Cape Vultures (Gyps coprotheres) and the threat of wind farms: a race to extinction?
- Authors: Brooke, Francis Rae
- Date: 2022-04
- Subjects: Wind Turbines --Blades --Materials , Gyps --South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55910 , vital:54399
- Description: The development of wind energy is increasing globally and is often considered more environmentally friendly when compared to fossil fuel technologies. However, one of the ecological drawbacks of wind energy are the collisions of wildlife with turbine blades. In addition, the resulting anthropogenic landscape transformation can negatively impact populations. The Cape Vulture (Gyps coprotheres), a large endangered southern African endemic species, thus may be at risk from turbine development. The species has decreased dramatically in the past 50 years and understanding how additional mortalities from wind turbine impacts affect the population is needed to ensure effective conservation efforts. This study aimed to determine the population response to this emerging threat. This study first reviewed the species-, site- and wind farm- specific traits that make Gyps species vulnerable to collision with wind energy infrastructure. It examined the monitoring practices employed during the pre- and post-construction phase and mitigation measures in South Africa and compared it with international standards. Furthermore, wind energy development may disrupt landscape connectivity and understanding which, and how habitat patches are used is needed. Using network theory combined with telemetry data from tagged individuals across three age classes, habitat patch use was identified. Further, environmental variables associated with identified habitat patches were identified. Additionally, considering the wind energy industry is expanding in South Africa, exploring how the Cape Vulture population will respond to this novel and emerging threat may aid future conservation management plans. Therefore, using a population viability analysis approach, the study explored how present and future wind turbine mortality scenarios impact the Cape Vulture population and how the population will respond to increased wind turbine development. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2022
- Full Text:
- Date Issued: 2022-04
- Authors: Brooke, Francis Rae
- Date: 2022-04
- Subjects: Wind Turbines --Blades --Materials , Gyps --South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55910 , vital:54399
- Description: The development of wind energy is increasing globally and is often considered more environmentally friendly when compared to fossil fuel technologies. However, one of the ecological drawbacks of wind energy are the collisions of wildlife with turbine blades. In addition, the resulting anthropogenic landscape transformation can negatively impact populations. The Cape Vulture (Gyps coprotheres), a large endangered southern African endemic species, thus may be at risk from turbine development. The species has decreased dramatically in the past 50 years and understanding how additional mortalities from wind turbine impacts affect the population is needed to ensure effective conservation efforts. This study aimed to determine the population response to this emerging threat. This study first reviewed the species-, site- and wind farm- specific traits that make Gyps species vulnerable to collision with wind energy infrastructure. It examined the monitoring practices employed during the pre- and post-construction phase and mitigation measures in South Africa and compared it with international standards. Furthermore, wind energy development may disrupt landscape connectivity and understanding which, and how habitat patches are used is needed. Using network theory combined with telemetry data from tagged individuals across three age classes, habitat patch use was identified. Further, environmental variables associated with identified habitat patches were identified. Additionally, considering the wind energy industry is expanding in South Africa, exploring how the Cape Vulture population will respond to this novel and emerging threat may aid future conservation management plans. Therefore, using a population viability analysis approach, the study explored how present and future wind turbine mortality scenarios impact the Cape Vulture population and how the population will respond to increased wind turbine development. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2022
- Full Text:
- Date Issued: 2022-04
Spatial and temporal analysis of the critical zone in the Western rift valley corridor: towards earth stewardship science in East Africa
- Authors: Miller, Warren David
- Date: 2022-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/59771 , vital:62423
- Description: Over the coming decades, Africa is expected to experience disturbing effects due to climate change and increased land cover change due to human influences presenting a significant concern for the future well-being of human and biological systems, the latter being the foundation of ecosystem services supplied to humanity. Therefore, unprecedented transdisciplinary cooperation, coordination, and integration amongst researchers, government, and civil society are necessary to increase the resiliency of these systems. This study aims to provide an outline of the Africa Alive Corridors (AAC) as an essential model for the encouragement of sustainable development through Earth Stewardship science. These aims are accompanied by the quantification and forward modelling for land cover change of the Critical Zone over 10 Great Lake Basins across one of the AAC, the Western Rift Valley Corridor (WRVC), in East Africa between the years 2018 and 2060. This approach provides the foundation for implementing improved regional governance, better encouragement of sustainable development beyond the 2030 United Nations Sustainable Development Goals, and education programs, such as the AAC, that promote socio-ecological resilience through Earth Stewardship Science. The AAC archives a portion of East Africa as the WRVC, a corridor along the western branch of the East African Rift System that highlights twenty heritage nodes, primarily great lakes, mountain ranges, national parks, and biological hotspots. These heritage entities are associated with ca. 12-million-years of evolution and transformation of the East African topography and related African Great Lake (AGL) systems. The thesis defines the study area by delineating AGL basins intersected by the WRVC. Across these basins, land cover change analysis provides a platform for an integrated assessment of the projected health of the corridor region. Existing land cover datasets provide the initial conditions of the study area for 2008 and 2013. Land cover between 2008 and 2013 is cross-tabulated using the Land Cover Module in the Terrset software, followed by the iii delineation of sub-models and driver variable identification. The Multi-Layer Perceptron algorithm provides the transition potentials between tree cover, urban area, cropland, wetland, and open area classes. Change quantification and prediction using Markov Chain analysis are then established for 2018, 2030, and 2060. The model successfully simulated future land cover change and concluded that: (1) proximity to existing human activity, proximity to existing tree cover, and population are the primary drivers of change; (2) the dominant land cover of the ten lake basins for 2018 was cropland at ca. 48%, followed by tree cover at ca. 33%; (3) total anthropogenic change over the coming four decades equates to over ca. 52 000 km2 (5 200 000 ha), and particularly (4) an urban area is expected to increase by >130%. This assessment ultimately provides a platform for regional governance development at the basin scale and Earth Stewardship science in East Africa. These changes require transdisciplinary action from researchers to civil society. The AAC provides the foundation for understanding the dynamics of the systems that support life across broader spatial and temporal resolutions in Africa, highlighting the need for future generations to build socio-ecological resilience to anticipate challenges such as biodiversity loss posed by climate change and excessive land cover change. , Thesis (DSc) -- Faculty of Science, School of Environmental Sciences, 2022
- Full Text:
- Date Issued: 2022-12
- Authors: Miller, Warren David
- Date: 2022-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/59771 , vital:62423
- Description: Over the coming decades, Africa is expected to experience disturbing effects due to climate change and increased land cover change due to human influences presenting a significant concern for the future well-being of human and biological systems, the latter being the foundation of ecosystem services supplied to humanity. Therefore, unprecedented transdisciplinary cooperation, coordination, and integration amongst researchers, government, and civil society are necessary to increase the resiliency of these systems. This study aims to provide an outline of the Africa Alive Corridors (AAC) as an essential model for the encouragement of sustainable development through Earth Stewardship science. These aims are accompanied by the quantification and forward modelling for land cover change of the Critical Zone over 10 Great Lake Basins across one of the AAC, the Western Rift Valley Corridor (WRVC), in East Africa between the years 2018 and 2060. This approach provides the foundation for implementing improved regional governance, better encouragement of sustainable development beyond the 2030 United Nations Sustainable Development Goals, and education programs, such as the AAC, that promote socio-ecological resilience through Earth Stewardship Science. The AAC archives a portion of East Africa as the WRVC, a corridor along the western branch of the East African Rift System that highlights twenty heritage nodes, primarily great lakes, mountain ranges, national parks, and biological hotspots. These heritage entities are associated with ca. 12-million-years of evolution and transformation of the East African topography and related African Great Lake (AGL) systems. The thesis defines the study area by delineating AGL basins intersected by the WRVC. Across these basins, land cover change analysis provides a platform for an integrated assessment of the projected health of the corridor region. Existing land cover datasets provide the initial conditions of the study area for 2008 and 2013. Land cover between 2008 and 2013 is cross-tabulated using the Land Cover Module in the Terrset software, followed by the iii delineation of sub-models and driver variable identification. The Multi-Layer Perceptron algorithm provides the transition potentials between tree cover, urban area, cropland, wetland, and open area classes. Change quantification and prediction using Markov Chain analysis are then established for 2018, 2030, and 2060. The model successfully simulated future land cover change and concluded that: (1) proximity to existing human activity, proximity to existing tree cover, and population are the primary drivers of change; (2) the dominant land cover of the ten lake basins for 2018 was cropland at ca. 48%, followed by tree cover at ca. 33%; (3) total anthropogenic change over the coming four decades equates to over ca. 52 000 km2 (5 200 000 ha), and particularly (4) an urban area is expected to increase by >130%. This assessment ultimately provides a platform for regional governance development at the basin scale and Earth Stewardship science in East Africa. These changes require transdisciplinary action from researchers to civil society. The AAC provides the foundation for understanding the dynamics of the systems that support life across broader spatial and temporal resolutions in Africa, highlighting the need for future generations to build socio-ecological resilience to anticipate challenges such as biodiversity loss posed by climate change and excessive land cover change. , Thesis (DSc) -- Faculty of Science, School of Environmental Sciences, 2022
- Full Text:
- Date Issued: 2022-12
The effect of Cannabis extract on the morphological and metabolic characteristics of various fat depots in diet-induced Obese and STZ-induced male wistar rats
- Authors: Ramlugon, Sonaal
- Date: 2023-04
- Subjects: Rats as laboratory animals , Diabetes in practice , Cannabis -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/61282 , vital:70044
- Description: To investigate the potential anti-diabetic/obesity properties of oral cannabis administration in an obese and streptozotocin (STZ)-induced diabetic rat model, as well as an obese rat model, and to determine the mechanism of action, with a focus on the peritoneal and intramuscular fat depots. Experimental Design: Obese and STZ-induced diabetic rats were allocated a high fat diet (HFD) and intraperitoneally injected with STZ to mimic an obese and diabetic state. The rats were then orally administered cannabis extract (CE) of 1.25, 2.5 and 5.0 mg/kg body weight (relative to tetrahydrocannabinol (THC) content) or metformin as a positive control. For the obese rat model, the rats were allocated either a high carbohydrate diet (HCD) or high fat diet (HFD) and orally administered with cannabis extract of 1.25 mg/kg body weight (relative to THC content). Weight, blood and insulin-resistant parameters of the rats were monitored. The mitochondrial to genomic DNA ratio (MT:18S DNA), average adipocyte area of the various adipose tissues, citrate synthase and carnitine palmitoyltransferase 1 (CPT1) enzyme activities of the peritoneal and intramuscular fat were measured. Gene expression levels of uncoupling protein 1 (UCP1), cell-death inducing DNA fragmentation factor alpha like effector-a (Cidea), perilipin, hormone-sensitive lipase (HSL) and mitochondrial transcription factor A (TFAM) were measured in peritoneal fat, intramuscular fat and brown adipose tissue (BAT). Main Findings: Obese and STZ-induced diabetic rat model: Due to the biphasic nature of cannabinoids, cannabis dosage plays an important role in the observed effects. CE1.25 was the only cannabis treatment effective in improving the insulinresistant parameters of the rats unlike the other higher cannabis concentrations (CE2.5 and CE5.0). In the peritoneal fat, CE1.25 increased MT:18S DNA, increased citrate synthase activity, and decreased the average adipocyte area when compared to the STZ group. CE1.25 also induced fat beigeing by upregulating gene expression levels of UCP1 and Cidea. XIX Furthermore, an increase in gene expression levels of perilipin, HSL, and TFAM showed increased fat mobilization and metabolic activity. In the intramuscular fat, CE1.25 also reduced the average adipocytes area. However, a different mechanism of action was observed where CE1.25 did not induce fat beigeing, but instead increased both citrate synthase and CPT1 enzyme activities and gene expression levels of HSL, thereby indicating increased fat oxidation and mitochondrial activity. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-04
