons from all the other successions in the CB date predominantly at 950-1050 Ma and 500-800 Ma. These are derived from sediment recycling of late-Mesoproterozoic (Kibaran type-II) and late- Neoproterozoic (Pan African) sources in the Central African Republic (CAR) and Chad. A distinct unconformity across the Karoo Supergroup in the CB is overlain by 500- 1000 m Jurassic-Cretaceous sequences, here named the Congo Supergroup. During initial rapid subsidence [10-50 m/Ma], late-Jurassic (Kimmeridgian) shallow marine to continental sedimentation attests to a short transgression of proto-Indian Ocean waters into the northern CB (at 160 m above present day sea-level), succeeded by widespread deposition of aeolian dunes that extend from the southern CB to the PB in South America. The youngest zircons from these aeolian sediments in the CB date at 190 Ma and 240-290 Ma, and most likely indicate the influence of extensive silicic volcanic ash derived from the proto-Andes along the south-western margin of Gondwana. Two superimposed mid-Cretaceous (Albian-Cenomanian) lacustrine sequences in the central CB record a succeeding, slower [10-15 m/Ma], phase of basin subsidence during the opening of the South Atlantic (ca. 85-135 Ma). These Cretaceous sequences are in turn truncated by another regional peneplanation surface covered by Cenozoic (Eocene) silcretized sands and alluviums of the Kalahari Group, only 50-250 m thick in the centre of the CB. Southward, on top of the Kalahari Plateau in the central desert region of north-west Botswana, new boreholes intercepted laterally equivalent condensed lacustrine carbonates and calcretes (20-50 m thick) covered by sands. These terrestrial sequences are key archives of late-Mesozoic – Cenozoic paleo-climate changes, yet they remain stratigraphically unresolved. This new analysis of the Phanerozoic continental basins of south-central Africa and their equivalents in South America, opens a fresh continental-scale window into how West Gondwana break-up and concomitant epeirogenic uplifts of Kalahari (>2 km) and Congo (>200 m) are linked to interactions between the lithosphere and mantle geodynamics, and how these processes likely affected global climate changes.
- Full Text:
- Date Issued: 2013
Implementation of novel flow cytometric methods to assess the in vitro antidiabetic mechanism of a Sutherlandia Frutescens extract
- Authors: Elliot, Gayle Pamela
- Date: 2010
- Subjects: Insulin resistance -- South Africa , Insulin -- Therapeutic use -- South Africa , Medicinal plants -- South Africa , Non-insulin-dependent diabetes -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10304 , http://hdl.handle.net/10948/1439 , Insulin resistance -- South Africa , Insulin -- Therapeutic use -- South Africa , Medicinal plants -- South Africa , Non-insulin-dependent diabetes -- South Africa
- Description: The ability of insulin to stimulate glucose uptake into muscle and adipose tissue is central to the maintenance of whole-body glucose homeostasis. Deregulation of insulin action manifests itself as insulin resistance, a key component of type 2 diabetes. Insulin resistance is also observed in HIV patients receiving protease inhibitors. An agent that can reversibly induce an insulin-resistant state would be a very useful tool in developing model systems that mimic the pathogenesis of type 2 diabetes. Insulin resistance can arise from defects in insulin signal transduction, changes in the expression of proteins or genes that are targets of insulin action, cross talk from other hormonal systems or metabolic abnormalities. Deterioration of the insulin-receptor-signalling pathway at different levels leading to decreased levels of signalling pathway intermediates and/or decreased activation through phosphorylation accounts for the evolution from an insulin-resistant state to type 2 diabetes. In addition, defects in GLUT4 glucose transporter translocation are observed, further fuelling impairments in skeletal muscle glucose uptake. Levels of insulin-induced GLUT4 translocation in the skeletal muscle of type 2 diabetic patients are typically reduced by 90%. Many cellular pathways & their intermediates are in some way or another linked to insulin signalling. This study focused on three of these namely the PI3-kinase/Akt pathway, the Mitogen Activated Protein Kinase (MAPK) cascade and the AMP Kinase pathway, with successful monitoring of the PI3-K pathway. Investigations involved observing and evaluating the effects of various compounds as well as an indigenous medicinal plant, Sutherlandia frutescens on the activities of key insulin signalling pathway intermediates within the three fore mentioned pathways including Akt, AMPK and MEK1/2 as well as membrane surface GLUT4 levels. Scientific research has in the past leant heavily on Western blotting as the method of choice for gaining vital information relating to signal transduction pathways, however for research into cellular mechanisms the negatives of this method outweigh the positives. The drawbacks include a need for large amount of cells, multiple washing steps which may be disadvantageous to any weak and transient interactions as well as lysing of cells which may interfere with the maintenance of the subcellular localisation of a