Development of density-dependent and density-independent competition models to understand single tree growth responses in eucalyptus stands
- Authors: Kepe, Lulama Patrick
- Date: 2024-12
- Subjects: Forests and forestry -- Mathematical models , Trees -- Growth -- Mathematical models , Eucalyptus grandis
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68906 , vital:77161
- Description: In commercial forest production, predicted yields based on mensuration recommendations are seldom realized, and minimal silvicultural standards based on results from trial blocks do not account for the relationship between initial planting density and final stocking. Growth models designed to investigate management options must employ competition indices to provide reliable predictions under extreme silviculture. The competition a tree experiences until the day of harvest is a strong driver for quality and volume of timber. Hence, this turns the regulation of competition into an integral part of silviculture. According to Little et al. (2003), it is known that, at some stage after canopy closure, individual trees in a stand will begin to compete for resources. To investigate competition amongst individual trees, a re-purposed Bayesian mixed effects model, similar in characteristics to a Sire model used for estimating breeding values, is proposed. In animal breeding models, the Sire Model allows for the inclusion of a numerator relationship matrix containing inbreeding coefficients. In a similar way, documented competition indices are included in the model in an attempt to estimate posterior probabilities of specifically selected individual trees being the strongest growers during different stages in the tree growth cycle. Estimated tree growth indices were determined and used to make probability statements in order to rank the individually selected trees based on the amount of growth observed. A tree growth index is a measurement of a tree’s average growth performance in relation to the average growth performance of all trees on the same plot. As different competition indices are introduced into the model, changes in the probabilities are observed and compared to what is visually observed on the plot, i.e. if the tree with the highest probability of being the strongest grower, is actually not necessarily the largest tree of the group of selected trees, but rather the tree that presented the largest amount of growth of the selected group of trees during that specific growth season. From a randomly selected plot, a group of neighboring trees were randomly selected. Four specifically selected target trees were then identified from this group of 25 selected trees, and analyzed. For this discussion, for example, from our randomly selected group of 25 neighboring trees, tree 54, tree 56, tree 86, and tree 88 were specifically selected for further analysis. For these specifically selected trees, marginal posterior densities for the variance components and random effects were then estimated using the Gibbs Sampler, where competition between the trees was assumed present, as well as for the case where it was assumed that no competition takes place between the individually selected trees. In the latter case, an identity matrix was utilized in the Gibbs sampling algorithm where it was assumed that there is no competition between the trees. Both a distance independent competition index (Lorimer,1983), and a distance dependent index (Hegyi, 1974), were used to generate the numerator relationship matrix A that was used by the Gibbs sampling algorithm in the case where competition was assumed between individual trees. Also a new distance dependent index was proposed and tested in this study as well. Results from the selected plot, with a 1500 stems per hectare (sph) density, indicated that there were no significant differences in the average growth between these selected trees. However, the marginal posterior densities of the fixed effects indicated that there was a significant difference in the average growth rates between the base level conditions and other levels determined for each of these fixed effect factors for the selected trees, since their 95% equal tails credibility intervals, did not contain zero. This therefore indicated that the specific treatment applied on the plot, had a significant effect on the individual tree growth. Results when competition was assumed present, revealed that the estimated marginal posterior densities for the error variance as well as tree variance, were severely positively skewed. , Thesis (PhD) -- Faculty of Science, School of Natural Resource Science & Management, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Kepe, Lulama Patrick
- Date: 2024-12
- Subjects: Forests and forestry -- Mathematical models , Trees -- Growth -- Mathematical models , Eucalyptus grandis
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68906 , vital:77161
- Description: In commercial forest production, predicted yields based on mensuration recommendations are seldom realized, and minimal silvicultural standards based on results from trial blocks do not account for the relationship between initial planting density and final stocking. Growth models designed to investigate management options must employ competition indices to provide reliable predictions under extreme silviculture. The competition a tree experiences until the day of harvest is a strong driver for quality and volume of timber. Hence, this turns the regulation of competition into an integral part of silviculture. According to Little et al. (2003), it is known that, at some stage after canopy closure, individual trees in a stand will begin to compete for resources. To investigate competition amongst individual trees, a re-purposed Bayesian mixed effects model, similar in characteristics to a Sire model used for estimating breeding values, is proposed. In animal breeding models, the Sire Model allows for the inclusion of a numerator relationship matrix containing inbreeding coefficients. In a similar way, documented competition indices are included in the model in an attempt to estimate posterior probabilities of specifically selected individual trees being the strongest growers during different stages in the tree growth cycle. Estimated tree growth indices were determined and used to make probability statements in order to rank the individually selected trees based on the amount of growth observed. A tree growth index is a measurement of a tree’s average growth performance in relation to the average growth performance of all trees on the same plot. As different competition indices are introduced into the model, changes in the probabilities are observed and compared to what is visually observed on the plot, i.e. if the tree with the highest probability of being the strongest grower, is actually not necessarily the largest tree of the group of selected trees, but rather the tree that presented the largest amount of growth of the selected group of trees during that specific growth season. From a randomly selected plot, a group of neighboring trees were randomly selected. Four specifically selected target trees were then identified from this group of 25 selected trees, and analyzed. For this discussion, for example, from our randomly selected group of 25 neighboring trees, tree 54, tree 56, tree 86, and tree 88 were specifically selected for further analysis. For these specifically selected trees, marginal posterior densities for the variance components and random effects were then estimated using the Gibbs Sampler, where competition between the trees was assumed present, as well as for the case where it was assumed that no competition takes place between the individually selected trees. In the latter case, an identity matrix was utilized in the Gibbs sampling algorithm where it was assumed that there is no competition between the trees. Both a distance independent competition index (Lorimer,1983), and a distance dependent index (Hegyi, 1974), were used to generate the numerator relationship matrix A that was used by the Gibbs sampling algorithm in the case where competition was assumed between individual trees. Also a new distance dependent index was proposed and tested in this study as well. Results from the selected plot, with a 1500 stems per hectare (sph) density, indicated that there were no significant differences in the average growth between these selected trees. However, the marginal posterior densities of the fixed effects indicated that there was a significant difference in the average growth rates between the base level conditions and other levels determined for each of these fixed effect factors for the selected trees, since their 95% equal tails credibility intervals, did not contain zero. This therefore indicated that the specific treatment applied on the plot, had a significant effect on the individual tree growth. Results when competition was assumed present, revealed that the estimated marginal posterior densities for the error variance as well as tree variance, were severely positively skewed. , Thesis (PhD) -- Faculty of Science, School of Natural Resource Science & Management, 2024
- Full Text:
- Date Issued: 2024-12
Exploiting continuous flow technology to develop synthetic processes for active pharmaceutical ingredients: prilocaine and betrixaban
- Authors: Sagandira, Mellisa Brenda
- Date: 2024-12
- Subjects: Pharmaceutical technology , Drug development , Pharmaceutical biotechnology
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/69464 , vital:77259
- Description: The dilemma of providing affordable health care has long haunted African countries due to the continuously growing disease burden as the population increases. Africa accounts for only 3 % of global drug production and imports over 90 % of its life saving medicines at a yearly cost of US$14 billion according to the African Development Bank (AfDB). Attaining Africa’s Agenda 2063, Universal Health Coverage (UHC) and Sustainable development Goal 3 (SDG3) aspirations of ensuring healthy and well-nourished citizens remain difficult given this situation. This over-dependence on imports has led to drug shortages, high pricing, poor quality medicines and unguaranteed supply chains, thus there still remains an unmet need. The advent of the COVID-19 pandemic worsened this situation as many countries curbed exports resulting in a crisis across the continent. Africa experienced high demand of medicines compared to prepandemic level, which threatened the health care of the continent. This situation can be addressed by establishment of local pharmaceutical manufacturing capability through adoption of advanced manufacturing technologies such as continuous flow chemistry. In this research, we therefore seek to exploit continuous flow chemistry, an enabling technology to develop safe and efficient synthetic processes for active pharmaceutical ingredients: prilocaine and betrixaban as case studies. To the best of our knowledge there is no reported work on synthetic processes towards prilocaine and betrixaban under continuous flow conditions, thus this research extensively unearthed interesting continuous flow processes towards these APIs. In a broader view, establishment of local APIs production will ease Africa’s over-dependence on imports, which will in turn address issues such as drug shortages, poor quality and high pricing. This work aims to demonstrate how continuous flow technology can be useful for the establishment of local APIs manufacturing, which will inherently revolutionize medicines availability, affordability and accessibility