- Authors: Ramlugon, Sonaal
- Date: 2023-04
- Subjects: Rats as laboratory animals , Diabetes in practice , Cannabis -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/61282 , vital:70044
- Description: To investigate the potential anti-diabetic/obesity properties of oral cannabis administration in an obese and streptozotocin (STZ)-induced diabetic rat model, as well as an obese rat model, and to determine the mechanism of action, with a focus on the peritoneal and intramuscular fat depots. Experimental Design: Obese and STZ-induced diabetic rats were allocated a high fat diet (HFD) and intraperitoneally injected with STZ to mimic an obese and diabetic state. The rats were then orally administered cannabis extract (CE) of 1.25, 2.5 and 5.0 mg/kg body weight (relative to tetrahydrocannabinol (THC) content) or metformin as a positive control. For the obese rat model, the rats were allocated either a high carbohydrate diet (HCD) or high fat diet (HFD) and orally administered with cannabis extract of 1.25 mg/kg body weight (relative to THC content). Weight, blood and insulin-resistant parameters of the rats were monitored. The mitochondrial to genomic DNA ratio (MT:18S DNA), average adipocyte area of the various adipose tissues, citrate synthase and carnitine palmitoyltransferase 1 (CPT1) enzyme activities of the peritoneal and intramuscular fat were measured. Gene expression levels of uncoupling protein 1 (UCP1), cell-death inducing DNA fragmentation factor alpha like effector-a (Cidea), perilipin, hormone-sensitive lipase (HSL) and mitochondrial transcription factor A (TFAM) were measured in peritoneal fat, intramuscular fat and brown adipose tissue (BAT). Main Findings: Obese and STZ-induced diabetic rat model: Due to the biphasic nature of cannabinoids, cannabis dosage plays an important role in the observed effects. CE1.25 was the only cannabis treatment effective in improving the insulinresistant parameters of the rats unlike the other higher cannabis concentrations (CE2.5 and CE5.0). In the peritoneal fat, CE1.25 increased MT:18S DNA, increased citrate synthase activity, and decreased the average adipocyte area when compared to the STZ group. CE1.25 also induced fat beigeing by upregulating gene expression levels of UCP1 and Cidea. XIX Furthermore, an increase in gene expression levels of perilipin, HSL, and TFAM showed increased fat mobilization and metabolic activity. In the intramuscular fat, CE1.25 also reduced the average adipocytes area. However, a different mechanism of action was observed where CE1.25 did not induce fat beigeing, but instead increased both citrate synthase and CPT1 enzyme activities and gene expression levels of HSL, thereby indicating increased fat oxidation and mitochondrial activity. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-04
An exploration of the Participatory Guarantee System (PGS) facilitating the growth and certification of small-scale organic farmers: Giyani, Garden Route and Overberg case studies
- Authors: Mashele,N’wa-Jama
- Date: 2023-04
- Subjects: Organic farming – Case studies --South Africa , Organic farming research
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/60741 , vital:66574
- Description: In this study, I evaluated the Participatory Guarantee System (PGS) as a framework to support the growth and certification of small-scale organic farmers. I used the interpretivism and constructivism lenses to understand the PGS from the perspective of members of three PGS groups. The research was qualitative, treating the three PGS groups as case studies. I collected data using focus groups, semi-structured interviews, questionnaires, field notes and observations. The theoretical frameworks that guided the research and data analysis were Socio-ecological Systems (SES) based principles and the Multi-Level-Perspective (MLP) framework. The data were analysed using Atlas.ti content analysis software. The key results were grouped into four themes: capacity; market and logistics; learning process; and disturbance, shock and stress. The theme of ‘capacity’ dealt with the functioning of a PGS, where three categories were identified: group composition and capacity; resource limitations and institutional support; marketing and consumer education. The more diversity in age, education and culture of PGS stakeholders, the better performance and chances of continuity and propagation. PGS has limited capacity partly due to its voluntary nature and infancy. It needs institutional support to grow and be useful for members. Department of Agriculture extension officers knew little about organic farming, thus limiting their engagement and assistance to such farmers. The theme of ‘market and logistics’ looked at the various factors that influence the farmers’ market reach. The perception from the members was that there was minimal consumer awareness about organic agriculture and the PGS. The marketing of organic produce relied largely on the individual farmer’s efforts and ability to search for and secure markets. The theme of the ‘learning process’ was categorised into learning and knowledge exchange. Members of the PGS groups highly regarded the invaluable knowledge shared through farm visits and online platforms, such as their WhatsApp groups. This knowledge improved and informed their farming techniques and led to the growth of v their skill base and experimentation. They viewed the way knowledge was exchanged as non-threatening and highly useful. The fourth theme of ‘disturbance, shock and stress’ dealt with the effects of COVID19. The three groups were all affected by lockdown restrictions (at the time of data collection) and were initially cut off from their usual markets. This led to a loss of income, loss of farm staff and a loss of the desired growth of the farms. The group’s diverse farming practices bolstered their resilience, enabling them to adapt and try alternative marketing strategies. , Thesis (MSc) -- Faculty of Science, School of Natural Resource Management, 2023
- Full Text:
- Date Issued: 2023-04
- Authors: Mashele,N’wa-Jama
- Date: 2023-04
- Subjects: Organic farming – Case studies --South Africa , Organic farming research
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/60741 , vital:66574
- Description: In this study, I evaluated the Participatory Guarantee System (PGS) as a framework to support the growth and certification of small-scale organic farmers. I used the interpretivism and constructivism lenses to understand the PGS from the perspective of members of three PGS groups. The research was qualitative, treating the three PGS groups as case studies. I collected data using focus groups, semi-structured interviews, questionnaires, field notes and observations. The theoretical frameworks that guided the research and data analysis were Socio-ecological Systems (SES) based principles and the Multi-Level-Perspective (MLP) framework. The data were analysed using Atlas.ti content analysis software. The key results were grouped into four themes: capacity; market and logistics; learning process; and disturbance, shock and stress. The theme of ‘capacity’ dealt with the functioning of a PGS, where three categories were identified: group composition and capacity; resource limitations and institutional support; marketing and consumer education. The more diversity in age, education and culture of PGS stakeholders, the better performance and chances of continuity and propagation. PGS has limited capacity partly due to its voluntary nature and infancy. It needs institutional support to grow and be useful for members. Department of Agriculture extension officers knew little about organic farming, thus limiting their engagement and assistance to such farmers. The theme of ‘market and logistics’ looked at the various factors that influence the farmers’ market reach. The perception from the members was that there was minimal consumer awareness about organic agriculture and the PGS. The marketing of organic produce relied largely on the individual farmer’s efforts and ability to search for and secure markets. The theme of the ‘learning process’ was categorised into learning and knowledge exchange. Members of the PGS groups highly regarded the invaluable knowledge shared through farm visits and online platforms, such as their WhatsApp groups. This knowledge improved and informed their farming techniques and led to the growth of v their skill base and experimentation. They viewed the way knowledge was exchanged as non-threatening and highly useful. The fourth theme of ‘disturbance, shock and stress’ dealt with the effects of COVID19. The three groups were all affected by lockdown restrictions (at the time of data collection) and were initially cut off from their usual markets. This led to a loss of income, loss of farm staff and a loss of the desired growth of the farms. The group’s diverse farming practices bolstered their resilience, enabling them to adapt and try alternative marketing strategies. , Thesis (MSc) -- Faculty of Science, School of Natural Resource Management, 2023
- Full Text:
- Date Issued: 2023-04
Flash floods prediction in South African urban areas: Jukskei river catchment as case study
- Authors: Mawasha, Tshepo Sylvester
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , Geographic information systems
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/52059 , vital:43429
- Description: This study explored the change relation of multi-temporal land-use/land-cover (LULC) conditions in order to determine how they contribute to change in surface runoff volumes and peak discharge, in an effort to predict flash flooding within the Jukskei River catchment. The research is divided into three main parts: (1) LULC change modeling, (2) rainfall-runoff modeling, and (3) flash floods prediction. Three multi-temporal satellite images of Landsat-5 MMS (1987), Landsat-5 TM (2001) and Landsat-8 OLI (2015) were used for LULC modeling. The analysis of the LULC model revealed that there is a continuous increment in built-up area, from 37.7% to 56.2%, in the expense of other LULC classes for the 28-years preceding this study (i.e., 1987 to 2015). Rainfall-runoff model output results revealed that, for these 28 years, there has been an increase in surface runoff due to change in LULC by 21.5%, 32.9% and 45.5% for 1987, 2001 and 2015, respectively. Due to an increase in surface runoff volume and impervious surface over time, the analysis of HEC-RAS/GeoRAS showed that floodplain extent, flood depth, flood velocity, depth-velocity and the level of damage increases especially in low elevation areas and areas at closed proximity to the Jukskei River. Thus, the building structures and infrastructures are at risk of being affected by flash floods during the rainy season. The findings of this study are expected to be used as basic data for the identification of causative factors of flash floods, areas that generate high surface runoff volume, and the prediction of flash floods within the catchment in future. The flood damage maps developed in this study will be useful to policy-makers and the relevant authorities, as well as to local residents, in finding suitable measures for residential development along the floodplain while reducing flood risk in the study area. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2021
- Full Text: false
- Date Issued: 2021-04
- Authors: Mawasha, Tshepo Sylvester
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , Geographic information systems
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/52059 , vital:43429
- Description: This study explored the change relation of multi-temporal land-use/land-cover (LULC) conditions in order to determine how they contribute to change in surface runoff volumes and peak discharge, in an effort to predict flash flooding within the Jukskei River catchment. The research is divided into three main parts: (1) LULC change modeling, (2) rainfall-runoff modeling, and (3) flash floods prediction. Three multi-temporal satellite images of Landsat-5 MMS (1987), Landsat-5 TM (2001) and Landsat-8 OLI (2015) were used for LULC modeling. The analysis of the LULC model revealed that there is a continuous increment in built-up area, from 37.7% to 56.2%, in the expense of other LULC classes for the 28-years preceding this study (i.e., 1987 to 2015). Rainfall-runoff model output results revealed that, for these 28 years, there has been an increase in surface runoff due to change in LULC by 21.5%, 32.9% and 45.5% for 1987, 2001 and 2015, respectively. Due to an increase in surface runoff volume and impervious surface over time, the analysis of HEC-RAS/GeoRAS showed that floodplain extent, flood depth, flood velocity, depth-velocity and the level of damage increases especially in low elevation areas and areas at closed proximity to the Jukskei River. Thus, the building structures and infrastructures are at risk of being affected by flash floods during the rainy season. The findings of this study are expected to be used as basic data for the identification of causative factors of flash floods, areas that generate high surface runoff volume, and the prediction of flash floods within the catchment in future. The flood damage maps developed in this study will be useful to policy-makers and the relevant authorities, as well as to local residents, in finding suitable measures for residential development along the floodplain while reducing flood risk in the study area. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2021
- Full Text: false
- Date Issued: 2021-04
The synthesis, empirical and theoretical studies of various (N→B) diarylborinate esters
- Authors: Manana, Pholani Sakhile
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53869 , vital:46027