specific signalling event. Based on these, the need for a better method in terms of speed & reliability to monitor phosphorylation states of signal transduction pathway intermediates & GLUT4 translocation was evident and was one VII of the main aims & successes of this study. The method created used the mouse muscle cell line C2C12 in conjunction with the quick, sensitive method of flow cytometry which allowed us to monitor these processes in these cells through immune-labelling. Adherent cell cultures such as the C2C12 cell line pose the problem of possible damage to plasma membrane receptors (including insulin receptors) during harvesting to obtain a cell suspension for flow cytometry. We however used C2C12 mouse myocytes to optimize a method yielding insulin responsive cells in suspension that were successfully used for flow cytometry after immunelabelling of insulin signalling intermediates. Insulin (0.1μM) significantly raised the levels of both P-Akt and GLUT4 above basal levels. This effect was shown to be dose dependent. At a concentration of 50μg/ml, Sutherlandia frutescens was able to act as an insulin-mimetic in terms of its ability to increase P-Akt levels, GLUT4 translocation and glucose utilisation in an acute manner. These increases could be reduced with the addition of wortmannin, a PI3-K inhibitor. Therefore, these results suggest the mechanism of the plant extract’s insulin-like activity may be in part due to the activation of the insulin signalling pathway leading to GLUT4 translocation, which involves the phosphorylation of insulin receptor- and subsequent PI3-K activity, leading to P-Akt activity. These results provide further evidence of this plant extract’s anti-diabetic potential. The effect of Sutherlandia frutescens on insulin secretion, calcium signalling and proliferation in INS-1 rat pancreatic cells was also investigated and it was found to increase the activities of all of these processes. However no change in the levels of GLUT2 glucose transporter was seen. Ritonavir is prescribed by the South African Department of Health in co-formulation with other protease inhibitors within its second regime in the treatment of HIV and AIDS. Using C2C12 cells, ritonavir decreased glucose uptake acutely and had no effect on GLUT4 translocation however surprisingly increased P-Akt levels. In conclusion, it was found that Sutherlandia frutescens has antidiabetic benefits, diverse in nature depending on tissue type as well as length of time administered. The establishment of novel flow cytometry techniques to assess antidiabetic properties using in vitro cell culture was achieved. These methods will be useful in the future for the assessment of insulin sensitivity and in the identification of novel compounds that stimulate the insulin signalling pathways.
- Full Text:
- Date Issued: 2010
- Authors: Elliot, Gayle Pamela
- Date: 2010
- Subjects: Insulin resistance -- South Africa , Insulin -- Therapeutic use -- South Africa , Medicinal plants -- South Africa , Non-insulin-dependent diabetes -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10304 , http://hdl.handle.net/10948/1439 , Insulin resistance -- South Africa , Insulin -- Therapeutic use -- South Africa , Medicinal plants -- South Africa , Non-insulin-dependent diabetes -- South Africa
- Description: The ability of insulin to stimulate glucose uptake into muscle and adipose tissue is central to the maintenance of whole-body glucose homeostasis. Deregulation of insulin action manifests itself as insulin resistance, a key component of type 2 diabetes. Insulin resistance is also observed in HIV patients receiving protease inhibitors. An agent that can reversibly induce an insulin-resistant state would be a very useful tool in developing model systems that mimic the pathogenesis of type 2 diabetes. Insulin resistance can arise from defects in insulin signal transduction, changes in the expression of proteins or genes that are targets of insulin action, cross talk from other hormonal systems or metabolic abnormalities. Deterioration of the insulin-receptor-signalling pathway at different levels leading to decreased levels of signalling pathway intermediates and/or decreased activation through phosphorylation accounts for the evolution from an insulin-resistant state to type 2 diabetes. In addition, defects in GLUT4 glucose transporter translocation are observed, further fuelling impairments in skeletal muscle glucose uptake. Levels of insulin-induced GLUT4 translocation in the skeletal muscle of type 2 diabetic patients are typically reduced by 90%. Many cellular pathways & their intermediates are in some way or another linked to insulin signalling. This study focused on three of these namely the PI3-kinase/Akt pathway, the Mitogen Activated Protein Kinase (MAPK) cascade and the AMP Kinase pathway, with successful monitoring of the PI3-K pathway. Investigations involved observing and evaluating the effects of various compounds as well as an indigenous medicinal plant, Sutherlandia frutescens on the activities of key insulin signalling pathway intermediates within the three fore mentioned pathways including Akt, AMPK and MEK1/2 as well as membrane surface GLUT4 levels. Scientific research has in the past leant heavily on