to the greater population. Chapter one begins with a brief overview on Africa’s disease burden and pharmaceutical supply chain. Continuous flow chemistry is introduced with its benefits and limitations discussed. Lastly a mini review of examples of APIs synthesised in continuous flow is presented. In chapter two, we demonstrate how continuous flow technology can be exploited to develop synthetic processes towards prilocaine as our first case study. This chapter clearly demonstrates how highly exothermic nitration reactions can be safely handled by using continuous flow systems. Additionally, the use of a micro structured mixer facilitated biphasic nitration of toluene to be carried out with enhanced mass transfer, which inherently led to improved selectivity of ortho-nitrotoluene (preferred isomer) to 79 % compared to 59 % achieved in batch mode. A two-step synthesis of ortho-toluidine via biphasic nitration of toluene and nitroreduction was demonstrated with the incorporation of a Zaiput liquid/liquid separator to facilitate in-line separation. Comprehensive optimisation studies were carried out in flow. Prilocaine was synthesised in 74 % overall yield in a 13.6 min residence time for all processes. In chapter three, we demonstrate how continuous flow technology can be exploited to develop synthetic processes towards betrixaban. Synthetic routes towards betrixaban feature two amide bond formation transformations. Pleasingly, we explored multistep chemistry to develop amide synthesis protocols in flow without interruption for work up and isolation. An overall yield of 92 % was achieved to get to key intermediate to betrixaban in 8 min total residence time. Chapter four demonstrates the robustness of developed amide synthesis protocols, a key transformation in synthetic routes towards prilocaine and betrixaban in continuous flow systems. A total of 22 amides were synthesised via flow multistep processes with isolated yields greater than 82 %. All the compounds were characterized using infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Quantification of the reaction mixtures were carried out using highperformance liquid chromatography (HPLC) and gas chromatography (GC). , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Sagandira, Mellisa Brenda
- Date: 2024-12
- Subjects: Pharmaceutical technology , Drug development , Pharmaceutical biotechnology
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/69464 , vital:77259
- Description: The dilemma of providing affordable health care has long haunted African countries due to the continuously growing disease burden as the population increases. Africa accounts for only 3 % of global drug production and imports over 90 % of its life saving medicines at a yearly cost of US$14 billion according to the African Development Bank (AfDB). Attaining Africa’s Agenda 2063, Universal Health Coverage (UHC) and Sustainable development Goal 3 (SDG3) aspirations of ensuring healthy and well-nourished citizens remain difficult given this situation. This over-dependence on imports has led to drug shortages, high pricing, poor quality medicines and unguaranteed supply chains, thus there still remains an unmet need. The advent of the COVID-19 pandemic worsened this situation as many countries curbed exports resulting in a crisis across the continent. Africa experienced high demand of medicines compared to prepandemic level, which threatened the health care of the continent. This situation can be addressed by establishment of local pharmaceutical manufacturing capability through adoption of advanced manufacturing technologies such as continuous flow chemistry. In this research, we therefore seek to exploit continuous flow chemistry, an enabling technology to develop safe and efficient synthetic processes for active pharmaceutical ingredients: prilocaine and betrixaban as case studies. To the best of our knowledge there is no reported work on synthetic processes towards prilocaine and betrixaban under continuous flow conditions, thus this research extensively unearthed interesting continuous flow processes towards these APIs. In a broader view, establishment of local APIs production will ease Africa’s over-dependence on imports, which will in turn address issues such as drug shortages, poor quality and high pricing. This work aims to demonstrate how continuous flow technology can be useful for the establishment of local APIs manufacturing, which will inherently revolutionize medicines availability, affordability and accessibility to the greater population. Chapter one begins with a brief overview on Africa’s disease burden and pharmaceutical supply chain. Continuous flow chemistry is introduced with its benefits and limitations discussed. Lastly a mini review of examples of APIs synthesised in continuous flow is presented. In chapter two, we demonstrate how continuous flow technology can be exploited to develop synthetic processes towards prilocaine as our first case study. This chapter clearly demonstrates how highly exothermic nitration reactions can be safely handled by using continuous flow systems. Additionally, the use of a micro structured mixer facilitated biphasic nitration of toluene to be carried out with enhanced mass transfer, which inherently led to improved selectivity of ortho-nitrotoluene (preferred isomer) to 79 % compared to 59 % achieved in batch mode. A two-step synthesis of ortho-toluidine via biphasic nitration of toluene and nitroreduction was demonstrated with the incorporation of a Zaiput liquid/liquid separator to facilitate in-line separation. Comprehensive optimisation studies were carried out in flow. Prilocaine was synthesised in 74 % overall yield in a 13.6 min residence time for all processes. In chapter three, we demonstrate how continuous flow technology can be exploited to develop synthetic processes towards betrixaban. Synthetic routes towards betrixaban feature two amide bond formation transformations. Pleasingly, we explored multistep chemistry to develop amide synthesis protocols in flow without interruption for work up and isolation. An overall yield of 92 % was achieved to get to key intermediate to betrixaban in 8 min total residence time. Chapter four demonstrates the robustness of developed amide synthesis protocols, a key transformation in synthetic routes towards prilocaine and betrixaban in continuous flow systems. A total of 22 amides were synthesised via flow multistep processes with isolated yields greater than 82 %. All the compounds were characterized using infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Quantification of the reaction mixtures were carried out using highperformance liquid chromatography (HPLC) and gas chromatography (GC). , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Exploring children’s understandings of gender using critical literacy in a reading club
- Jansen, Lincoln Lee, Surname, name
- Authors: Jansen, Lincoln Lee , Surname, name
- Date: 2024-12
- Subjects: Book clubs (Discussion groups) -- South Africa , Literacy -- Study and teaching (Elementary) , Literacy -- Study and teaching (Middle school)
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68333 , vital:76976
- Description: School literacy practices have always favoured traditional, gender stereotypical portrayals of characters in books. These portrayals are not troublesome as it helps children build a sense of identity. However, these portrayals often fail to represent people in more diverse ways and thus does not reflect how societies have progressed. These narrow portrayals are also often limiting and do not take into consideration people’s personal interests which can lead to them being ostracised and marginalised. The People’s Republic of China is the context for this study where traditional, conservative views are upheld about ways of being and doing for males and females. This is a qualitative study within the interpretivist paradigm which recognised the individual perceptions of participants within their specific sociocultural context. By establishing a reading club as a Third Space for literacy engagement, this study sought to explore how grade 2 learners at a school in Beijing, China responded to traditional and diverse portrayals of characters in books. This study regarded the establishment of a reading club as an empowering practice as it allowed a safe space for the participants to freely share their deliberations about ways of being in the world. Coupled with critical literacy as a practice, participants took a critical stance in instances of gender bias and injustices and in doing so, allowed them to accentuate their morality. Findings of this study suggest that the Chinese participants had very flexible ideas about ways of being and doing in the world as long as these did not conflict with their understandings of the law. Participants also upheld that gender performances and gendered behaviour are open to all with impunity. The findings of this study also highlight the importance of providing diverse literature to children as this helps them to deal with, and examine, issues they might not ordinarily encounter in a safe way and in doing so, expand their worldviews and cultivate empathy. , Thesis (PhD) -- Faculty of Education, School of Primary Schooling, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Jansen, Lincoln Lee , Surname, name
- Date: 2024-12
- Subjects: Book clubs (Discussion groups) -- South Africa , Literacy -- Study and teaching (Elementary) , Literacy -- Study and teaching (Middle school)
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68333 , vital:76976
- Description: School literacy practices have always favoured traditional, gender stereotypical portrayals of characters in books. These portrayals are not troublesome as it helps children build a sense of identity. However, these portrayals often fail to represent people in more diverse ways and thus does not reflect how societies have progressed. These narrow portrayals are also often limiting and do not take into consideration people’s personal interests which can lead to them being ostracised and marginalised. The People’s Republic of China is the context for this study where traditional, conservative views are upheld about ways of being and doing for males and females. This is a qualitative study within the interpretivist paradigm which recognised the individual perceptions of participants within their specific sociocultural context. By establishing a reading club as a Third Space for literacy engagement, this study sought to explore how grade 2 learners at a school in Beijing, China responded to traditional and diverse portrayals of characters in books. This study regarded the establishment of a reading club as an empowering practice as it allowed a safe space for the participants to freely share their deliberations about ways of being in the world. Coupled with critical literacy as a practice, participants took a critical stance in instances of gender bias and injustices and in doing so, allowed them to accentuate their morality. Findings of this study suggest that the Chinese participants had very flexible ideas about ways of being and doing in the world as long as these did not conflict with their understandings of the law. Participants also upheld that gender performances and gendered behaviour are open to all with impunity. The findings of this study also highlight the importance of providing diverse literature to children as this helps them to deal with, and examine, issues they might not ordinarily encounter in a safe way and in doing so, expand their worldviews and cultivate empathy. , Thesis (PhD) -- Faculty of Education, School of Primary Schooling, 2024