- Description: A series of core-functionalized borinic acids was synthesized from Grignard reagents and tributylborate and reacted with ethanolamine, amino acids, 2-pyridylmethanol as well as 2-(ethyl amino ethanol). Among the borinic acids synthesized were the ones bearing: para-(2, 15, 16, 22, 27)-methyl, (3, 20, 25)-chloro, (4, 23, 26)-fluoro, (5)-methoxy; meta-(7, 17)-methyl, (9)-fluoro; ortho-(6)-methyl, (8)-chloro, (10, 18, 19)-methoxy substituents on their respective aromatic systems. All compounds obtained by condensation of the borinic acids with the aforementioned nitrogen-containing substrates were characterized structurally by means of diffraction studies based on single crystals and found to constitute chelate esters/amides featuring covalent B-O and dative N→B bonds. The chelate compounds researched in this study could be classified into four families and represent the compounds: ethanol amine: (1) 2,2-diphenyl-1,3,2-oxazaborolidines, (2) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (3) 2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (4) 2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (5) 2,2-bis(p-methoxyphenyl)-1,3,2-oxazaborolidines, (6) 2,2-bis(o-tolyl)-1,3,2-oxazaborolidines, (7) 2,2-bis(m-tolyl)-1,3,2-oxazaborolidines, (8) 2,2-bis(o-chlorophenyl)-1,3,2-oxazaborolidines, (9) 2,2-bis(m-fluorophenyl)-1,3,2-oxazaborolidines, (10) 2,2-bis(o-methoxyphenyl)-1,3,2-oxazaborolidines. α-amino acids : (14) 4-methyl-2,2-diphenyl-1,3,2-oxazaborolidin-5-ones, (15) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (16) 4-methyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (17) 4-isopropyl-2,2-bis(m-tolyl)-1,3,2-oxazaborolidin-5-ones, (18) 4-methyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (19) 4-acetamidyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (20) 4-phenylethane-2,2-bis(p-chlorophenyl)-1,3,2 oxazaborolidin-5-ones. 2-pyridylmethanol: (21) 1,3-hydroxypyridyl-2,2-diphenyl 1,3,2-oxazaborolidines, (22) 1,3-hydroxypyridyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (23) 1,3-hydroxypyridyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines 2-(ethyl amino ethanol): (24) 3-ethyl-2,2-diphenyl-1,3,2-oxazaborolidines, (25) 3-ethyl-2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (26) 3-ethyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (27) 3-ethyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines. Apart from structural studies in the solid state, the compounds were also characterized by means of multinuclear NMR spectroscopy (1H, 11B, 13C) as well as UV/vis and FTIR. The typical 11B resonances were found in the range of (4-10 ppm). A series of characteristic metrical parameters for the compounds in the solid state as well as typical NMR shifts for the chelate target molecules was established that allowed for the determination of the coordination induced shift. The carbon atom bonded to the oxygen atom shifted upfield, while the carbon atom bonded to the nitrogen atom shifted downfield. Factors mentioned in the literature that has an influence on the hydrolytic stability on the heterocyclic borinate motif have been taken into consideration and verified for the systems researched in this study. The substitution at the nitrogen atom with one ethyl group caused the greatest increases in the N→B bond length (27) 1.714 Å, due to the increase in the nitrogen Lewis basicity, making it the least hydrolytically stable, these include compounds (24-26). Furthermore, DFT calculations were performed by employing Becke’s three parameter hybrid exchange functional with Lee–Yang–Parr functional (B3LYP) method using the Gaussian 16 program package (Rev. B01) employing the basis set 6-311++G(d,p), to corroborate and correlate the experimental findings, which gave a general R-squared value of 0.9978 for calculated vs experimental 13C chemical shifts. Thermal properties are recorded for select compounds, indicating the ΔH and the melting points. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text:
- Date Issued: 2021-12
- Authors: Manana, Pholani Sakhile
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53869 , vital:46027
- Description: A series of core-functionalized borinic acids was synthesized from Grignard reagents and tributylborate and reacted with ethanolamine, amino acids, 2-pyridylmethanol as well as 2-(ethyl amino ethanol). Among the borinic acids synthesized were the ones bearing: para-(2, 15, 16, 22, 27)-methyl, (3, 20, 25)-chloro, (4, 23, 26)-fluoro, (5)-methoxy; meta-(7, 17)-methyl, (9)-fluoro; ortho-(6)-methyl, (8)-chloro, (10, 18, 19)-methoxy substituents on their respective aromatic systems. All compounds obtained by condensation of the borinic acids with the aforementioned nitrogen-containing substrates were characterized structurally by means of diffraction studies based on single crystals and found to constitute chelate esters/amides featuring covalent B-O and dative N→B bonds. The chelate compounds researched in this study could be classified into four families and represent the compounds: ethanol amine: (1) 2,2-diphenyl-1,3,2-oxazaborolidines, (2) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (3) 2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (4) 2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (5) 2,2-bis(p-methoxyphenyl)-1,3,2-oxazaborolidines, (6) 2,2-bis(o-tolyl)-1,3,2-oxazaborolidines, (7) 2,2-bis(m-tolyl)-1,3,2-oxazaborolidines, (8) 2,2-bis(o-chlorophenyl)-1,3,2-oxazaborolidines, (9) 2,2-bis(m-fluorophenyl)-1,3,2-oxazaborolidines, (10) 2,2-bis(o-methoxyphenyl)-1,3,2-oxazaborolidines. α-amino acids : (14) 4-methyl-2,2-diphenyl-1,3,2-oxazaborolidin-5-ones, (15) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (16) 4-methyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (17) 4-isopropyl-2,2-bis(m-tolyl)-1,3,2-oxazaborolidin-5-ones, (18) 4-methyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (19) 4-acetamidyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (20) 4-phenylethane-2,2-bis(p-chlorophenyl)-1,3,2 oxazaborolidin-5-ones. 2-pyridylmethanol: (21) 1,3-hydroxypyridyl-2,2-diphenyl 1,3,2-oxazaborolidines, (22) 1,3-hydroxypyridyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (23) 1,3-hydroxypyridyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines 2-(ethyl amino ethanol): (24) 3-ethyl-2,2-diphenyl-1,3,2-oxazaborolidines, (25) 3-ethyl-2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (26) 3-ethyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (27) 3-ethyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines. Apart from structural studies in the solid state, the compounds were also characterized by means of multinuclear NMR spectroscopy (1H, 11B, 13C) as well as UV/vis and FTIR. The typical 11B resonances were found in the range of (4-10 ppm). A series of characteristic metrical parameters for the compounds in the solid state as well as typical NMR shifts for the chelate target molecules was established that allowed for the determination of the coordination induced shift. The carbon atom bonded to the oxygen atom shifted upfield, while the carbon atom bonded to the nitrogen atom shifted downfield. Factors mentioned in the literature that has an influence on the hydrolytic stability on the heterocyclic borinate motif have been taken into consideration and verified for the systems researched in this study. The substitution at the nitrogen atom with one ethyl group caused the greatest increases in the N→B bond length (27) 1.714 Å, due to the increase in the nitrogen Lewis basicity, making it the least hydrolytically stable, these include compounds (24-26). Furthermore, DFT calculations were performed by employing Becke’s three parameter hybrid exchange functional with Lee–Yang–Parr functional (B3LYP) method using the Gaussian 16 program package (Rev. B01) employing the basis set 6-311++G(d,p), to corroborate and correlate the experimental findings, which gave a general R-squared value of 0.9978 for calculated vs experimental 13C chemical shifts. Thermal properties are recorded for select compounds, indicating the ΔH and the melting points. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text:
- Date Issued: 2021-12
Applying a systems analysis approach to support marine spatial planning in Algoa Bay, South Africa
- Authors: Vermeulen, Estee Ann
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/54121 , vital:46312
- Description: Ocean health provides the foundation for human health through the provisioning of ecosystem services. Increasing demands on ocean space and resources are, however, resulting in a decline in ocean health, with direct and indirect knock-on effects on marine uses and ultimately on human health. In response, there is a growing need to acknowledge and better manage complex human-ocean interactions. This has been recognised in global sustainable development goals and in integrated ocean management processes, leading to widespread endorsement of an ecosystem-based marine spatial planning (MSP) process, including in South Africa. In support of the national MSP process, significant progress has been made in understanding the spatial extent of marine activities and associated marine pressures, but the temporal dynamics of marine activities and interconnections with the marine environment are less well understood. To plan for the growth of marine activities and associated user conflicts, the drivers of these temporal dynamics and associated feedback effects need to be analysed and potential policy and management interventions identified and tested. To support South Africa’s national MSP process, this study adopts a systems analysis approach, using system dynamics modelling, to explore the temporal change in marine uses under alternative growth scenarios in Algoa Bay. Algoa Bay is an appropriate study area because it is experiencing a rapid expansion of marine activities, coupled with a growing uncertainty regarding marine sustainability outcomes. To assist future marine management decisions, the Algoa Marine Systems Analysis Tool (Algoa MSAT) was developed, comprising seven sub-models. Five of the sub-models represent selected marine uses in Algoa Bay, whereas the sixth and seventh integrate the outputs from each marine use in terms of sustainable management indicators (marine health, marine wealth and marine labour). Model development primarily adopted an expert-based model ling approach, although the involvement of stakeholders, through a collaborative modelling process, assisted in integrating knowledge on different marine sectors’ activities, impacts and planning visions into the model framework. Model results were generated under different scenarios to investigate changes in the growth of marine activities and marine sustainability indicators under different levels of ocean governance. Under the baseline (or business-as-usual) model scenario, marine activities were shown to grow increasingly within their respective management limits, with an increase in marine wealth and labour and a consequential decrease in marine health. This scenario particularly highlights that current ocean governance practices are ineffective in sustaining the projected growth of the marine uses, particularly for those that are vulnerable to negative changes in marine health. Conversely, sectors that hold more value in marine wealth and are more resilient to changes in marine health, may continue to grow regardless of negative knock-on effects of the health of the marine environment and on other uses in the bay. This emphasises that an alternative governance strategy is needed to achieve the long-term goal of an ecosystem-based MSP process, as required by South African MSP legislation. To achieve this will require multiple, adaptive cross-sectoral management interventions that are directed towards the ‘deeper leverage points’ that are able to maintain the growth of marine activities within appropriate limits defined by marine health. Using the model interface developed in this project, decision-makers and stakeholders can use the model to explore the temporal dynamics in marine activities under different governance scenarios. Although the model is limited to Algoa Bay, the model boundary can be adapted to assist in marine planning processes at national or trans-national scales. Such analytical assessments and tools are critical to progress the ecosystem-based management approach in MSP, as is required to achieve global sustainable development goals. , Thesis (PhD) -- Faculty of Science, Coastal and Marine Research Unit, 2021
- Full Text:
- Date Issued: 2021-12
- Authors: Vermeulen, Estee Ann
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/54121 , vital:46312
- Description: Ocean health provides the foundation for human health through the provisioning of ecosystem services. Increasing demands on ocean space and resources are, however, resulting in a decline in ocean health, with direct and indirect knock-on effects on marine uses and ultimately on human health. In response, there is a growing need to acknowledge and better manage complex human-ocean interactions. This has been recognised in global sustainable development goals and in integrated ocean management processes, leading to widespread endorsement of an ecosystem-based marine spatial planning (MSP) process, including in South Africa. In support of the national MSP process, significant progress has been made in understanding the spatial extent of marine activities and associated marine pressures, but the temporal dynamics of marine activities and interconnections with the marine environment are less well understood. To plan for the growth of marine activities and associated user conflicts, the drivers of these temporal dynamics and associated feedback effects need to be analysed and potential policy and management interventions identified and tested. To support South Africa’s national MSP process, this study adopts a systems analysis approach, using system dynamics modelling, to explore the temporal change in marine uses under alternative growth scenarios in Algoa Bay. Algoa Bay is an appropriate study area because it is experiencing a rapid expansion of marine activities, coupled with a growing uncertainty regarding marine sustainability outcomes. To assist future marine management decisions, the Algoa Marine Systems Analysis Tool (Algoa MSAT) was developed, comprising seven sub-models. Five of the sub-models represent selected marine uses in Algoa Bay, whereas the sixth and seventh integrate the outputs from each marine use in terms of sustainable management indicators (marine health, marine wealth and marine labour). Model development primarily adopted an expert-based model ling approach, although the involvement of stakeholders, through a collaborative modelling process, assisted in integrating knowledge on different marine sectors’ activities, impacts and planning visions into the model framework. Model results were generated under different scenarios to investigate changes in the growth of marine activities and marine sustainability indicators under different levels of ocean governance. Under the baseline (or business-as-usual) model scenario, marine activities were shown to grow increasingly within their respective management limits, with an increase in marine wealth and labour and a consequential decrease in marine health. This scenario particularly highlights that current ocean governance practices are ineffective in sustaining the projected growth of the marine uses, particularly for those that are vulnerable to negative changes in marine health. Conversely, sectors that hold more value in marine wealth and are more resilient to changes in marine health, may continue to grow regardless of negative knock-on effects of the health of the marine environment and on other uses in the bay. This emphasises that an alternative governance strategy is needed to achieve the long-term goal of an ecosystem-based MSP process, as required by South African MSP legislation. To achieve this will require multiple, adaptive cross-sectoral management interventions that are directed towards the ‘deeper leverage points’ that are able to maintain the growth of marine activities within appropriate limits defined by marine health. Using the model interface developed in this project, decision-makers and stakeholders can use the model to explore the temporal dynamics in marine activities under different governance scenarios. Although the model is limited to Algoa Bay, the model boundary can be adapted to assist in marine planning processes at national or trans-national scales. Such analytical assessments and tools are critical to progress the ecosystem-based management approach in MSP, as is required to achieve global sustainable development goals. , Thesis (PhD) -- Faculty of Science, Coastal and Marine Research Unit, 2021