Western blotting as the method of choice for gaining vital information relating to signal transduction pathways, however for research into cellular mechanisms the negatives of this method outweigh the positives. The drawbacks include a need for large amount of cells, multiple washing steps which may be disadvantageous to any weak and transient interactions as well as lysing of cells which may interfere with the maintenance of the subcellular localisation of a specific signalling event. Based on these, the need for a better method in terms of speed & reliability to monitor phosphorylation states of signal transduction pathway intermediates & GLUT4 translocation was evident and was one VII of the main aims & successes of this study. The method created used the mouse muscle cell line C2C12 in conjunction with the quick, sensitive method of flow cytometry which allowed us to monitor these processes in these cells through immune-labelling. Adherent cell cultures such as the C2C12 cell line pose the problem of possible damage to plasma membrane receptors (including insulin receptors) during harvesting to obtain a cell suspension for flow cytometry. We however used C2C12 mouse myocytes to optimize a method yielding insulin responsive cells in suspension that were successfully used for flow cytometry after immunelabelling of insulin signalling intermediates. Insulin (0.1μM) significantly raised the levels of both P-Akt and GLUT4 above basal levels. This effect was shown to be dose dependent. At a concentration of 50μg/ml, Sutherlandia frutescens was able to act as an insulin-mimetic in terms of its ability to increase P-Akt levels, GLUT4 translocation and glucose utilisation in an acute manner. These increases could be reduced with the addition of wortmannin, a PI3-K inhibitor. Therefore, these results suggest the mechanism of the plant extract’s insulin-like activity may be in part due to the activation of the insulin signalling pathway leading to GLUT4 translocation, which involves the phosphorylation of insulin receptor- and subsequent PI3-K activity, leading to P-Akt activity. These results provide further evidence of this plant extract’s anti-diabetic potential. The effect of Sutherlandia frutescens on insulin secretion, calcium signalling and proliferation in INS-1 rat pancreatic cells was also investigated and it was found to increase the activities of all of these processes. However no change in the levels of GLUT2 glucose transporter was seen. Ritonavir is prescribed by the South African Department of Health in co-formulation with other protease inhibitors within its second regime in the treatment of HIV and AIDS. Using C2C12 cells, ritonavir decreased glucose uptake acutely and had no effect on GLUT4 translocation however surprisingly increased P-Akt levels. In conclusion, it was found that Sutherlandia frutescens has antidiabetic benefits, diverse in nature depending on tissue type as well as length of time administered. The establishment of novel flow cytometry techniques to assess antidiabetic properties using in vitro cell culture was achieved. These methods will be useful in the future for the assessment of insulin sensitivity and in the identification of novel compounds that stimulate the insulin signalling pathways.
- Full Text:
- Date Issued: 2010
Vapour phase dehydrogenation of cyclohexane on microstructured reactors
- Authors: Mpuhlu, Batsho
- Date: 2012
- Subjects: Dehydrogenation , Cyclohexane
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: http://hdl.handle.net/10948/8661 , vital:26418
- Description: The work that is described in this thesis forms part of the research and development projects at InnoVenton: NMMU Institute of Chemical Technology in collaboration with Sasol Technologies. The broader view of the project was testing on the so-called “Small Production Platforms” (SPP’s). In particular the main aim of this study was to investigate the effect of micro-structuring on the heterogeneous catalysed, vapour-phase oxidative dehydrogenation of cyclohexane in the presence of air. Ground work studies were done to provide a proper comparison of the micro-structured reactor with a traditional fixed-bed reactor. These included evaluation of a proper vanadium pyrophosphate catalyst for the reaction, testing of reaction parameters for the oxidative dehydrogenation reaction on a fixed-bed reactor and lastly comparing the performance of the micro-structured reactor to that of the fixed-bed reactor Various vanadium pyrophosphate catalysts that were tested for activity included: bulk (VO)2P2O7, bulk (VO)2P2O7 promoted with Fe, (VO)2P2O7 supported on -Al2O3 and Fe promoted (VO)2P2O7 supported on -Al2O3. These catalysts showed significant differences in TOF, however it was not conclusive from the results whether these differences may be traced to increased activity for dehydrogenation for different catalysts since all reactions were run under conditions of oxygen deficiency. It is, however, clear that Fe promotion significantly increase activity, irrespective of the relative degrees of oxidative dehydrogenation and normal dehydrogenation. The Fe promoted catalyst was further tested for long term stability in-view of using it as the catalyst in the micro-structured reactor. These studies