- Full Text:
- Date Issued: 2024-12
Formulation of Fish Feed for Aquaculture using Olive Pomace Extract as an Antioxidant
- Authors: Koza, Nondumiso Norma
- Date: 2024-12
- Subjects: Fishes -- Feeding and feeds , Fishes -- Ecology , Sustainable aquaculture
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69318 , vital:77205
- Description: Olive pomace is a significant by-product of the olive oil extraction process and is an environmental issue in olive-producing countries. This project aimed to add extracts from olive pomace as an antioxidant to a fish feed formulation without compromising growth performance and meat quality, thereby contributing to the aquaculture industry. To produce the olive pomace extracts, Coratina cultivar olives were collected from a farm near Oudtshoorn, and the fresh pomace was immediately frozen at -22oC for preservation. The extracts were obtained using a large-scale extraction method using a solvent blend of n-heptane, ethanol, and water. A pressure filtration and centrifuge method were then applied to separate any residue from the extracts. An HPLC method was developed to characterise the extracts' content, identifying various bioactive compounds such as squalene, α-tocopherol, and water-soluble polyphenols like oleuropein, hydroxytyrosol, and tyrosol. In a fish feeding trial it was concluded that the fish fed with the feed without olive pomace gained more weight than those fed the feed with the added pomace extract. Overall, the results indicate that fish sustained on the feed without the olive pomace extract ate more food, consuming more energy to support weight gain but that this did not necessarily translate to an improved feed conversion ratio. The morphometric variables suggest that fish used in the trial remained healthy, implying that there may be a taste or palatability difference between feeds that could explain why less of the feed with olive pomace extract was eaten. Overall, the observed feed conversion ratio values were somewhat lower than the expected values for tilapia (FCR: 1.5-2.0). The peroxide value of fish feed with an addition of 0.3% olive pomace extract was lower than that of the feed without olive pomace extract after 12 weeks of stability testing at room temperature. The results showed a value of 1.48 MeqO2/kg for the feed containing olive pomace extract compared to the peroxide value for the fish feed without olive pomace extract, which was 2.75 MeqO2/kg. This indicates that the nutritional content of the feed was preserved. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Koza, Nondumiso Norma
- Date: 2024-12
- Subjects: Fishes -- Feeding and feeds , Fishes -- Ecology , Sustainable aquaculture
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69318 , vital:77205
- Description: Olive pomace is a significant by-product of the olive oil extraction process and is an environmental issue in olive-producing countries. This project aimed to add extracts from olive pomace as an antioxidant to a fish feed formulation without compromising growth performance and meat quality, thereby contributing to the aquaculture industry. To produce the olive pomace extracts, Coratina cultivar olives were collected from a farm near Oudtshoorn, and the fresh pomace was immediately frozen at -22oC for preservation. The extracts were obtained using a large-scale extraction method using a solvent blend of n-heptane, ethanol, and water. A pressure filtration and centrifuge method were then applied to separate any residue from the extracts. An HPLC method was developed to characterise the extracts' content, identifying various bioactive compounds such as squalene, α-tocopherol, and water-soluble polyphenols like oleuropein, hydroxytyrosol, and tyrosol. In a fish feeding trial it was concluded that the fish fed with the feed without olive pomace gained more weight than those fed the feed with the added pomace extract. Overall, the results indicate that fish sustained on the feed without the olive pomace extract ate more food, consuming more energy to support weight gain but that this did not necessarily translate to an improved feed conversion ratio. The morphometric variables suggest that fish used in the trial remained healthy, implying that there may be a taste or palatability difference between feeds that could explain why less of the feed with olive pomace extract was eaten. Overall, the observed feed conversion ratio values were somewhat lower than the expected values for tilapia (FCR: 1.5-2.0). The peroxide value of fish feed with an addition of 0.3% olive pomace extract was lower than that of the feed without olive pomace extract after 12 weeks of stability testing at room temperature. The results showed a value of 1.48 MeqO2/kg for the feed containing olive pomace extract compared to the peroxide value for the fish feed without olive pomace extract, which was 2.75 MeqO2/kg. This indicates that the nutritional content of the feed was preserved. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Graphene@microalgae-based nanohybrid structures as adsorbents for removal of Cr(VI) ions in aqueous solutions
- Authors: Mulovhedzi, Rolivhuwa
- Date: 2024-12
- Subjects: Nanoscience , Nanotechnology , Nonaqueous solvents
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69404 , vital:77252
- Description: iv ABSTRACT The efficient removal of heavy metals using carbon-based nanoadsorbents poses a substantial challenge in the domain of water purification. Graphene-based materials have been extensively utilised in the treatment of water and wastewater due to their tremendous surface areas, porosity, turntable nature to different functional groups, and photo-catalytic properties. In this project, graphene oxide (GO) was synthesised via the modified Hummers method. A similar method was used to produce nitrogen-doped graphene oxide (NGO), with urea as the nitrogen precursor. Utilising biomass materials to dope graphene-based nanocomposites can effectively enhance their application in water treatment. In this work, graphene oxide-microalgae (GO@Algae) and N-doped graphene oxide-microalgae (NGO@Algae) nanocomposites were synthesised by combining GO or NGO with green Scenedesmus microalgae. This was done through a solution self-assembly mixing method using ultrasonication. The resulting nanocomposites were used to remove Cr(VI) from water solutions. The influence of microalgae content deposited on GO and NGO nanosheets at different weight ratios (1:1, 3:1, and 1:3) on the chemical, structural, morphological, and thermal characteristics of nanoadsorbents was evaluated using various techniques such as Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The flat nanosheet-like morphology of GO@Algae and NGO@Algae nanostructured materials was observed through SEM, confirming microalgae's incorporation within the GO and NGO matrices. The thermal stability and surface area properties of GO and NGO nanocomposite materials decreased with the incorporation of microalgae content. The incorporation of microalgae into GO nanosheets showed enhancements in chemical and structural properties due to the presence of the strong covalent interaction (oxygen and nitrogen-containing groups) between the interfaces of nanocomposites. XPS and FT-IR analyses revealed the existence of amides, carboxylic acids, and phosphates, which exhibited positive charges below the pH 2.03 point-of-zero charge. The second phase of the study involved assessing the adsorption capabilities of the GO, NGO nanosheets, and GO@Algae and NGO@Algae nanocomposites in removing Cr(VI)from the water solution. Adsorption parameters such as the effect of solution pH, contact time, adsorbent dosage and metal ion concentrations were evaluated for Cr(VI) removal. When comparing GO, NGO, GO@Algae, and NGO@Algae, it was found that GO@Algae and NGO@Algae exhibited superior adsorption performance due to the available functional groups and well-developed pores. Additionally, a mixed ratio of GO or NGO and algae at a ratio of 1:3 was found to be the most suitable for GO@Algae and NGO@Algae. The adsorption efficiency of nanostructured materials for Cr(VI) is significantly influenced by their surface charge, porosity and specific surface area. The results revealed that the adsorption capabilities of GO@Algae (1:3) and NGO@Algae (1:3) were 2.24 and 2.01 times higher than GO and NGO which were 1.64 and 1.89, respectively, at a solution of pH 2 where HCrO4− species are predominant compared to a solution of pH 5 which predominate a mix of Cr2O72− and CrO42- species. The enhanced performance of the GO@Algae and NGO@Algae nanocomposites is attributed due to their increased surface functionalities and porosity. The adsorption of Cr(VI) ions by the GO/NGO@Algae nanocomposites declined with increasing initial concentration of Cr(VI) species in the water medium. The adsorption kinetics data for GO, NGO, GO@Algae (1:3), and NGO@Algae (1:3) exhibited a good fit with the pseudo-second-order model (R2 > 0.995) suggesting that chemisorption governed the adsorption process. Similarly, the isotherm adsorption findings showed a good fit with the Freundlich model (R2 > 0.961). The findings indicated that the adsorption mechanism process was characterised by monolayer adsorption onto a heterogeneous adsorbent surface. Furthermore, the GO@Algae (1:3) was found to have the maximum adsorption capacity of 10.85 mg/g surpassing the capacities of both unmodified and NGO@Algae counterparts. The application of GO@Algae and NGO@Algae has the potential to promote the green reuse of graphene-based nanomaterials. In summary, GO@Algae and NGO@Algae show great potential as eco-friendly adsorbents for the feasible treatment of heavy metal-contaminated water. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Mulovhedzi, Rolivhuwa
- Date: 2024-12
- Subjects: Nanoscience , Nanotechnology , Nonaqueous solvents
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69404 , vital:77252