- Full Text:
- Date Issued: 2021-12
Use of flow reactors for an improved synthesis of Tenofovir derivatives
- Authors: Sonti, Thembela
- Date: 2023-04
- Subjects: Antiviral agents -- South Africa , HIV infections –Treatment
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/61190 , vital:69792
- Description: Tenofovir disoproxil fumarate (TDF) is a prescription drug used to treat and prevent human immunodeficiency virus (HIV) infections. It aids in the reduction of HIV in the body, allowing the immune system to function more effectively. This reduces the risk of HIV complications, such as infections, whilst improving the quality of life. TDF belongs to the nucleotide reverse transcriptase inhibitors category of drugs. These drugs limit the ability of the reverse transcriptase, an enzyme essential for each virus to replicate itself. A reduction in the cost of HIV treatment could improve supply security and make it more accessible to patients in need. Thus, this project aims to use flow technology to achieve a guaranteed supply chain and access. In this thesis, a method for the synthesis of TDF was developed using microreactors starting from the readily available adenine. The method was adapted from the traditional batch synthesis as currently there is no literature on the synthesis of TDF in flow chemistry. The batch methods used for the synthesis of the working standards were successfully translated to flow systems. For the best results to be obtained, optimisation of the reaction temperature, reagent molar equivalents and concentration was critical. From the optimisation studies, an improvement in conversion is evident throughout all stages. The flow synthesis of the first intermediate resulted in a conversion of 100 % in N,N-dimethylformamide in 6 min residence time. This study was conducted at 200 °C, which is higher than the boiling point of the solvent with the aid of a back pressure regulator. A key reagent in the synthesis of tenofovir, namely ((tosyloxy)methyl)phosphonic acid, had to be synthesised and it was successfully produced in 96 % yield. The second intermediate was synthesised through a successful coupling reaction between (R)-9-(2-hydroxypropyl)adenine and ((tosyloxy)methyl)- phosphonic acid, which afforded a 100 % conversion of tenofovir in 20 min total residence time. The multistep synthesis of tenofovir was a success as it afforded a 65 % overall conversion. The prodrug TDF was successfully synthesised at 120 °C with a 30 min residence time, yielding a conversion of 100 %. ii | P a g e This thesis consists of four chapters. Chapter one describes the background on HIV and a literature review on HIV drugs. This chapter also demonstrates flow chemistry and microreactors in detail and different routes for the synthesis of TDF in traditional batch methods. Chapter two provides a detailed methodology for batch synthesis and flow synthesis with analytical data. 1H-NMR, 13C-NMR and FTIR spectroscopy was used to evaluate all the compounds synthesised in this chapter. Chapter three thoroughly discusses the results that were obtained graphically, showing that the flow synthesis gives better yields than batch synthesis. In chapter 4, the conclusion of the whole investigation is stated along with the future work for the preparation of TDF. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-04
- Authors: Sonti, Thembela
- Date: 2023-04
- Subjects: Antiviral agents -- South Africa , HIV infections –Treatment
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/61190 , vital:69792
- Description: Tenofovir disoproxil fumarate (TDF) is a prescription drug used to treat and prevent human immunodeficiency virus (HIV) infections. It aids in the reduction of HIV in the body, allowing the immune system to function more effectively. This reduces the risk of HIV complications, such as infections, whilst improving the quality of life. TDF belongs to the nucleotide reverse transcriptase inhibitors category of drugs. These drugs limit the ability of the reverse transcriptase, an enzyme essential for each virus to replicate itself. A reduction in the cost of HIV treatment could improve supply security and make it more accessible to patients in need. Thus, this project aims to use flow technology to achieve a guaranteed supply chain and access. In this thesis, a method for the synthesis of TDF was developed using microreactors starting from the readily available adenine. The method was adapted from the traditional batch synthesis as currently there is no literature on the synthesis of TDF in flow chemistry. The batch methods used for the synthesis of the working standards were successfully translated to flow systems. For the best results to be obtained, optimisation of the reaction temperature, reagent molar equivalents and concentration was critical. From the optimisation studies, an improvement in conversion is evident throughout all stages. The flow synthesis of the first intermediate resulted in a conversion of 100 % in N,N-dimethylformamide in 6 min residence time. This study was conducted at 200 °C, which is higher than the boiling point of the solvent with the aid of a back pressure regulator. A key reagent in the synthesis of tenofovir, namely ((tosyloxy)methyl)phosphonic acid, had to be synthesised and it was successfully produced in 96 % yield. The second intermediate was synthesised through a successful coupling reaction between (R)-9-(2-hydroxypropyl)adenine and ((tosyloxy)methyl)- phosphonic acid, which afforded a 100 % conversion of tenofovir in 20 min total residence time. The multistep synthesis of tenofovir was a success as it afforded a 65 % overall conversion. The prodrug TDF was successfully synthesised at 120 °C with a 30 min residence time, yielding a conversion of 100 %. ii | P a g e This thesis consists of four chapters. Chapter one describes the background on HIV and a literature review on HIV drugs. This chapter also demonstrates flow chemistry and microreactors in detail and different routes for the synthesis of TDF in traditional batch methods. Chapter two provides a detailed methodology for batch synthesis and flow synthesis with analytical data. 1H-NMR, 13C-NMR and FTIR spectroscopy was used to evaluate all the compounds synthesised in this chapter. Chapter three thoroughly discusses the results that were obtained graphically, showing that the flow synthesis gives better yields than batch synthesis. In chapter 4, the conclusion of the whole investigation is stated along with the future work for the preparation of TDF. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-04
Microstructural characterization of Swift Heavy Ion (SHI) induced rotation in single crystal NiO
- Authors: Douglas-Henry, Danielle
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53648 , vital:45685
- Description: Swift Heavy Ions (SHI) are characterised by having energies greater than 1 MeV per nucleon with an atomic mass greater than 6 amu. Exposure to irradiation of this type has been known to produce latent tracks in insulators. This is due to the energy loss through the material being governed by electronic excitation processes. The extent of the track formation and microstructural changes induced has been reported to be material specific. Models such as the thermal spike model have been used to explain these changes, however rough approximations are still made. A particularly under studied phenomena is the collective rotation seen in materials exposed to off-normal incidence irradiation. To date the only available experimental data is X-Ray Diffraction (XRD) spectra and surface shifts. This does not allow for depth-dependent rotation studies and very little can be deduced regarding the microstructure of the modified volume. In this study, the microstructural changes in single crystal Nickel Oxide (NiO) have been studied using electron microscopy techniques. A depth dependent investigation of the crystal rotation was performed using Selected Area Electron Diffraction (SAED), Transmission Kikuchi Diffraction (TKD) and Electron Backscatter Diffraction (EBSD). Transmission Electron Microscopy (TEM) and Scanning Transmission Electron Microscopy (STEM) were utilized to interrogate the microstructural changes facilitating the bulk rotation. Five different NiO specimens were investigated. Specimens had surfaces parallel to either the {0 0 1} or {1 1 1} planes. Ion energies used were 593 MeV, 940 MeV and 1.6 GeV, while fluences ranged from 1.0 x 1011 ions/cm² to 9.6 x 1014 ions/cm². Latent track formation in both low fluence (nonoverlapping regime) and high fluence (overlapping regime) specimens were investigated and compared. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-12
- Authors: Douglas-Henry, Danielle
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53648 , vital:45685
- Description: Swift Heavy Ions (SHI) are characterised by having energies greater than 1 MeV per nucleon with an atomic mass greater than 6 amu. Exposure to irradiation of this type has been known to produce latent tracks in insulators. This is due to the energy loss through the material being governed by electronic excitation processes. The extent of the track formation and microstructural changes induced has been reported to be material specific. Models such as the thermal spike model have been used to explain these changes, however rough approximations are still made. A particularly under studied phenomena is the collective rotation seen in materials exposed to off-normal incidence irradiation. To date the only available experimental data is X-Ray Diffraction (XRD) spectra and surface shifts. This does not allow for depth-dependent rotation studies and very little can be deduced regarding the microstructure of the modified volume. In this study, the microstructural changes in single crystal Nickel Oxide (NiO) have been studied using electron microscopy techniques. A depth dependent investigation of the crystal rotation was performed using Selected Area Electron Diffraction (SAED), Transmission Kikuchi Diffraction (TKD) and Electron Backscatter Diffraction (EBSD). Transmission Electron Microscopy (TEM) and Scanning Transmission Electron Microscopy (STEM) were utilized to interrogate the microstructural changes facilitating the bulk rotation. Five different NiO specimens were investigated. Specimens had surfaces parallel to either the {0 0 1} or {1 1 1} planes. Ion energies used were 593 MeV, 940 MeV and 1.6 GeV, while fluences ranged from 1.0 x 1011 ions/cm² to 9.6 x 1014 ions/cm². Latent track formation in both low fluence (nonoverlapping regime) and high fluence (overlapping regime) specimens were investigated and compared. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-12
A case study assessment of the ecological and social status of the South African boat-based whale watching industry
- Authors: Tolsma, Minke
- Date: 2022-04
- Subjects: Whale watching --South Africa , Dolphin watching
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55887 , vital:54397
- Description: Boat-based whale-watching (BBWW) is a rapidly growing marine tourism industry globally and in South Africa (SA). BBWW in SA was established in 1998, and since then the number of permits available has doubled from 20 to 40. However, the establishment and past growth of the industry was undertaken without ecological research or impact assessments. Global research has shown that BBWW has the potential to cause short-term changes in cetacean behaviour and movement, which in turn can have long-term population-level consequences. National policies to grow ocean economies in SA may encourage excessive growth in the BBWW industry, impacting the ecological sustainability. In the absence of long-term impact data, the BBWW industry should be managed to minimise short-term changes. This study aimed to determine the social and ecological status of the SA BBWW industry, using Plettenberg Bay as a case study, to inform its long term sustainability. To achieve this aim: 1) the short-term behavioural and movement responses of six cetacean species to encounters with commercial BBWW vessels were measured; 2) the efficacy of three permit regulations (approach speed, approach angle, and encounter duration) to prevent short-term behavioural changes in three cetacean species was measured; 3) rates of compliance of BBWWoperators with current regulations were recorded; 4) BBWW tourists’ expectations of and satisfaction with the industry were investigated; as well as 5) operators’ views on the current permit regulations of the industry All research was conducted between September 2018 and November 2020 in Plettenberg Bay (SA) where two BBWW companies operating two vessels each are active. Three dolphin (bottlenose, common and humpback dolphins) and three whale (Bryde’s, humpback and southern right whales) species are targeted by the industry, and were encountered during this study. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2022