showed the catalyst to have a high degree of stability with minimal structural changes under the reaction conditions used. Various response surface models describing the variation in each of the cyclohexane conversion, cyclohexene selectivity, and benzene selectivity, respectively when changing reaction condition, were derived by means of multiple regression. To obtain some idea of the degree and nature of the normal dehydrogenation reaction, the amount of deficit oxygen was estimated from the measured results for cyclohexane conversion and cyclohexene and benzene selectivities. These estimated values were also modelled as described above. The regression models were used to interpret specific trends in the responses for the oxidative dehydrogenation of cyclohexane and account for the oxygen deficit in the system. The performance of a fixed bed tubular reactor (FBR) and micro-structured sandwich reactor (MSSR) were compared over an Fe promoted vanadium pyrophosphate. Reactor performance was evaluated by varying specific reaction conditions (temperature and space velocity). Subsequently the turn-over frequencies, conversion and selectivities from the two reactors were compared. The conversion achieved in the micro-structured reactor was observed to be significantly higher than that achieved in the fixed-bed reactor at all reaction parameters. This is despite the fact that the total amount of catalyst in the micro-structured reactor is approximately 5 times less than that used in the fixed bed reactor. In addition, the contact time (1/MHSV) in the micro-structured reactor is also significantly shorter than in the fixed-bed reactor.
- Full Text:
- Date Issued: 2012
- Authors: Mpuhlu, Batsho
- Date: 2012
- Subjects: Dehydrogenation , Cyclohexane
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: http://hdl.handle.net/10948/8661 , vital:26418
- Description: The work that is described in this thesis forms part of the research and development projects at InnoVenton: NMMU Institute of Chemical Technology in collaboration with Sasol Technologies. The broader view of the project was testing on the so-called “Small Production Platforms” (SPP’s). In particular the main aim of this study was to investigate the effect of micro-structuring on the heterogeneous catalysed, vapour-phase oxidative dehydrogenation of cyclohexane in the presence of air. Ground work studies were done to provide a proper comparison of the micro-structured reactor with a traditional fixed-bed reactor. These included evaluation of a proper vanadium pyrophosphate catalyst for the reaction, testing of reaction parameters for the oxidative dehydrogenation reaction on a fixed-bed reactor and lastly comparing the performance of the micro-structured reactor to that of the fixed-bed reactor Various vanadium pyrophosphate catalysts that were tested for activity included: bulk (VO)2P2O7, bulk (VO)2P2O7 promoted with Fe, (VO)2P2O7 supported on -Al2O3 and Fe promoted (VO)2P2O7 supported on -Al2O3. These catalysts showed significant differences in TOF, however it was not conclusive from the results whether these differences may be traced to increased activity for dehydrogenation for different catalysts since all reactions were run under conditions of oxygen deficiency. It is, however, clear that Fe promotion significantly increase activity, irrespective of the relative degrees of oxidative dehydrogenation and normal dehydrogenation. The Fe promoted catalyst was further tested for long term stability in-view of using it as the catalyst in the micro-structured reactor. These studies showed the catalyst to have a high degree of stability with minimal structural changes under the reaction conditions used. Various response surface models describing the variation in each of the cyclohexane conversion, cyclohexene selectivity, and benzene selectivity, respectively when changing reaction condition, were derived by means of multiple regression. To obtain some idea of the degree and nature of the normal dehydrogenation reaction, the amount of deficit oxygen was estimated from the measured results for cyclohexane conversion and cyclohexene and benzene selectivities. These estimated values were also modelled as described above. The regression models were used to interpret specific trends in the responses for the oxidative dehydrogenation of cyclohexane and account for the oxygen deficit in the system. The performance of a fixed bed tubular reactor (FBR) and micro-structured sandwich reactor (MSSR) were compared over an Fe promoted vanadium pyrophosphate. Reactor performance was evaluated by varying specific reaction conditions (temperature and space velocity). Subsequently the turn-over frequencies, conversion and selectivities from the two reactors were compared. The conversion achieved in the micro-structured reactor was observed to be significantly higher than that achieved in the fixed-bed reactor at all reaction parameters. This is despite the fact that the total amount of catalyst in the micro-structured reactor is approximately 5 times less than that used in the fixed bed reactor. In addition, the contact time (1/MHSV) in the micro-structured reactor is also significantly shorter than in the fixed-bed reactor.
- Full Text:
- Date Issued: 2012