- Description: iv ABSTRACT The efficient removal of heavy metals using carbon-based nanoadsorbents poses a substantial challenge in the domain of water purification. Graphene-based materials have been extensively utilised in the treatment of water and wastewater due to their tremendous surface areas, porosity, turntable nature to different functional groups, and photo-catalytic properties. In this project, graphene oxide (GO) was synthesised via the modified Hummers method. A similar method was used to produce nitrogen-doped graphene oxide (NGO), with urea as the nitrogen precursor. Utilising biomass materials to dope graphene-based nanocomposites can effectively enhance their application in water treatment. In this work, graphene oxide-microalgae (GO@Algae) and N-doped graphene oxide-microalgae (NGO@Algae) nanocomposites were synthesised by combining GO or NGO with green Scenedesmus microalgae. This was done through a solution self-assembly mixing method using ultrasonication. The resulting nanocomposites were used to remove Cr(VI) from water solutions. The influence of microalgae content deposited on GO and NGO nanosheets at different weight ratios (1:1, 3:1, and 1:3) on the chemical, structural, morphological, and thermal characteristics of nanoadsorbents was evaluated using various techniques such as Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The flat nanosheet-like morphology of GO@Algae and NGO@Algae nanostructured materials was observed through SEM, confirming microalgae's incorporation within the GO and NGO matrices. The thermal stability and surface area properties of GO and NGO nanocomposite materials decreased with the incorporation of microalgae content. The incorporation of microalgae into GO nanosheets showed enhancements in chemical and structural properties due to the presence of the strong covalent interaction (oxygen and nitrogen-containing groups) between the interfaces of nanocomposites. XPS and FT-IR analyses revealed the existence of amides, carboxylic acids, and phosphates, which exhibited positive charges below the pH 2.03 point-of-zero charge. The second phase of the study involved assessing the adsorption capabilities of the GO, NGO nanosheets, and GO@Algae and NGO@Algae nanocomposites in removing Cr(VI)from the water solution. Adsorption parameters such as the effect of solution pH, contact time, adsorbent dosage and metal ion concentrations were evaluated for Cr(VI) removal. When comparing GO, NGO, GO@Algae, and NGO@Algae, it was found that GO@Algae and NGO@Algae exhibited superior adsorption performance due to the available functional groups and well-developed pores. Additionally, a mixed ratio of GO or NGO and algae at a ratio of 1:3 was found to be the most suitable for GO@Algae and NGO@Algae. The adsorption efficiency of nanostructured materials for Cr(VI) is significantly influenced by their surface charge, porosity and specific surface area. The results revealed that the adsorption capabilities of GO@Algae (1:3) and NGO@Algae (1:3) were 2.24 and 2.01 times higher than GO and NGO which were 1.64 and 1.89, respectively, at a solution of pH 2 where HCrO4− species are predominant compared to a solution of pH 5 which predominate a mix of Cr2O72− and CrO42- species. The enhanced performance of the GO@Algae and NGO@Algae nanocomposites is attributed due to their increased surface functionalities and porosity. The adsorption of Cr(VI) ions by the GO/NGO@Algae nanocomposites declined with increasing initial concentration of Cr(VI) species in the water medium. The adsorption kinetics data for GO, NGO, GO@Algae (1:3), and NGO@Algae (1:3) exhibited a good fit with the pseudo-second-order model (R2 > 0.995) suggesting that chemisorption governed the adsorption process. Similarly, the isotherm adsorption findings showed a good fit with the Freundlich model (R2 > 0.961). The findings indicated that the adsorption mechanism process was characterised by monolayer adsorption onto a heterogeneous adsorbent surface. Furthermore, the GO@Algae (1:3) was found to have the maximum adsorption capacity of 10.85 mg/g surpassing the capacities of both unmodified and NGO@Algae counterparts. The application of GO@Algae and NGO@Algae has the potential to promote the green reuse of graphene-based nanomaterials. In summary, GO@Algae and NGO@Algae show great potential as eco-friendly adsorbents for the feasible treatment of heavy metal-contaminated water. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Ground- and marine water inputs into supratidal microbialite systems along the Nelson Mandela Bay coastline
- Authors: O’Connell, Tristin Wade
- Date: 2024-12
- Subjects: Groundwater -- South Africa -- Nelson Mandela Bay , Earth sciences , Geology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69415 , vital:77253
- Description: Extant supratidal microbialite systems are especially numerous and well-developed along the rocky coastline of Nelson Mandela Bay (NMB), South Africa. Precipitating in a hydrological environment formed by the input of constant, fresh groundwater discharge and periodic marine water intrusion these systems form part of the longest uninterrupted geological record of life on Earth (~3.4 billion years ago). Microbialites are layered organosedimentary deposits which potentially provide a window into historical environmental conditions. This study focusses on the fresh groundwater and saline marine water inputs of these microbialite pools, and the corresponding microbialite accretion rates. Severe regional drought in the NMB area resulted in rapid anthropogenic groundwater abstraction of the coastal aquifers on which the microbialite systems rely for groundwater inflow. This study provides insight into the current state of the coastal aquifers of NMB through the quantification of groundwater discharge via microbialite systems in terms of volume and flow rate. This is paired with in situ hourly microbialite pool water temperature and conductivity data to determine the effect of marine intrusion and the role of tidal flushing in these pools. A spatial assessment of groundwater discharge conducted using quantitative and semi-quantitative measurement techniques indicated that the total discharge of the study area is ~45.8 L/s or 3.8 ML/d. Over 1,500 freshwater seeps were identified, of which 78% showed microbialite deposits. Topography of the coast indicated that this might influence the flowrate. Calcareous sediment of sandy beaches within the study area supported lower discharge, while rocky shores with lithified rock had higher discharge. Seasonal differences in the volume discharged were evident, with winter having higher flowrates. Flow paths and discharge rates are affected by inland lithological differences and indicate variability linked to rainfall events that show lag effects depending on aquifer origins. This study is the first spatial analysis of the volume of groundwater discharging through microbialite-fed seeps. Marine intrusion and the corresponding pool flushing dynamics identified three types of microbailite systems: groundwater-dominant, dynamic input, and fast-reacting sites. A novel measurement technique for microbialite accretion determined accretion rates for systems under varying pool conditions. Although the average accretion rates of the Nelson Mandela Bay microbialites were in the order of erosion of 0.35 mm per year, there was significant variability in these measurements likely linked to differential localised vulnerability to storm events or responses to groundwater ix flow variability. It remains to be determined whether these factors are definitive risks to the sensitive supratidal microbialite systems. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: O’Connell, Tristin Wade
- Date: 2024-12
- Subjects: Groundwater -- South Africa -- Nelson Mandela Bay , Earth sciences , Geology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69415 , vital:77253
- Description: Extant supratidal microbialite systems are especially numerous and well-developed along the rocky coastline of Nelson Mandela Bay (NMB), South Africa. Precipitating in a hydrological environment formed by the input of constant, fresh groundwater discharge and periodic marine water intrusion these systems form part of the longest uninterrupted geological record of life on Earth (~3.4 billion years ago). Microbialites are layered organosedimentary deposits which potentially provide a window into historical environmental conditions. This study focusses on the fresh groundwater and saline marine water inputs of these microbialite pools, and the corresponding microbialite accretion rates. Severe regional drought in the NMB area resulted in rapid anthropogenic groundwater abstraction of the coastal aquifers on which the microbialite systems rely for groundwater inflow. This study provides insight into the current state of the coastal aquifers of NMB through the quantification of groundwater discharge via microbialite systems in terms of volume and flow rate. This is paired with in situ hourly microbialite pool water temperature and conductivity data to determine the effect of marine intrusion and the role of tidal flushing in these pools. A spatial assessment of groundwater discharge conducted using quantitative and semi-quantitative measurement techniques indicated that the total discharge of the study area is ~45.8 L/s or 3.8 ML/d. Over 1,500 freshwater seeps were identified, of which 78% showed microbialite deposits. Topography of the coast indicated that this might influence the flowrate. Calcareous sediment of sandy beaches within the study area supported lower discharge, while rocky shores with lithified rock had higher discharge. Seasonal differences in the volume discharged were evident, with winter having higher flowrates. Flow paths and discharge rates are affected by inland lithological differences and indicate variability linked to rainfall events that show lag effects depending on aquifer origins. This study is the first spatial analysis of the volume of groundwater discharging through microbialite-fed seeps. Marine intrusion and the corresponding pool flushing dynamics identified three types of microbailite systems: groundwater-dominant, dynamic input, and fast-reacting sites. A novel measurement technique for microbialite accretion determined accretion rates for systems under varying pool conditions. Although the average accretion rates of the Nelson Mandela Bay microbialites were in the order of erosion of 0.35 mm per year, there was significant variability in these measurements likely linked to differential localised vulnerability to storm events or responses to groundwater ix flow variability. It remains to be determined whether these factors are definitive risks to the sensitive supratidal microbialite systems. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Gymnopilus junonius and Rhodofomitopsis lilacinogilva: In vitro evaluation of antimycobacterial activity, safety assessment and isolation of active compounds
- Authors: Didloff, Jenske
- Date: 2024-12
- Subjects: Antibacterial agents , Plants, Useful -- South Africa , Medicinal plants -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68840 , vital:77122
- Description: Tuberculosis remains a significant public health challenge due to the complexity and compliance issues of its treatment, the prevalence of latent infections, the high rate of HIV co-infection, and the spread of drug-resistant strains. This highlights the need to search for new antimycobacterial drugs. Natural products have historically been used as sources for the discovery of pharmaceuticals. Although medicinal macrofungi have been exploited in traditional folk medicines for the treatment of various diseases, research into their antimycobacterial activity remains limited.The aim of this study was to isolate, identify, and characterise the antimycobacterial compound(s) present in ethanol fruiting body extracts of Gymnopilus junonius (Fr.) P.D. Orton (Hymenogastraceae) and Rhodofomitopsis lilacinogilva (Berk.) B.K. Cui, M.L. Han, & Y.C. Dai (Fomitopsidaceae), as well as to investigate their mechanism of action and potential toxicity using in vitro and in vivo screening methods.Bioassay-guided fractionation was conducted using column chromatography and preparative thin-layer chromatography to isolate the active antimycobacterial fraction/compound from ethanol extracts of G. junonius and R. lilacinogilva. Antimycobacterial activity against M. tuberculosis H37Rv was screened using a resazurin microplate assay (REMA). The chemical structure was elucidated employing 1D-(1H NMR) and 2D NMR spectroscopy (HSQC, HMBC) techniques, along with High- Performance Liquid Chromatography High-Resolution Electron Spray Ionisation Mass Spectrometry (HPLC-HRESI-MS). Transmission electron microscopy (TEM) was utilised to observe the ultrastructural changes in M. tuberculosis induced by the active fraction/compound. Toxicity assessment was performed on African green monkeykidney (Vero) and human hepatoma (C3A) cell lines using various staining techniques to observe the potential risk for hepatotoxicity (CellRox orange, TMRE, and MTG staining) and genotoxicity (NucRed staining). In vivo toxicity of