- Full Text:
- Date Issued: 2022-04
- Authors: Tolsma, Minke
- Date: 2022-04
- Subjects: Whale watching --South Africa , Dolphin watching
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55887 , vital:54397
- Description: Boat-based whale-watching (BBWW) is a rapidly growing marine tourism industry globally and in South Africa (SA). BBWW in SA was established in 1998, and since then the number of permits available has doubled from 20 to 40. However, the establishment and past growth of the industry was undertaken without ecological research or impact assessments. Global research has shown that BBWW has the potential to cause short-term changes in cetacean behaviour and movement, which in turn can have long-term population-level consequences. National policies to grow ocean economies in SA may encourage excessive growth in the BBWW industry, impacting the ecological sustainability. In the absence of long-term impact data, the BBWW industry should be managed to minimise short-term changes. This study aimed to determine the social and ecological status of the SA BBWW industry, using Plettenberg Bay as a case study, to inform its long term sustainability. To achieve this aim: 1) the short-term behavioural and movement responses of six cetacean species to encounters with commercial BBWW vessels were measured; 2) the efficacy of three permit regulations (approach speed, approach angle, and encounter duration) to prevent short-term behavioural changes in three cetacean species was measured; 3) rates of compliance of BBWWoperators with current regulations were recorded; 4) BBWW tourists’ expectations of and satisfaction with the industry were investigated; as well as 5) operators’ views on the current permit regulations of the industry All research was conducted between September 2018 and November 2020 in Plettenberg Bay (SA) where two BBWW companies operating two vessels each are active. Three dolphin (bottlenose, common and humpback dolphins) and three whale (Bryde’s, humpback and southern right whales) species are targeted by the industry, and were encountered during this study. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2022
- Full Text:
- Date Issued: 2022-04
An evaluation of the effectiveness of area-based conservation interventions in avoiding biodiversity loss in South Africa
- Authors: Von Staden, Lize
- Date: 2023-04
- Subjects: Environmental policy , Conservation of natural resources -- Government policy -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/61115 , vital:69762
- Description: Counterfactual impact evaluation studies form an important evidence base for the effectiveness of conservation projects, programs, and policies (collectively referred to as conservation interventions). In South Africa, counterfactual impact evaluation methods have rarely been applied to local conservation interventions, and therefore evidence for the effectiveness of key strategic national conservation approaches is lacking. This study evaluated three area-based interventions that together aim to avoid the loss of areas most important for the persistence of biodiversity in the terrestrial realm as evidence towards the effectiveness of South Africa’s landscape approach to biodiversity conservation. The first intervention, South Africa’s National Protected Area Expansion Strategy (NPAES), set ambitious targets to double the extent of South Africa’s protected area network while ensuring that the expansion preferentially occurs in areas of under-represented biodiversity. The strategy was evaluated in terms of its effectiveness in guiding protected area expansion towards more equitable representation of South Africa’s biodiversity through an assessment of changes in indicators of protected area expansion decision-making before and after the implementation of the strategy. The second intervention is the use of maps of biodiversity priorities to guide land use change decisions outside protected areas. Impact was evaluated as avoided loss of Critical Biodiversity Areas (CBAs), which need to remain in a natural condition to meet in situ conservation targets for species, ecosystems, and ecological processes. Avoided loss in CBAs was benchmarked against avoided loss in protected areas, to contextualize the effectiveness of land use planning as a conservation intervention. Lastly, the effectiveness of stricter land use regulations for threatened ecosystems to reduce land conversion pressure on these ecosystems was evaluated. Key findings were that protected areas are highly effective conservation interventions where they can be implemented, but their capacity for conservation impact is limited by severe constraints on strategic expansion. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2023
- Full Text:
- Date Issued: 2023-04
- Authors: Von Staden, Lize
- Date: 2023-04
- Subjects: Environmental policy , Conservation of natural resources -- Government policy -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/61115 , vital:69762
- Description: Counterfactual impact evaluation studies form an important evidence base for the effectiveness of conservation projects, programs, and policies (collectively referred to as conservation interventions). In South Africa, counterfactual impact evaluation methods have rarely been applied to local conservation interventions, and therefore evidence for the effectiveness of key strategic national conservation approaches is lacking. This study evaluated three area-based interventions that together aim to avoid the loss of areas most important for the persistence of biodiversity in the terrestrial realm as evidence towards the effectiveness of South Africa’s landscape approach to biodiversity conservation. The first intervention, South Africa’s National Protected Area Expansion Strategy (NPAES), set ambitious targets to double the extent of South Africa’s protected area network while ensuring that the expansion preferentially occurs in areas of under-represented biodiversity. The strategy was evaluated in terms of its effectiveness in guiding protected area expansion towards more equitable representation of South Africa’s biodiversity through an assessment of changes in indicators of protected area expansion decision-making before and after the implementation of the strategy. The second intervention is the use of maps of biodiversity priorities to guide land use change decisions outside protected areas. Impact was evaluated as avoided loss of Critical Biodiversity Areas (CBAs), which need to remain in a natural condition to meet in situ conservation targets for species, ecosystems, and ecological processes. Avoided loss in CBAs was benchmarked against avoided loss in protected areas, to contextualize the effectiveness of land use planning as a conservation intervention. Lastly, the effectiveness of stricter land use regulations for threatened ecosystems to reduce land conversion pressure on these ecosystems was evaluated. Key findings were that protected areas are highly effective conservation interventions where they can be implemented, but their capacity for conservation impact is limited by severe constraints on strategic expansion. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2023
- Full Text:
- Date Issued: 2023-04
The effect of silicon on palladium migration in pyrolytic carbon and graphite
- Authors: Downey, Justin Michael
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53665 , vital:45684
- Description: The pebble-bed reactor (PBR) is a graphite-moderated, gas-cooled high temperature nuclear reactor design and it is one of six nuclear reactor concepts included in the Generation IV initiative. Pebble-bed reactors use spherical fuel elements (called pebbles) which consist of pyrolytic graphite (which acts as the moderator) and contain thousands of micro-fuel particles called tristructural isotropic (TRISO) particles. These TRISO fuel particles consist of a fissile material (such as U235 in oxide or carbide form) surrounded by a carbon buffer layer, a pyrolytic carbon (PyC) layer, a silicon carbide (SiC) ceramic layer for structural integrity and metallic fission product containment, and an outer PyC layer. The PBR is claimed to be a passively safe design. The commercial development of the first pebble bed reactor was that of the German AVR reactor (German: Arbeitsgemeinschaft Versuchsreaktor) developed during the 1960s. The AVR design was later updated and marketed by a company called HTR. In 1999 the South African electricity company ESKOM obtained the right to access the HTR engineering database that included details of the Siemens/Interatom HTR-Module design. ESKOM worked with HTR on a new design and dubbed it the pebble bed modular reactor (PBMR). The PBMR Co. Ltd. was formed in 1999 and mandated to license and build PBMR reactors. One of the safety considerations which emerged from research is that of metal fission product release from the TRISO fuel particles. Ag110m is a radioactive metallic fission product found to have been released from intact TRISO particles. The release of this Ag isotope is of particular concern because it is highly gamma active and has a half-life of approximately 250 days, resulting in unsafe environments for maintenance workers of PBRs. During the past four decades, many different mechanisms for Ag transport in SiC and release from TRISO particles have been proposed. A promising more recent mechanism suggests that the metallic fission product palladium (Pd) plays a significant role in the transport and release of Ag from intact TRISO particles. In this mechanism Ag transport in irradiated TRISO particle fuel takes place in the presence of the fission product Pd. The Pd reacts with the SiC layer and penetrates the SiC layer along grain boundaries to form a silicide layer which provides a rapid diffusion path for Ag in the SiC. The presence of thin silicide layers in irradiated TRISO particles was subsequently confirmed. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-12
- Authors: Downey, Justin Michael
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53665 , vital:45684
- Description: The pebble-bed reactor (PBR) is a graphite-moderated, gas-cooled high temperature nuclear reactor design and it is one of six nuclear reactor concepts included in the Generation IV initiative. Pebble-bed reactors use spherical fuel elements (called pebbles) which consist of pyrolytic graphite (which acts as the moderator) and contain thousands of micro-fuel particles called tristructural isotropic (TRISO) particles. These TRISO fuel particles consist of a fissile material (such as U235 in oxide or carbide form) surrounded by a carbon buffer layer, a pyrolytic carbon (PyC) layer, a silicon carbide (SiC) ceramic layer for structural integrity and metallic fission product containment, and an outer PyC layer. The PBR is claimed to be a passively safe design. The commercial development of the first pebble bed reactor was that of the German AVR reactor (German: Arbeitsgemeinschaft Versuchsreaktor) developed during the 1960s. The AVR design was later updated and marketed by a company called HTR. In 1999 the South African electricity company ESKOM obtained the right to access the HTR engineering database that included details of the Siemens/Interatom HTR-Module design. ESKOM worked with HTR on a new design and dubbed it the pebble bed modular reactor (PBMR). The PBMR Co. Ltd. was formed in 1999 and mandated to license and build PBMR reactors. One of the safety considerations which emerged from research is that of metal fission product release from the TRISO fuel particles. Ag110m is a radioactive metallic fission product found to have been released from intact TRISO particles. The release of this Ag isotope is of particular concern because it is highly gamma active and has a half-life of approximately 250 days, resulting in unsafe environments for maintenance workers of PBRs. During the past four decades, many different mechanisms for Ag transport in SiC and release from TRISO particles have been proposed. A promising more recent mechanism suggests that the metallic fission product palladium (Pd) plays a significant role in the transport and release of Ag from intact TRISO particles. In this mechanism Ag transport in irradiated TRISO particle fuel takes place in the presence of the fission product Pd. The Pd reacts with the SiC layer and penetrates the SiC layer along grain boundaries to form a silicide layer which provides a rapid diffusion path for Ag in the SiC. The presence of thin silicide layers in irradiated TRISO particles was subsequently confirmed. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-12
Investigation of thermal and electrical characteristics of crystalline silicon photovoltaic modules under varying operational conditions
- Authors: Vumbugwa, Monphias
- Date: 2022-12
- Subjects: Photovoltaic power generation -- South Africa , Silicon crystals -- South Africa , Solar cells
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/60014 , vital:62733
- Description: Solar energy has become an attractive and environmentally mindful method in electrical power generation as it contributes significantly to meeting the high demand for the power needed for socio and economic developments. The rise in deployment of Photovoltaic (PV) facilities with large capacity creates the need for accurate and reliable PV inspection techniques for optimum performance, the longevity of PV modules and quick return on PV investment. The performance of PV modules in the field is often monitored through several inspection methods that require a rapid throughput such as Thermal Infrared (TIR) imaging and current-voltage (I-V) measurements. Unmanned Aerial Vehicle (UAV) based TIR imaging is widely applied in large PV plants since it is cost-effective and is usually conducted in-situ while the plant is operating at irradiance levels above 600 W.m-2 . One of the outcomes of the interpretations of TIR images is an attempt to quantify the energy loss in PV plants associated with the abnormal thermal signatures identified on TIR images. No standard procedure has yet outlined the quantification of energy loss related to TIR images of underperforming modules since the interpretation of TIR images remains a challenge. PV modules operate under dynamic operating conditions which can influence the results and interpretation of thermal and electrical characterisation measurements. Dynamic operation conditions refer to any disorders in the operation of the modules and cells which cause a change in the current and voltage characteristics of the PV source. These dynamic operation conditions include; changesin load conditions, irradiance, soiling and shading levels. The tests were done under steady state conditions. Although measurements are generally done while the operating conditions are as steady as possible, some changes in conditions have a profound effect on thermal and electrical measurements. In this study, these effects and some of the changes in conditions that cause them were studied. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2022
- Full Text:
- Date Issued: 2022-12
- Authors: Vumbugwa, Monphias
- Date: 2022-12
- Subjects: Photovoltaic power generation -- South Africa , Silicon crystals -- South Africa , Solar cells
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/60014 , vital:62733
- Description: Solar energy has become an attractive and environmentally mindful method in electrical power generation as it contributes significantly to meeting the high demand for the power needed for socio and economic developments. The rise in deployment of Photovoltaic (PV) facilities with large capacity creates the need for accurate and reliable PV inspection techniques for optimum performance, the longevity of PV modules and quick return on PV investment. The performance of PV modules in the field is often monitored through several inspection methods that require a rapid throughput such as Thermal Infrared (TIR) imaging and current-voltage (I-V) measurements. Unmanned Aerial Vehicle (UAV) based TIR imaging is widely applied in large PV plants since it is cost-effective and is usually conducted in-situ while the plant is operating at irradiance levels above 600 W.m-2 . One of the outcomes of the interpretations of TIR images is an attempt to quantify the energy loss in PV plants associated with the abnormal thermal signatures identified on TIR images. No standard procedure has yet outlined the quantification of energy loss related to TIR images of underperforming modules since the interpretation of TIR images remains a challenge. PV modules operate under dynamic operating conditions which can influence the results and interpretation of thermal and electrical characterisation measurements. Dynamic operation conditions refer to any disorders in the operation of the modules and cells which cause a change in the current and voltage characteristics of the PV source. These dynamic operation conditions include; changesin load conditions, irradiance, soiling and shading levels. The tests were done under steady state conditions. Although measurements are generally done while the operating conditions are as steady as possible, some changes in conditions have a profound effect on thermal and electrical measurements. In this study, these effects and some of the changes in conditions that cause them were studied. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2022
- Full Text:
- Date Issued: 2022-12
Score driven volatility models based on skewed-t distributions
- Authors: Janse van Rensburg, Stéfan
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , GARCH Model
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/52010 , vital:43425
- Description: Score driven (SD) conditional volatility models allow for rich volatility dynamics and realistic distributional assumptions. These models link the evolution of time-varying volatility to the shape of the predictive density, which often results in models that are robust against outliers. These models also allow for conditional skewness. The combination of skewness and robustness may improve in-sample fit, conditional volatility forecasts and tail-risk forecasts. Therefore, this study proposes novel SD conditional volatility models with Skewed-t distributed innovations. For some of these models, the formof skewness partially negates robustness against outliers. This result demonstrates that the formof skewness requires careful consideration in the specification of SD conditional volatility models. The study also expands upon earlier observations that the assumption of negative conditional skewness may induce a form of volatility asymmetry in SD conditional volatility models that is incompatible with the leverage effect typically observed in equity markets. A simulation experiment shows that neglected leverage, therefore, biases maximum likelihood estimates. Additionally, the study considers SD conditional volatility models that account for leverage effects and have Skewed-t distributed innovations. An empirical application to the daily Johannesburg Stock Exchange (JSE) / Financial Times Stock Exchange (FTSE) All Share Index returns demonstrates the utility of SD conditional volatility models with Skewed-t distributed innovations. Extensions of these models that account for leverage prove competitive with more traditional conditional volatility models in terms of in-sample fit and tail-risk forecasts. These results suggest that the models considered in this study are useful within the context of financial risk management. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-04
- Authors: Janse van Rensburg, Stéfan
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , GARCH Model
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/52010 , vital:43425
- Description: Score driven (SD) conditional volatility models allow for rich volatility dynamics and realistic distributional assumptions. These models link the evolution of time-varying volatility to the shape of the predictive density, which often results in models that are robust against outliers. These models also allow for conditional skewness. The combination of skewness and robustness may improve in-sample fit, conditional volatility forecasts and tail-risk forecasts. Therefore, this study proposes novel SD conditional volatility models with Skewed-t distributed innovations. For some of these models, the formof skewness partially negates robustness against outliers. This result demonstrates that the formof skewness requires careful consideration in the specification of SD conditional volatility models. The study also expands upon earlier observations that the assumption of negative conditional skewness may induce a form of volatility asymmetry in SD conditional volatility models that is incompatible with the leverage effect typically observed in equity markets. A simulation experiment shows that neglected leverage, therefore, biases maximum likelihood estimates. Additionally, the study considers SD conditional volatility models that account for leverage effects and have Skewed-t distributed innovations. An empirical application to the daily Johannesburg Stock Exchange (JSE) / Financial Times Stock Exchange (FTSE) All Share Index returns demonstrates the utility of SD conditional volatility models with Skewed-t distributed innovations. Extensions of these models that account for leverage prove competitive with more traditional conditional volatility models in terms of in-sample fit and tail-risk forecasts. These results suggest that the models considered in this study are useful within the context of financial risk management. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-04
A Functional Data Analysis approach to understand patterns imbedded within various data types
- Authors: Mangisa, Siphumlile
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , Data mining
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/52091 , vital:43426
- Description: The thesis investigates the use of the novel Functional Data Analysis (FDA) methods in tackling various data types. Strong motivation is provided for the use of interesting opportunities offered by FDA to analyse not only economic data, but generally, data from any domain. The use of these methods is illustrated using three unique self-contained case-studies from econometrics. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-04
- Authors: Mangisa, Siphumlile
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , Data mining
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/52091 , vital:43426
- Description: The thesis investigates the use of the novel Functional Data Analysis (FDA) methods in tackling various data types. Strong motivation is provided for the use of interesting opportunities offered by FDA to analyse not only economic data, but generally, data from any domain. The use of these methods is illustrated using three unique self-contained case-studies from econometrics. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text: false
- Date Issued: 2021-04
The use of psychometric test systems as a pre-selection tool for identifying successful harvesting machine operators
- Authors: Schwegman, Kylle
- Date: 2022-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55246 , vital:51102
- Description: A shift towards fully mechanized forest activities, such as harvesting and, more recently, silviculture, has occurred from the early 2 000’s. The reason for mechanizing these activities differs for each country, although for most countries there is concern relating to the health and safety of forest workers. With mechanization in harvesting, the forest worker has moved away from the physical intensity of having to fell, debranch, debark and cross-cut trees into logs using either an axe or chainsaw, to operating a machine. Studies revolving around the human element (operator) have been conducted specifically relating to the ergonomics of the machines and how operators may influence machine productivity. Results showed that due to the repetitive nature of the work, the operators are exposed to associated stresses for longer periods. Typical injuries associated to these kinds of stressors are whole body vibrations (WBVs), repetitive hand and arm movements, non-neutral body postures and manual lifting, which lead to musculoskeletal symptoms in the lower back, neck and shoulders. However, as machine technology improves so does the ergonomic conditions which are experienced by machine operators. Machine productivity can be influenced by various factors, with the most influential being tree volume. However, a recent study showed that over 40% of variation in machine productivity has been observed amongst different machine operators operating similar machines. The specific reason for these differences has yet to be determined. However, decision making, motivation, planning capacity, concentration, memory, motor coordination, pattern recognition, logic reasoning, and spatial perception are abilities that have been described as important for successful harvesting work. The pre-selection of operators using psychometric and cognitive tests is not new to forestry, although very little information is available relating to the aptitude test known as the Vienna test system as well as the best possible demographic associated with successful harvesting operators. The overall aim of this study was to determine whether the high variation found amongst harvesting machine operators could be reduced initially through a preselection process which involves the use of aptitude tests (Vienna Test System) and demographic questionnaires. A study was implemented in Zululand, South Africa, testing whether there were significant productivity differences between nine machine operators. , Thesis (PhD) -- Faculty of Science, School of Natural Resource Management, 2022
- Full Text:
- Date Issued: 2022-04
- Authors: Schwegman, Kylle
- Date: 2022-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55246 , vital:51102
- Description: A shift towards fully mechanized forest activities, such as harvesting and, more recently, silviculture, has occurred from the early 2 000’s. The reason for mechanizing these activities differs for each country, although for most countries there is concern relating to the health and safety of forest workers. With mechanization in harvesting, the forest worker has moved away from the physical intensity of having to fell, debranch, debark and cross-cut trees into logs using either an axe or chainsaw, to operating a machine. Studies revolving around the human element (operator) have been conducted specifically relating to the ergonomics of the machines and how operators may influence machine productivity. Results showed that due to the repetitive nature of the work, the operators are exposed to associated stresses for longer periods. Typical injuries associated to these kinds of stressors are whole body vibrations (WBVs), repetitive hand and arm movements, non-neutral body postures and manual lifting, which lead to musculoskeletal symptoms in the lower back, neck and shoulders. However, as machine technology improves so does the ergonomic conditions which are experienced by machine operators. Machine productivity can be influenced by various factors, with the most influential being tree volume. However, a recent study showed that over 40% of variation in machine productivity has been observed amongst different machine operators operating similar machines. The specific reason for these differences has yet to be determined. However, decision making, motivation, planning capacity, concentration, memory, motor coordination, pattern recognition, logic reasoning, and spatial perception are abilities that have been described as important for successful harvesting work. The pre-selection of operators using psychometric and cognitive tests is not new to forestry, although very little information is available relating to the aptitude test known as the Vienna test system as well as the best possible demographic associated with successful harvesting operators. The overall aim of this study was to determine whether the high variation found amongst harvesting machine operators could be reduced initially through a preselection process which involves the use of aptitude tests (Vienna Test System) and demographic questionnaires. A study was implemented in Zululand, South Africa, testing whether there were significant productivity differences between nine machine operators. , Thesis (PhD) -- Faculty of Science, School of Natural Resource Management, 2022
- Full Text:
- Date Issued: 2022-04
Chemical analysis of selected Eastern Cape medicinal plants