extracts was evaluated using a zebrafish embryo/larvae model to observe developmental and teratogenic effects.The bioassay-guided fractionation of G. junonius and R. lilacinogilva extracts yielded an active compound and a fraction displaying inhibitory activity against M. tuberculosis, with MIC values of 31.25 μg/mL and 250 μg/mL, respectively. Gymnopilene was identified as the main active compound isolated from G. junonius, while fraction 8 from R. lilacinogilva contained a predominant constituent resembling a pachymic acid derivative. Transmission electron microscopy revealed ultrastructural damage to M. tuberculosis cells upon treatment with gymnopilene and fraction 8, which was observed as the disruption and disintegration of the cell wall. In vitro toxicity assessment indicated a reduction in the cell density in both Vero and C3A cell lines following exposure to the fractions/gymnopilene. Although there were no significant alterations in the production of reactive oxygen species, changes in mitochondrial dynamics were observed. Genotoxic assessment showed no significant changes. In vivo toxicity assessment showed no significant effects for G. junonius against the zebrafish embryos/larvae, whereas R. lilacinogilva remained toxic and induced developmental abnormalities over a 72-hour time period.The findings of this study highlight the potential of macrofungi as a valuable source of bioactive compounds, confirming the significance of natural products in drug discovery. Notably, this research represents the first to demonstrate that the predominant compound, gymnopilene, isolated from G. junonius exhibits inhibitory activity against M. tuberculosis, contributing to the novelty of the study. Furthermore, the study expands our understanding of the antimycobacterial properties of the selected macrofungal species, G. junonius and R. lilacinogilva, by demonstrating the ultrastructural damage to M. tuberculosis cell wall induced by treatment. However, it is important to recognise the potential toxicity identified through in vitro and/or in vivo screening assays. The observed toxicity may hamper their suitability formdrug development. Future investigations could explore the inclusion of additional in vitro based models, perhaps more complex and physiologically relevant models alongside the in vivo screening model to assess the therapeutic potential of isolated fractions/compounds. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Didloff, Jenske
- Date: 2024-12
- Subjects: Antibacterial agents , Plants, Useful -- South Africa , Medicinal plants -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68840 , vital:77122
- Description: Tuberculosis remains a significant public health challenge due to the complexity and compliance issues of its treatment, the prevalence of latent infections, the high rate of HIV co-infection, and the spread of drug-resistant strains. This highlights the need to search for new antimycobacterial drugs. Natural products have historically been used as sources for the discovery of pharmaceuticals. Although medicinal macrofungi have been exploited in traditional folk medicines for the treatment of various diseases, research into their antimycobacterial activity remains limited.The aim of this study was to isolate, identify, and characterise the antimycobacterial compound(s) present in ethanol fruiting body extracts of Gymnopilus junonius (Fr.) P.D. Orton (Hymenogastraceae) and Rhodofomitopsis lilacinogilva (Berk.) B.K. Cui, M.L. Han, & Y.C. Dai (Fomitopsidaceae), as well as to investigate their mechanism of action and potential toxicity using in vitro and in vivo screening methods.Bioassay-guided fractionation was conducted using column chromatography and preparative thin-layer chromatography to isolate the active antimycobacterial fraction/compound from ethanol extracts of G. junonius and R. lilacinogilva. Antimycobacterial activity against M. tuberculosis H37Rv was screened using a resazurin microplate assay (REMA). The chemical structure was elucidated employing 1D-(1H NMR) and 2D NMR spectroscopy (HSQC, HMBC) techniques, along with High- Performance Liquid Chromatography High-Resolution Electron Spray Ionisation Mass Spectrometry (HPLC-HRESI-MS). Transmission electron microscopy (TEM) was utilised to observe the ultrastructural changes in M. tuberculosis induced by the active fraction/compound. Toxicity assessment was performed on African green monkeykidney (Vero) and human hepatoma (C3A) cell lines using various staining techniques to observe the potential risk for hepatotoxicity (CellRox orange, TMRE, and MTG staining) and genotoxicity (NucRed staining). In vivo toxicity of extracts was evaluated using a zebrafish embryo/larvae model to observe developmental and teratogenic effects.The bioassay-guided fractionation of G. junonius and R. lilacinogilva extracts yielded an active compound and a fraction displaying inhibitory activity against M. tuberculosis, with MIC values of 31.25 μg/mL and 250 μg/mL, respectively. Gymnopilene was identified as the main active compound isolated from G. junonius, while fraction 8 from R. lilacinogilva contained a predominant constituent resembling a pachymic acid derivative. Transmission electron microscopy revealed ultrastructural damage to M. tuberculosis cells upon treatment with gymnopilene and fraction 8, which was observed as the disruption and disintegration of the cell wall. In vitro toxicity assessment indicated a reduction in the cell density in both Vero and C3A cell lines following exposure to the fractions/gymnopilene. Although there were no significant alterations in the production of reactive oxygen species, changes in mitochondrial dynamics were observed. Genotoxic assessment showed no significant changes. In vivo toxicity assessment showed no significant effects for G. junonius against the zebrafish embryos/larvae, whereas R. lilacinogilva remained toxic and induced developmental abnormalities over a 72-hour time period.The findings of this study highlight the potential of macrofungi as a valuable source of bioactive compounds, confirming the significance of natural products in drug discovery. Notably, this research represents the first to demonstrate that the predominant compound, gymnopilene, isolated from G. junonius exhibits inhibitory activity against M. tuberculosis, contributing to the novelty of the study. Furthermore, the study expands our understanding of the antimycobacterial properties of the selected macrofungal species, G. junonius and R. lilacinogilva, by demonstrating the ultrastructural damage to M. tuberculosis cell wall induced by treatment. However, it is important to recognise the potential toxicity identified through in vitro and/or in vivo screening assays. The observed toxicity may hamper their suitability formdrug development. Future investigations could explore the inclusion of additional in vitro based models, perhaps more complex and physiologically relevant models alongside the in vivo screening model to assess the therapeutic potential of isolated fractions/compounds. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Investigating the implementation of teaching strategies used by foundation phase teachers in multilingual classrooms
- Authors: Green, Marizanne
- Date: 2024-12
- Subjects: Multiculturalism -- Study and teaching , Language and languages -- Study and teaching , Education, Bilingual -- South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68322 , vital:76974
- Description: In South Africa, there are eleven official languages: English and Afrikaans and nine indigenous languages. However, the dominant language of learning and teaching in multilingual classrooms is English. Teachers are not all equipped to cater for a multilingual classroom that is conducive to learning. Hence, it is important that teaching strategies teachers used need to support learners’ access to knowledge and their language proficiency through the learning process. This qualitative case study aimed at investigating the teaching strategies used by Foundation Phase teachers in multilingual classrooms. The study was guided by an interpretivist paradigm which was helpful in providing in-depth knowledge on multilingual Foundation Phase classrooms and the teaching strategies that teachers implement. The study used a purposive sampling strategy with 4 Foundation phase teachers teaching Grades R-4. Drawing upon classroom observations and semi-structured individual interviews as the primary methods of data collection, the study explored the teaching strategies teachers use in multilingual foundation phase classrooms. A thematic data analysis was employed. Findings revealed a need for inclusive practices in FP multilingual classrooms, need to support learning using various teaching strategies, need to recognize realities in multilingual classrooms and a role that stakeholders can play in learning. Recommendations are provided for SGB’s, Curriculum designers, FP teachers and parents. , Thesis (MEd) -- Faculty of Education, School of Primary School Education, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Green, Marizanne
- Date: 2024-12
- Subjects: Multiculturalism -- Study and teaching , Language and languages -- Study and teaching , Education, Bilingual -- South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68322 , vital:76974
- Description: In South Africa, there are eleven official languages: English and Afrikaans and nine indigenous languages. However, the dominant language of learning and teaching in multilingual classrooms is English. Teachers are not all equipped to cater for a multilingual classroom that is conducive to learning. Hence, it is important that teaching strategies teachers used need to support learners’ access to knowledge and their language proficiency through the learning process. This qualitative case study aimed at investigating the teaching strategies used by Foundation Phase teachers in multilingual classrooms. The study was guided by an interpretivist paradigm which was helpful in providing in-depth knowledge on multilingual Foundation Phase classrooms and the teaching strategies that teachers implement. The study used a purposive sampling strategy with 4 Foundation phase teachers teaching Grades R-4. Drawing upon classroom observations and semi-structured individual interviews as the primary methods of data collection, the study explored the teaching strategies teachers use in multilingual foundation phase classrooms. A thematic data analysis was employed. Findings revealed a need for inclusive practices in FP multilingual classrooms, need to support learning using various teaching strategies, need to recognize realities in multilingual classrooms and a role that stakeholders can play in learning. Recommendations are provided for SGB’s, Curriculum designers, FP teachers and parents. , Thesis (MEd) -- Faculty of Education, School of Primary School Education, 2024
- Full Text:
- Date Issued: 2024-12
Investigation of potential in-situ polymerization reactions for use in lithium-ion batteries
- Authors: Dube, Tafara
- Date: 2024-12
- Subjects: Lithium ion batteries , Lithium cells , Electrochemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68851 , vital:77127
- Description: With the rise in popularity of electric vehicles and portable electronic devices, having a reliable, lightweight, and long-lasting battery is crucial. This has led to the mass commercialisation of lithium-ion batteries (LIB’s) because they offer several advantages over other battery technologies. Over the years, one of the concerns was with the ease with which the batteries can burn or explode when subjected to certain extreme conditions. In order to build trust in these products and to expand the technology into more diverse applications, safety aspects of the batteries has become of widespread concern resulting in a key area of research. One aspect of improving the safety is by reducing the flammability of the battery by the addition of certain chemicals that stop or suppress the thermal runaway effect. However, this in-turn reduces the battery’s capacity and life-cycle performance. Researchers have used the idea of encapsulating these chemicals thereby physically separating them within the lithium-ion battery (LIB) electrolyte system with a minimum effect on performance. This research aims to explore use of R-diols and R-amines as additives that upon a thermal trigger would react with the lithium-ion battery electrolyte to stop the effect of the thermal runaway by forming carbamate derivatives which are gel-like or form solid aggregates. The R-diols or R-amines can react with electrolyte at higher temperatures with the lithium-hexafluorophosphate acting as a catalyst. This change in the physical state of the electrolyte increases the resistance inside the battery which then hinders ion movement and forms a physical barrier to reduce the effect of short circuiting when the separator or other components are damaged due to higher temperatures. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Dube, Tafara
- Date: 2024-12
- Subjects: Lithium ion batteries , Lithium cells , Electrochemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68851 , vital:77127
- Description: With the rise in popularity of electric vehicles and portable electronic devices, having a reliable, lightweight, and long-lasting battery is crucial. This has led to the mass commercialisation of lithium-ion batteries (LIB’s) because they offer several advantages over other battery technologies. Over the years, one of the concerns was with the ease with which the batteries can burn or explode when subjected to certain extreme conditions. In order to build trust in these products and to expand the technology into more diverse applications, safety aspects of the batteries has become of widespread concern resulting in a key area of research. One aspect of improving the safety is by reducing the flammability of the battery by the addition of certain chemicals that stop or suppress the thermal runaway effect. However, this in-turn reduces the battery’s capacity and life-cycle performance. Researchers have used the idea of encapsulating these chemicals thereby physically separating them within the lithium-ion battery (LIB) electrolyte system with a minimum effect on performance. This research aims to explore use of R-diols and R-amines as additives that upon a thermal trigger would react with the lithium-ion battery electrolyte to stop the effect of the thermal runaway by forming carbamate derivatives which are gel-like or form solid aggregates. The R-diols or R-amines can react with electrolyte at higher temperatures with the lithium-hexafluorophosphate acting as a catalyst. This change in the physical state of the electrolyte increases the resistance inside the battery which then hinders ion movement and forms a physical barrier to reduce the effect of short circuiting when the separator or other components are damaged due to higher temperatures. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Low-income area electrification systems
- Authors: Tshabeni, Thulisa
- Date: 2024-12
- Subjects: Rural electrification -- Economic aspects -- South Africa , Rural electrification -- South Africa , Remote area power supply systems -- South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68807 , vital:77115
- Description: This research investigated electrification systems for low-income, informal settlement areas via grid extension, photovoltaic mini-grids and solar home system (SHS). Six electrification systems were analysed; four mini-grid systems, a 100 W solar home system and a grid extension. All have different maximum power capacities and differ in the way they contribute to sustainable development. Affordability for the consumer of the total energy required (electrical and other sources) is a key factor for the sustainability of any electrification system. Two battery technologies, lithium-ion and lead acid batteries were compared for each system based on technical and economic performance. The study determined that despite the intial very high cost, lithium-ion batteries can achieve a lower levelized cost of electricity (LCOE) due to their long life span. It was found that the batteries cost between 58% and 95% of the project’s capital cost. The battery cost occurs not only in the capital cost, but in the replacement cost. This cost is so high, that it makes all the solar systems uneconomic. This research found that extending the national power grid is still much more economically viable than all other PV electrification systems, but it requires land tenure. The issue of land tenure could be solved by making some agreement with the land owner for rental. It was found that the PV systems could only be economic if they increased the income of the communities substantially. , Thesis (MEg) -- Faculty of Engineering, the Built Environment, and Technology, School of Engineering, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Tshabeni, Thulisa
- Date: 2024-12
- Subjects: Rural electrification -- Economic aspects -- South Africa , Rural electrification -- South Africa , Remote area power supply systems -- South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68807 , vital:77115
- Description: This research investigated electrification systems for low-income, informal settlement areas via grid extension, photovoltaic mini-grids and solar home system (SHS). Six electrification systems were analysed; four mini-grid systems, a 100 W solar home system and a grid extension. All have different maximum power capacities and differ in the way they contribute to sustainable development. Affordability for the consumer of the total energy required (electrical and other sources) is a key factor for the sustainability of any electrification system. Two battery technologies, lithium-ion and lead acid batteries were compared for each system based on technical and economic performance. The study determined that despite the intial very high cost, lithium-ion batteries can achieve a lower levelized cost of electricity (LCOE) due to their long life span. It was found that the batteries cost between 58% and 95% of the project’s capital cost. The battery cost occurs not only in the capital cost, but in the replacement cost. This cost is so high, that it makes all the solar systems uneconomic. This research found that extending the national power grid is still much more economically viable than all other PV electrification systems, but it requires land tenure. The issue of land tenure could be solved by making some agreement with the land owner for rental. It was found that the PV systems could only be economic if they increased the income of the communities substantially. , Thesis (MEg) -- Faculty of Engineering, the Built Environment, and Technology, School of Engineering, 2024
- Full Text:
- Date Issued: 2024-12
Portfolio effect and bet-hedging adaptations in sea turtles
- Authors: Hoekstra, Shaun
- Date: 2024-12
- Subjects: Wildlife conservation , Sea turtles -- South Africa , Animal behavior
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68873 , vital:77153
- Description: A great proportion of marine species are at risk of going extinct as a result of profound changes in the world’s oceans, primarily driven by human activities. Sea turtles are not exempt from this fate. Despite sea turtles being exposed to a range of environmental conditions and threats that vary in frequency and intensity, these ancient marine reptiles have persisted for millennia. In the past, sea turtles have been able to adapt to natural perturbations while other animal groups have not. The ability of sea turtles to adapt to contemporary changes in conditions, produced by human activities, has become limited. The persistence of sea turtles may be explained by the application of a concept termed “portfolio effect”. An aggregate system is more stable and less prone to fluctuations over time (i.e. portfolio effect) if a diversity of finer components comprises the entire system and displays asynchronous fluctuations over time. Biological entities (e.g. species measured by the abundance trend) may achieve long-term stability even though the individual components (e.g. populations measured in abundance trend) display weak or negative correlations with each other in space and time. Different sea turtle populations may display independent trends in abundances over time, resulting in a portfolio effect at species levels. Trends in sea turtle abundances may be affected by individual behaviour. The adoption of bet-hedging adaptations may enable populations to thrive despite environmental changes or stochasticity, by lowering short-term fitness in exchange for maximising long-term fitness. Individual sea turtles may exhibit bet-hedging adaptations through changes in their temporal nesting behaviour, including the remigration interval. Since remigration interval length regulates the number of nesting females per nesting season, changes in remigration interval will affect abundance trends. The ability of individuals to change their remigration interval allows them to “skip” the breeding migration when environmental conditions seem unfavourable. The overall aim of this thesis was to investigate potential reasons for observed sea turtle abundance trends at species, population, and rookery levels. I tested whether the portfolio effect applies to sea turtles by analysing and interpreting spatiotemporal trends in loggerhead (Caretta caretta) and leatherback (Dermochelys coriacea) abundances at the population and species levels using global datasets. The application of bet-hedging strategies was tested at a local level using data from the long-term monitoring program for South African nesting sea turtles. The majority of loggerhead rookeries displayed an increase in abundance over time, while most leatherback rookeries declined (Chapter 2). Population growth rates also differed among rookeries within Regional Management Units (RMUs) (Chapter 2). This diversity in abundance trends among rookeries suggested spatiotemporal variation in environmental conditions, threats and/or level of protection accompanying sea turtles. The species-level growth rate for both species displayed an overall increase in abundance over time. However, larger (more turtles) leatherback rookeries/RMUs experienced more rapid declines in abundance compared to smaller rookeries/RMUs, resulting in a recent species-level decline. Uncorrelated trends in abundances at the RMU-level could have stabilised species-level trends. Differences in the remigration intervals as a possible bet-hedging adaptation could potentially explain differences in population recovery rates between South Africa’s loggerhead and leatherback sea turtles (Chapter 3), but found no evidence that individuals from either species exhibit bet-hedging adaptations. Loggerheads, however, have increased their remigration intervals over time, while leatherbacks have not. These increases were accompanied by declines in adult body size (previously established) which could be an effect of diminishing foraging area quality. The increased remigration interval shown by loggerheads may be a response rather than an adaptation to the prevailing environmental conditions that impact their food supply in their foraging areas. The population growth rate of leatherback sea turtles may surpass that of the loggerheads in the near future, although there is a global decline in abundance (Chapter 2). This dissertation provides information on possible reasons for observed trends in sea turtle abundances at various levels of biological organisation. While a variety of factors have the potential to influence trends in sea turtle abundance, the possible occurrence of portfolio effects and investigating nesting behaviour may resolve any uncertainties regarding the reasons for observed trends in abundance. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Hoekstra, Shaun