- Authors: Mahanjana, Lungelwa
- Date: 2022-04
- Subjects: Medicinal plants -- South Africa --Eastern Cape , Traditional medicine --South Africa -- Eastern Cape Maps
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55976 , vital:54560
- Description: In the rural parts of the Eastern Cape Province of South Africa, the use of medicinal plants to treat or manage diseases, including those associated with diabetes and HIV, is a common practice. However, the phytochemistry, safety and efficacy of these medicinal plants remain less investigated. Based on available traditional medicinal knowledge (through traditional healers, university library resources, ethnobotanical and science journals and other internet resources), traditional uses and availability, three plant species, namely Bulbine latifolia L. Wild, Dicerothamnus rhinocerotis Koek. and Olea europaea subsp. africana (Mill.) P.S. Green were selected and investigated for their hytoconstituents and biological effects. Phytochemical screening of the three medicinal plants was carried out quantitatively and qualitatively using spectrophotometric methods. Chemical profiling of the crude methanol extracts of all the plant species was successfully done by high-performance thin layer chromatography (HPTLC) and tentative identification of the secondary metabolites was achieved by liquid chromatography–mass spectrometry (LCMS). Cytotoxicity effect investigations on the crude extracts of the three species was done using the 3-[4,5- dimethylthiazole-2-yl]-2,5- hiphenyltetrazolium bromide (MTT) assay against HeLa cervical cancer cells. Isolation and purification of single compounds was done using chromatographic techniques (column chromatography (CC), and preparative thin-layer chromatography (PTLC)). Characterisation of single compounds was achieved using spectroscopic techniques such as Nuclear Magnetic Resonance (NMR), High Resolution Mass Spectrometry (HRMS), Ultra Violet Spectroscopy (UV-vis), Fourier-Transformed Infra-Red Spectroscopy (FTIR) and Single-Crystal X-ray Diffraction (XRD). For the first time from the methanol crude extract of the tubers of B. latifolia, the crystal structure of the phenylanthraquinone, knipholone (3.12) (1-(3-acetyl-2,6- dihydroxy-4- methoxyphenyl)-4,5-dihydroxy-2-methylanthraquinone), was isolated and elucidated along with its derivatives, isoknipholone (3.14), knipholone-6’-methyl (3.27). Moreover, two new compounds, (M)-8-O-β-D-glucopyranosyl-10’-α-L-rhamnopyranosyl-1,1',8',10'-tetrahydroxy 3,3'-dimethyl-[10,7'-bianthracene]-4,9,9'(10'H)-trione (3.23a) and (P)- 8-O-β-D glucopyranosyl-10’-α-L-rhamnopyranosyl-1,1',8',10'-tetrahydroxy-3,3'-dimethyl-[10,7'- bianthracene]-4,9,9'(10'H)-trione (3.23b) were isolated. , Thesis (PhD) -- Faculty of Science, School of Biomecular and Chemical Sciences, 2022
- Full Text:
- Date Issued: 2022-04
- Authors: Mahanjana, Lungelwa
- Date: 2022-04
- Subjects: Medicinal plants -- South Africa --Eastern Cape , Traditional medicine --South Africa -- Eastern Cape Maps
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/55976 , vital:54560
- Description: In the rural parts of the Eastern Cape Province of South Africa, the use of medicinal plants to treat or manage diseases, including those associated with diabetes and HIV, is a common practice. However, the phytochemistry, safety and efficacy of these medicinal plants remain less investigated. Based on available traditional medicinal knowledge (through traditional healers, university library resources, ethnobotanical and science journals and other internet resources), traditional uses and availability, three plant species, namely Bulbine latifolia L. Wild, Dicerothamnus rhinocerotis Koek. and Olea europaea subsp. africana (Mill.) P.S. Green were selected and investigated for their hytoconstituents and biological effects. Phytochemical screening of the three medicinal plants was carried out quantitatively and qualitatively using spectrophotometric methods. Chemical profiling of the crude methanol extracts of all the plant species was successfully done by high-performance thin layer chromatography (HPTLC) and tentative identification of the secondary metabolites was achieved by liquid chromatography–mass spectrometry (LCMS). Cytotoxicity effect investigations on the crude extracts of the three species was done using the 3-[4,5- dimethylthiazole-2-yl]-2,5- hiphenyltetrazolium bromide (MTT) assay against HeLa cervical cancer cells. Isolation and purification of single compounds was done using chromatographic techniques (column chromatography (CC), and preparative thin-layer chromatography (PTLC)). Characterisation of single compounds was achieved using spectroscopic techniques such as Nuclear Magnetic Resonance (NMR), High Resolution Mass Spectrometry (HRMS), Ultra Violet Spectroscopy (UV-vis), Fourier-Transformed Infra-Red Spectroscopy (FTIR) and Single-Crystal X-ray Diffraction (XRD). For the first time from the methanol crude extract of the tubers of B. latifolia, the crystal structure of the phenylanthraquinone, knipholone (3.12) (1-(3-acetyl-2,6- dihydroxy-4- methoxyphenyl)-4,5-dihydroxy-2-methylanthraquinone), was isolated and elucidated along with its derivatives, isoknipholone (3.14), knipholone-6’-methyl (3.27). Moreover, two new compounds, (M)-8-O-β-D-glucopyranosyl-10’-α-L-rhamnopyranosyl-1,1',8',10'-tetrahydroxy 3,3'-dimethyl-[10,7'-bianthracene]-4,9,9'(10'H)-trione (3.23a) and (P)- 8-O-β-D glucopyranosyl-10’-α-L-rhamnopyranosyl-1,1',8',10'-tetrahydroxy-3,3'-dimethyl-[10,7'- bianthracene]-4,9,9'(10'H)-trione (3.23b) were isolated. , Thesis (PhD) -- Faculty of Science, School of Biomecular and Chemical Sciences, 2022
- Full Text:
- Date Issued: 2022-04
Ocean structures and dynamics of two open bays on the eastern Agulhas Bank
- Authors: Dlomo, Xolisa
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53607 , vital:45680
- Description: Upwelling, bay-scale currents, fronts and mixing in Algoa Bay and St Francis Bay occur over both short and long time periods. These physical ocean dynamics drive the temporal and spatial distribution of nutrients in the bays, there by influencing primary and secondary production. Thermal gradients and fronts are driven by the wind and open ocean influences, such as the Agulhas Current, daily and seasonal variations in solar radiation, long and short period waves, air-sea fluxes, coastal trapped waves and terrestrial freshwater inflow. These phenomena are poorly understood along this part of the coastline and were the focus of this study. I investigated the dominant temperature scales of variability in both bays, to determine which isotherm is best suited to describe temperature fluctuations and thermocline spatiotemporal variability in and between the two bays. I investigated upwelling spatiotemporal variability in the two bays and tested whether upwelling occurs at the opposite sides of the bays with a change in wind direction. Thereafter studied the occurrence and drivers of winter upwelling events. The wind-driven current spatiotemporal variability and correlations were investigated at the extremities of the two bays. The daily, intra-seasonal and yearly variation in temperature structures in Algoa Bay and St. Francis Bay were mainly driven by the local winds, coastal topography, and bathymetry. The most suitable isotherm to describe thermal fluctuations and variability in Algoa Bay shallower sites was 16.5 °C and its mean depth was 16.2 m. The best isotherm for the deeper sites in Algoa Bay was 15.7 °C with a depth of 33.1 m. The average temperature and depth of the best isotherm to describe thermal fluctuations in St. Francis Bay for the shallower sites was15.80 °C and 16.83 m, and for the deeper sites it was 15.10 °C and 32.08 m. Algoa Bay showed an average cooling trend of -0.000172 °C per year, whereas in St. Francis Bay a warming average trend of 0.0188 °C per year was observed over the study period often and six years, respectively. The wind, Coriolis Effect and Ekman Transport were the main external forces that influenced upwelling throughout the year. Since the available mesoscale indices for upwelling intensity lack the resolution needed to characterize and compare inner-shelf upwelling regimes at small spatial scales, I developed a new local, quantitative index of thermal variability. Index calculations were based on hourly records of in site depth-averaged temperatures, measured at 6 sites in St. Francis Bay and at 8 sites in Algoa Bay. Using the Multivariate Upwelling Zone Index of Cooling (MUZIC) I found that Woody Cape and Blue Horizon Bay had the highest upwelling intensity in Algoa Bay and St. Francis Bay, respectively. The other sites were ordinated and ranked according to their upwelling rates and intensity. Evidence of wind-driven winter upwelling was found to be a common occurrence in both bays. There was no obvious current seasonality observed, however, strong spectral signals in the period of a weather band (4 –7 days) were present. Current structures were generally positively correlated with wind variations in both bays. Thus, when westerly/easterly winds blew the overall surface current direction was eastward/westward. I observed a pronounced current spatiotemporal variability that was driven by local winds. The Bird Island surface currents in Algoa Bay were strongly correlated at 0–lag day with the winds, however, in Cape Recife the strongest correlations were usually observed at 1–lag day highlighting the spatiotemporal influence of wind regimes on current structures in Algoa Bay. Bird Island current speeds were higher and had an obvious bimodal directional variation (south westward /north eastward) compared to Cape Recife currents, which generally had a slower current speed with a strong west-north westward direction. In St. Francis Bay, the Schoenmakerskop surface currents showed weak positive correlation with winds at 0–lag day, however, stronger negative correlations were observed at 4–lag days. The current surface speeds in Schoenmakerskop were the lowest and varied directionally between north-north eastward and south-south eastward. The basic data requirements (i.e. SST/ UTR and ADCP time series) and the simplicity of the calculations make these indices a useful tool to apply to a large number of sites nationally and internationally, and to examine the generality of community and population-level responses to physical forcing. , Thesis (PhD) -- Faculty of Science, Journalsim and Media Studies, 2021
- Full Text:
- Date Issued: 2021-12
- Authors: Dlomo, Xolisa
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53607 , vital:45680
- Description: Upwelling, bay-scale currents, fronts and mixing in Algoa Bay and St Francis Bay occur over both short and long time periods. These physical ocean dynamics drive the temporal and spatial distribution of nutrients in the bays, there by influencing primary and secondary production. Thermal gradients and fronts are driven by the wind and open ocean influences, such as the Agulhas Current, daily and seasonal variations in solar radiation, long and short period waves, air-sea fluxes, coastal trapped waves and terrestrial freshwater inflow. These phenomena are poorly understood along this part of the coastline and were the focus of this study. I investigated the dominant temperature scales of variability in both bays, to determine which isotherm is best suited to describe temperature fluctuations and thermocline spatiotemporal variability in and between the two bays. I investigated upwelling spatiotemporal variability in the two bays and tested whether upwelling occurs at the opposite sides of the bays with a change in wind direction. Thereafter studied the occurrence and drivers of winter upwelling events. The wind-driven current spatiotemporal variability and correlations were investigated at the extremities of the two bays. The daily, intra-seasonal and yearly variation in temperature structures in Algoa Bay and St. Francis Bay were mainly driven by the local winds, coastal topography, and bathymetry. The most suitable isotherm to describe thermal fluctuations and variability in Algoa Bay shallower sites was 16.5 °C and its mean depth was 16.2 m. The best isotherm for the deeper sites in Algoa Bay was 15.7 °C with a depth of 33.1 m. The average temperature and depth of the best isotherm to describe thermal fluctuations in St. Francis Bay for the shallower sites was15.80 °C and 16.83 m, and for the deeper sites it was 15.10 °C and 32.08 m. Algoa Bay showed an average cooling trend of -0.000172 °C per year, whereas in St. Francis Bay a warming average trend of 0.0188 °C per year was observed over the study period often and six years, respectively. The wind, Coriolis Effect and Ekman Transport were the main external forces that influenced upwelling throughout the year. Since the available mesoscale indices for upwelling intensity lack the resolution needed to characterize and compare inner-shelf upwelling regimes at small spatial scales, I developed a new local, quantitative index of thermal variability. Index calculations were based on hourly records of in site depth-averaged temperatures, measured at 6 sites in St. Francis Bay and at 8 sites in Algoa Bay. Using the Multivariate Upwelling Zone Index of Cooling (MUZIC) I found that Woody Cape and Blue Horizon Bay had the highest upwelling intensity in Algoa Bay and St. Francis Bay, respectively. The other sites were ordinated and ranked according to their upwelling rates and intensity. Evidence of wind-driven winter upwelling was found to be a common occurrence in both bays. There was no obvious current seasonality observed, however, strong spectral signals in the period of a weather band (4 –7 days) were present. Current structures were generally positively correlated with wind variations in both bays. Thus, when westerly/easterly winds blew the overall surface current direction was eastward/westward. I observed a pronounced current spatiotemporal variability that was driven by local winds. The Bird Island surface currents in Algoa Bay were strongly correlated at 0–lag day with the winds, however, in Cape Recife the strongest correlations were usually observed at 1–lag day highlighting the spatiotemporal influence of wind regimes on current structures in Algoa Bay. Bird Island current speeds were higher and had an obvious bimodal directional variation (south westward /north eastward) compared to Cape Recife currents, which generally had a slower current speed with a strong west-north westward direction. In St. Francis Bay, the Schoenmakerskop surface currents showed weak positive correlation with winds at 0–lag day, however, stronger negative correlations were observed at 4–lag days. The current surface speeds in Schoenmakerskop were the lowest and varied directionally between north-north eastward and south-south eastward. The basic data requirements (i.e. SST/ UTR and ADCP time series) and the simplicity of the calculations make these indices a useful tool to apply to a large number of sites nationally and internationally, and to examine the generality of community and population-level responses to physical forcing. , Thesis (PhD) -- Faculty of Science, Journalsim and Media Studies, 2021