- Date: 2024-12
- Subjects: Wildlife conservation , Sea turtles -- South Africa , Animal behavior
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68873 , vital:77153
- Description: A great proportion of marine species are at risk of going extinct as a result of profound changes in the world’s oceans, primarily driven by human activities. Sea turtles are not exempt from this fate. Despite sea turtles being exposed to a range of environmental conditions and threats that vary in frequency and intensity, these ancient marine reptiles have persisted for millennia. In the past, sea turtles have been able to adapt to natural perturbations while other animal groups have not. The ability of sea turtles to adapt to contemporary changes in conditions, produced by human activities, has become limited. The persistence of sea turtles may be explained by the application of a concept termed “portfolio effect”. An aggregate system is more stable and less prone to fluctuations over time (i.e. portfolio effect) if a diversity of finer components comprises the entire system and displays asynchronous fluctuations over time. Biological entities (e.g. species measured by the abundance trend) may achieve long-term stability even though the individual components (e.g. populations measured in abundance trend) display weak or negative correlations with each other in space and time. Different sea turtle populations may display independent trends in abundances over time, resulting in a portfolio effect at species levels. Trends in sea turtle abundances may be affected by individual behaviour. The adoption of bet-hedging adaptations may enable populations to thrive despite environmental changes or stochasticity, by lowering short-term fitness in exchange for maximising long-term fitness. Individual sea turtles may exhibit bet-hedging adaptations through changes in their temporal nesting behaviour, including the remigration interval. Since remigration interval length regulates the number of nesting females per nesting season, changes in remigration interval will affect abundance trends. The ability of individuals to change their remigration interval allows them to “skip” the breeding migration when environmental conditions seem unfavourable. The overall aim of this thesis was to investigate potential reasons for observed sea turtle abundance trends at species, population, and rookery levels. I tested whether the portfolio effect applies to sea turtles by analysing and interpreting spatiotemporal trends in loggerhead (Caretta caretta) and leatherback (Dermochelys coriacea) abundances at the population and species levels using global datasets. The application of bet-hedging strategies was tested at a local level using data from the long-term monitoring program for South African nesting sea turtles. The majority of loggerhead rookeries displayed an increase in abundance over time, while most leatherback rookeries declined (Chapter 2). Population growth rates also differed among rookeries within Regional Management Units (RMUs) (Chapter 2). This diversity in abundance trends among rookeries suggested spatiotemporal variation in environmental conditions, threats and/or level of protection accompanying sea turtles. The species-level growth rate for both species displayed an overall increase in abundance over time. However, larger (more turtles) leatherback rookeries/RMUs experienced more rapid declines in abundance compared to smaller rookeries/RMUs, resulting in a recent species-level decline. Uncorrelated trends in abundances at the RMU-level could have stabilised species-level trends. Differences in the remigration intervals as a possible bet-hedging adaptation could potentially explain differences in population recovery rates between South Africa’s loggerhead and leatherback sea turtles (Chapter 3), but found no evidence that individuals from either species exhibit bet-hedging adaptations. Loggerheads, however, have increased their remigration intervals over time, while leatherbacks have not. These increases were accompanied by declines in adult body size (previously established) which could be an effect of diminishing foraging area quality. The increased remigration interval shown by loggerheads may be a response rather than an adaptation to the prevailing environmental conditions that impact their food supply in their foraging areas. The population growth rate of leatherback sea turtles may surpass that of the loggerheads in the near future, although there is a global decline in abundance (Chapter 2). This dissertation provides information on possible reasons for observed trends in sea turtle abundances at various levels of biological organisation. While a variety of factors have the potential to influence trends in sea turtle abundance, the possible occurrence of portfolio effects and investigating nesting behaviour may resolve any uncertainties regarding the reasons for observed trends in abundance. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Prevalence and correlates of sickness presenteeism among secondary school teachers in the Bukedi region of eastern Uganda
- Authors: Majwala,Henry
- Date: 2024-12
- Subjects: Employees -- Mental health , Psychology, Industrial , Industrial psychiatry
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68355 , vital:76989
- Description: Education is regarded as one of the main cornerstones for sustainable development, especially if the majority of the global citizenry manage to achieve it at secondary school level. The efficaciousness thereof, however, almost entirely depends on the productivity and performance of teachers meant to instill various skill sets among secondary school learners. Sickness presenteeism among secondary school teachers has previously emerged and gained attention as the single most important antagonist of secondary school productivity. However, it has been reported to be increasing in magnitude as absenteeism has gradually decreased over the years. The aim of the study was to establish the prevalence and correlates of sickness presenteeism among secondary school teachers in the Bukedi region in Eastern Uganda. The study adopted a pragmatic philosophy and a sequential explanatory mixed methods design targeting 433 secondary school teachers in the Bukedi sub region of Eastern Uganda. The schools were stratified by district first and then each district was stratified by ownership. Simple random sampling was used to sample half the number of schools per stratum, simple random sampling was used to sample the teachers. Key informants such as principals and teachers were purposively sampled and engaged in key informant semi-structured interviews. Quantitative data emerging from an analysis of the questionnaires was analyzed in SPSS version 25 using the log-binomial model, while the qualitative data from the semi-structured interviews was analyzed thematically. This study disclosed that the majority (68.3%) of the teachers engaged in sickness presenteeism. Moon lighting, egocentrism and heavy workload were the significant intrapersonal correlates of sickness presenteeism, while under staffing was a prominent institutional correlate. This study confirms findings from global research that staff working in people-based service sectors are most likely to engage in sickness presenteeism. The recommendations include the following: MoES to formulate a comprehensive policy on sickness presenteeism for teachers, DEOs to make follow ups to address the prevalent sickness presenteeism among secondary school teachers, the school administration to set up a special committee dealing with teachers’ welfare regarding ill health and work, and teachers are to be educated, sensitized about the dangers associated with sickness presenteeism and how to handle it with the school administration. , Thesis (DPhil) -- Faculty of Education, School of Post Schooling, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Majwala,Henry
- Date: 2024-12
- Subjects: Employees -- Mental health , Psychology, Industrial , Industrial psychiatry
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68355 , vital:76989
- Description: Education is regarded as one of the main cornerstones for sustainable development, especially if the majority of the global citizenry manage to achieve it at secondary school level. The efficaciousness thereof, however, almost entirely depends on the productivity and performance of teachers meant to instill various skill sets among secondary school learners. Sickness presenteeism among secondary school teachers has previously emerged and gained attention as the single most important antagonist of secondary school productivity. However, it has been reported to be increasing in magnitude as absenteeism has gradually decreased over the years. The aim of the study was to establish the prevalence and correlates of sickness presenteeism among secondary school teachers in the Bukedi region in Eastern Uganda. The study adopted a pragmatic philosophy and a sequential explanatory mixed methods design targeting 433 secondary school teachers in the Bukedi sub region of Eastern Uganda. The schools were stratified by district first and then each district was stratified by ownership. Simple random sampling was used to sample half the number of schools per stratum, simple random sampling was used to sample the teachers. Key informants such as principals and teachers were purposively sampled and engaged in key informant semi-structured interviews. Quantitative data emerging from an analysis of the questionnaires was analyzed in SPSS version 25 using the log-binomial model, while the qualitative data from the semi-structured interviews was analyzed thematically. This study disclosed that the majority (68.3%) of the teachers engaged in sickness presenteeism. Moon lighting, egocentrism and heavy workload were the significant intrapersonal correlates of sickness presenteeism, while under staffing was a prominent institutional correlate. This study confirms findings from global research that staff working in people-based service sectors are most likely to engage in sickness presenteeism. The recommendations include the following: MoES to formulate a comprehensive policy on sickness presenteeism for teachers, DEOs to make follow ups to address the prevalent sickness presenteeism among secondary school teachers, the school administration to set up a special committee dealing with teachers’ welfare regarding ill health and work, and teachers are to be educated, sensitized about the dangers associated with sickness presenteeism and how to handle it with the school administration. , Thesis (DPhil) -- Faculty of Education, School of Post Schooling, 2024
- Full Text:
- Date Issued: 2024-12
Screening drug candidates for sars-cov-2 spike protein variants within the SANCDB (South African Natural Compounds Database) and drug bank