- Full Text:
- Date Issued: 2021-12
A social media analytics framework for decision-making in citizen relationship management
- Authors: Yakobi, Khulekani
- Date: 2022-12
- Subjects: Social Media Analytics -- South Africa , Decision making --Mathematical models , Service delivery
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/60048 , vital:62815
- Description: Globally social media has shown unprecedented levels of adoption and Social Media Analytics (SMA) is a rapidly growing topic. For governments, SMA holds the promise of providing tools and frameworks to collect, monitor, analyse and visualise social media data, usually driven by specific requirements from a target application. However, social media data is noisy and unstructured, and organisations struggle to extract knowledge from this data, and convert it into actual intelligence. This study argues that SMA can support intelligent decision-making for Citizen Relationship Management (CzRM). CzRM is a growing effort of governments around the world to strive to respond rapidly to their citizens by fostering a closer relationship thereby creating more effective and efficient service delivery. However, there is a little evidence in literature on empirical studies of any existing decision-making framework for CzRM and SMA adoption. In particular, there is a gap with regards incorporating SMA into decision-making for CzRM of governments, particularly in developing countries like South Africa. The aim of this study was to develop a framework that provides guidelines, including methods and tools, incorporating SMA into decision-making for CzRM in the Gauteng Provincial Government (GPG) and the Free State Provincial Government (FSPG) of South Africa. A Systematic Literature Review (SLR) and conceptual analysis method was conducted to design the Social Media Analytics Framework for Decision-making in the context of CzRM (the SMAF). The findings from the literature review revealed several benefits and challenges with SMA, in particular the shortage of skills, guidelines, methods and tools for SMA. These challenges were used to draft guidelines that were included in the framework, which consists of five components that can be used to derive intelligent information from SMA. The pragmatic philosophy and a case study design was used to generate an in-depth, multifaceted understanding of the underlying problems in the case of the GPG and the FSPG. The German North-West Metropolitan region was used as a third case study to provide a more global perspective and a case of a developed country in terms of Gross Domestic Product. The scope of the study was limited to social media posts by provincial citizens related to CzRM and service delivery. Both formative and summative evaluations of the proposed theoretical framework were conducted. The formative evaluation was conducted v | Page as an Expert Review to receive feedback of the framework from the experts in the field of Computer Science and Information Systems. The findings validated the framework and some minor improvements were made based on the experts’ recommendations. Focus Group Discussions (FGDs) with participants from government managers and decision makers in the three cases were conducted. Case documents for the three cases were collected and reviewed. All collected data was analysed using the Qualitative Content Analysis (QCA) method and common categories and themes were identified. Summative evaluations were conducted in the form of a Field Study, which consisted of an analysis of Twitter data from the three cases, and a closing FGD with Business Intelligence (BI) experts at the primary case of the e-Government department of the GPG. The findings revealed that SMA has been adopted in all three cases; however, while their strategies are comprehensive their implementations are very much in their early stages. The findings also highlighted the status of SMA in government and some potential gaps and areas for implementing the framework. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2022
- Full Text:
- Date Issued: 2022-12
- Authors: Yakobi, Khulekani
- Date: 2022-12
- Subjects: Social Media Analytics -- South Africa , Decision making --Mathematical models , Service delivery
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/60048 , vital:62815
- Description: Globally social media has shown unprecedented levels of adoption and Social Media Analytics (SMA) is a rapidly growing topic. For governments, SMA holds the promise of providing tools and frameworks to collect, monitor, analyse and visualise social media data, usually driven by specific requirements from a target application. However, social media data is noisy and unstructured, and organisations struggle to extract knowledge from this data, and convert it into actual intelligence. This study argues that SMA can support intelligent decision-making for Citizen Relationship Management (CzRM). CzRM is a growing effort of governments around the world to strive to respond rapidly to their citizens by fostering a closer relationship thereby creating more effective and efficient service delivery. However, there is a little evidence in literature on empirical studies of any existing decision-making framework for CzRM and SMA adoption. In particular, there is a gap with regards incorporating SMA into decision-making for CzRM of governments, particularly in developing countries like South Africa. The aim of this study was to develop a framework that provides guidelines, including methods and tools, incorporating SMA into decision-making for CzRM in the Gauteng Provincial Government (GPG) and the Free State Provincial Government (FSPG) of South Africa. A Systematic Literature Review (SLR) and conceptual analysis method was conducted to design the Social Media Analytics Framework for Decision-making in the context of CzRM (the SMAF). The findings from the literature review revealed several benefits and challenges with SMA, in particular the shortage of skills, guidelines, methods and tools for SMA. These challenges were used to draft guidelines that were included in the framework, which consists of five components that can be used to derive intelligent information from SMA. The pragmatic philosophy and a case study design was used to generate an in-depth, multifaceted understanding of the underlying problems in the case of the GPG and the FSPG. The German North-West Metropolitan region was used as a third case study to provide a more global perspective and a case of a developed country in terms of Gross Domestic Product. The scope of the study was limited to social media posts by provincial citizens related to CzRM and service delivery. Both formative and summative evaluations of the proposed theoretical framework were conducted. The formative evaluation was conducted v | Page as an Expert Review to receive feedback of the framework from the experts in the field of Computer Science and Information Systems. The findings validated the framework and some minor improvements were made based on the experts’ recommendations. Focus Group Discussions (FGDs) with participants from government managers and decision makers in the three cases were conducted. Case documents for the three cases were collected and reviewed. All collected data was analysed using the Qualitative Content Analysis (QCA) method and common categories and themes were identified. Summative evaluations were conducted in the form of a Field Study, which consisted of an analysis of Twitter data from the three cases, and a closing FGD with Business Intelligence (BI) experts at the primary case of the e-Government department of the GPG. The findings revealed that SMA has been adopted in all three cases; however, while their strategies are comprehensive their implementations are very much in their early stages. The findings also highlighted the status of SMA in government and some potential gaps and areas for implementing the framework. , Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2022
- Full Text:
- Date Issued: 2022-12
Coordination polymers for denitrogenation of fuel oils
- Authors: Dembaremba, Tendai O
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53630 , vital:45682
- Description: In this thesis, we present adsorptive removal of nitrogen-containing compounds from fuel oil as an alternative to complement conventional hydrotreatment to obtain ultra-low sulfur and nitrogen levels. This is in cognizance of the challenges nitrogen-containing compounds pose to the hydrotreatment process, particularly their inhibition and/or poisoning of the catalysts used in the process, of which basic nitrogen-containing compounds are the major culprits. Selectivity is the biggest challenge for adsorptive removal of nitrogen-containing compounds. We explore reticular synthesis of metal organic frameworks and the use of coordinatively unsaturated metal sites in 1-dimensional coordination polymers to achieve good selectivity for nitrogen-containing compounds. In the first part of the thesis, reticular synthesis of metal organic frameworks to control the size of the cavity, and strategically use the linkers and metal centres was envisaged. In this work we explored variation of the metal centres in the secondary building units (SBUs of the MOFs as the first step to the testing and implementation of the design strategies. Carbazole, representing carbazoles which the major compounds that remain in hydrotreated fuel, was the target compound. Four MOFs of zinc (Zn-CDC-bpe), copper (Cu-CDC-bpe), nickel (Ni-CDC-bpe) and cobalt (Co-CDC-bpe) based on the formation of a dinuclear metal paddlewheel SBUs with the ligand 9H-Carbazole-3,6-dicarboxylic acid (H2CDC) and occupation of the axial positions of the paddlewheel by 1,2-Bis(4-pyridyl)ethane (bpe) to form porous networks were synthesized. A fifth MOF containing only CDC which forms a [Zn4O(O2C-R)5(O2HC-R)] SBU was also synthesized (Zn-CDC). The ligand H2CDC was inspired by the possibility of improving selectivity for carbazole via π–π interactions through the more preferred parallel-offset stacking as well as the possibility for further substitution of the carbazole N-H to add groups that improve selectivity. The sizes of the MOF cavities can then be controlled by choosing different lengths of ligands analogous to 1,2-Bis(4-pyridyl)ethane (bpe), e.g. 4,4’-bipyridine and pyrazine. All the MOFs showed good selectivity of carbazole. The Zn-CDC MOF also had good selectivity for the basic nitrogen-containing compounds tested: quinoline, isoquinoline, quinaldine and 1-naphthylamine. Its uptake of carbazole was also slightly higher. This was attributed to the presence of an unsaturated Zn site in the SBU. Adsorption in all the MOFs was primarily due to physisorption. It was concluded that the role of the metal centre does not play a significant role in the adsorption of carbazole besides providing a template for reticular synthesis. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text: false
- Date Issued: 2021-12
- Authors: Dembaremba, Tendai O
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53630 , vital:45682
- Description: In this thesis, we present adsorptive removal of nitrogen-containing compounds from fuel oil as an alternative to complement conventional hydrotreatment to obtain ultra-low sulfur and nitrogen levels. This is in cognizance of the challenges nitrogen-containing compounds pose to the hydrotreatment process, particularly their inhibition and/or poisoning of the catalysts used in the process, of which basic nitrogen-containing compounds are the major culprits. Selectivity is the biggest challenge for adsorptive removal of nitrogen-containing compounds. We explore reticular synthesis of metal organic frameworks and the use of coordinatively unsaturated metal sites in 1-dimensional coordination polymers to achieve good selectivity for nitrogen-containing compounds. In the first part of the thesis, reticular synthesis of metal organic frameworks to control the size of the cavity, and strategically use the linkers and metal centres was envisaged. In this work we explored variation of the metal centres in the secondary building units (SBUs of the MOFs as the first step to the testing and implementation of the design strategies. Carbazole, representing carbazoles which the major compounds that remain in hydrotreated fuel, was the target compound. Four MOFs of zinc (Zn-CDC-bpe), copper (Cu-CDC-bpe), nickel (Ni-CDC-bpe) and cobalt (Co-CDC-bpe) based on the formation of a dinuclear metal paddlewheel SBUs with the ligand 9H-Carbazole-3,6-dicarboxylic acid (H2CDC) and occupation of the axial positions of the paddlewheel by 1,2-Bis(4-pyridyl)ethane (bpe) to form porous networks were synthesized. A fifth MOF containing only CDC which forms a [Zn4O(O2C-R)5(O2HC-R)] SBU was also synthesized (Zn-CDC). The ligand H2CDC was inspired by the possibility of improving selectivity for carbazole via π–π interactions through the more preferred parallel-offset stacking as well as the possibility for further substitution of the carbazole N-H to add groups that improve selectivity. The sizes of the MOF cavities can then be controlled by choosing different lengths of ligands analogous to 1,2-Bis(4-pyridyl)ethane (bpe), e.g. 4,4’-bipyridine and pyrazine. All the MOFs showed good selectivity of carbazole. The Zn-CDC MOF also had good selectivity for the basic nitrogen-containing compounds tested: quinoline, isoquinoline, quinaldine and 1-naphthylamine. Its uptake of carbazole was also slightly higher. This was attributed to the presence of an unsaturated Zn site in the SBU. Adsorption in all the MOFs was primarily due to physisorption. It was concluded that the role of the metal centre does not play a significant role in the adsorption of carbazole besides providing a template for reticular synthesis. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text: false
- Date Issued: 2021-12