- Authors: van der Merwe, Vicky
- Date: 2024-12
- Subjects: COVID-19 (Disease) , Vaccines -- Development , Viral vaccines
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69499 , vital:77263
- Description: The WHO declared the Coronavirus Infectious Disease 2019 (COVID-19) pandemic as over on the 5th of May 2023. However, the Severe Acute Respiratory Syndrome Coronavirus 2 Virus (SARS-CoV-2) is still prevalently spread within populations, causing hospitalization and death in serious infections. Most anti-COVID-19 agents are weakly or conditionally or even strongly recommended against in non-severe cases with low to medium risk of hospitalisation and further highlight the significance of effective treatments for SARS-CoV-2 infected patients. The host’s Angiotensin-Converting Enzyme 2 (ACE2) interaction with the viral spike protein’s Receptor-Binding Domain (RBD) of SARS-CoV-2 leads to the subsequent infection, viral replication, and further propagation of the virus. This establishes the spike protein’s RBD as a vital target for drug design. Through HADDOCK and AlphaFold driven structural refinement, the then novel SARS-CoV-2 delta [3.34 Å (PDB ID: 7WBQ)] and omicron [3.00 Å (PDB ID: 7WBP)] crystalline structures of the variants’ RBD, in complex with its host receptor human ACE2, were modelled to improve the low-resolution starting structures. Models predicted by HADDOCK independently yielded refined structures with improved resolutions of 2.49 Å (delta) and 2.41 Å (omicron). SARS-CoV-2 spike protein RBD of delta and omicron variants were screened for less frequently considered allosteric binding sites that could block ACE2-RBD engagement. Eight potential allosteric binding sites were identified through CavityPlus for both variants, with a single best druggable potential allosteric site identified for each. The search for potential inhibiting hit compounds involved using the SANCDB and DrugBank databanks and screening both the allosteric and orthosteric binding sites through molecular docking. Despite differences in mutated interacting residues and bond interactions, a lead compound for orthosteric binding sites (SANC00290) and potential allosteric modulators of both delta and omicron (SANC00746 and DB01029) were found. These compounds show promise in blocking ACE2-RBD engagement to potentially reduce viral interaction and infection of, and potentially withstanding further mutational residues. This study contributes to further investigation of affordable SA natural compound COVID-19 treatment and a starting point for in vitro analysis studies. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: van der Merwe, Vicky
- Date: 2024-12
- Subjects: COVID-19 (Disease) , Vaccines -- Development , Viral vaccines
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69499 , vital:77263
- Description: The WHO declared the Coronavirus Infectious Disease 2019 (COVID-19) pandemic as over on the 5th of May 2023. However, the Severe Acute Respiratory Syndrome Coronavirus 2 Virus (SARS-CoV-2) is still prevalently spread within populations, causing hospitalization and death in serious infections. Most anti-COVID-19 agents are weakly or conditionally or even strongly recommended against in non-severe cases with low to medium risk of hospitalisation and further highlight the significance of effective treatments for SARS-CoV-2 infected patients. The host’s Angiotensin-Converting Enzyme 2 (ACE2) interaction with the viral spike protein’s Receptor-Binding Domain (RBD) of SARS-CoV-2 leads to the subsequent infection, viral replication, and further propagation of the virus. This establishes the spike protein’s RBD as a vital target for drug design. Through HADDOCK and AlphaFold driven structural refinement, the then novel SARS-CoV-2 delta [3.34 Å (PDB ID: 7WBQ)] and omicron [3.00 Å (PDB ID: 7WBP)] crystalline structures of the variants’ RBD, in complex with its host receptor human ACE2, were modelled to improve the low-resolution starting structures. Models predicted by HADDOCK independently yielded refined structures with improved resolutions of 2.49 Å (delta) and 2.41 Å (omicron). SARS-CoV-2 spike protein RBD of delta and omicron variants were screened for less frequently considered allosteric binding sites that could block ACE2-RBD engagement. Eight potential allosteric binding sites were identified through CavityPlus for both variants, with a single best druggable potential allosteric site identified for each. The search for potential inhibiting hit compounds involved using the SANCDB and DrugBank databanks and screening both the allosteric and orthosteric binding sites through molecular docking. Despite differences in mutated interacting residues and bond interactions, a lead compound for orthosteric binding sites (SANC00290) and potential allosteric modulators of both delta and omicron (SANC00746 and DB01029) were found. These compounds show promise in blocking ACE2-RBD engagement to potentially reduce viral interaction and infection of, and potentially withstanding further mutational residues. This study contributes to further investigation of affordable SA natural compound COVID-19 treatment and a starting point for in vitro analysis studies. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Social dynamics of spotted hyaenas (Crocuta crocuta) in fenced protected areas: Implications for conservation management of a socially intelligent species
- Authors: Honiball, Terry-Lee
- Date: 2024-12
- Subjects: Spotted hyena -- Behavior -- South Africa , Wildlife conservation -- South Africa , Wildlife management -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68884 , vital:77159
- Description: It is important to understand the impact of fenced protected area management on the behaviour and fitness of less popular species, such as the spotted hyeana (Crocuta crocuta), that have been historically overlooked in species management across protected areas. As a result of this oversight, hyaena population densities have reached high levels, making it critical to study the effects of fenced protected area management on these species. There is a lack of understanding of how species adapt to the potentially high-pressure systems (through the restriction of resources spatially) created by fenced protected areas and the intrinsic effects that management regimes may have on wildlife. Due to the spotted hyaena’s high behavioural plasticity, they make excellent candidates to explore the effects of management regimes in fenced protected areas while enhancing our understanding of spotted hyaena ecology. Therefore, the aim of this study was to explore the ecology and social behaviour of high density spotted hyaena populations in fenced protected areas to understand the effects of different management regimes and how spotted hyaenas respond to these differing pressures. This was achieved through four main objectives which consider different aspects of spotted hyaena ecology and the influence of management regimes and environmental variables in two fenced protected areas in South Africa; Madikwe Game Reserve (a socio-economically incentivised reserve) and Addo Elephant National Park (a reserve incentivised by the promotion of biodiversity), between 2021 and 2023. This study explored 1) range residency patterns and third order habitat selection in spotted hyaena movement, 2) interspecific interactions at shared food sources to understand the role of lion, Panthera leo, and spotted hyaenas dynamics in top-down pressure in carnivore structure, 3) territorial interactions when defending resources to understand spotted hyaena social dominance when occurring at high densities, 4) welfare considerations and allostatic load of spotted hyaenas, and additionally we provided insight into the social hierarchy disruptions which occur when removing the matriarch from a clan through an opportunistic record. By assessing the effects of socio-economic or biodiversity driven management regimes, this study provided novel accounts of social behaviour and responses of spotted hyaenas to pressures in fenced protected areas, highlighting the top-down pressure that lions have on multiple aspects of spotted hyaena functioning. Road networks and infrastructure in fenced protected areas were generally utilised by spotted hyaenas and despite high abundance, prey availability remained an important aspect of spotted hyaena ecology regardless of management regimes. Further, we showed that when food is abundant, spotted hyaenas are tolerant of subordinate carnivores, which emphasises their dynamic behavioural plasticity. We showed that spotted hyaenas gauge territorial responses according to the perceived threat and are less tolerant to familiar intruders than to unfamiliar individuals, which is an important inbreeding avoidance tactic that remains in place in fenced protected areas. And lastly, we showed that management regimes influence the adrenal function of spotted hyaenas, where fenced protected areas incentivised by wildlife photographic tourism may negatively affect species fitness through elevated epidandrosterone levels over time. However, spotted hyaenas appear to have adapted to elevated hormone levels, thus not affecting fecundity in fenced protected areas, resulting in high density populations. This study provides a holistic overview of the effects of management regimes on spotted hyaenas in fenced protected areas and provides insights into how spotted hyaenas adapt to pressures when occurring at high densities in these areas. This study contributes to the understanding of spotted hyaena ecology and the intrinsic effects on wildlife of different approaches to management regimes in fenced protected areas. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Honiball, Terry-Lee
- Date: 2024-12
- Subjects: Spotted hyena -- Behavior -- South Africa , Wildlife conservation -- South Africa , Wildlife management -- South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/68884 , vital:77159
- Description: It is important to understand the impact of fenced protected area management on the behaviour and fitness of less popular species, such as the spotted hyeana (Crocuta crocuta), that have been historically overlooked in species management across protected areas. As a result of this oversight, hyaena population densities have reached high levels, making it critical to study the effects of fenced protected area management on these species. There is a lack of understanding of how species adapt to the potentially high-pressure systems (through the restriction of resources spatially) created by fenced protected areas and the intrinsic effects that management regimes may have on wildlife. Due to the spotted hyaena’s high behavioural plasticity, they make excellent candidates to explore the effects of management regimes in fenced protected areas while enhancing our understanding of spotted hyaena ecology. Therefore, the aim of this study was to explore the ecology and social behaviour of high density spotted hyaena populations in fenced protected areas to understand the effects of different management regimes and how spotted hyaenas respond to these differing pressures. This was achieved through four main objectives which consider different aspects of spotted hyaena ecology and the influence of management regimes and environmental variables in two fenced protected areas in South Africa; Madikwe Game Reserve (a socio-economically incentivised reserve) and Addo Elephant National Park (a reserve incentivised by the promotion of biodiversity), between 2021 and 2023. This study explored 1) range residency patterns and third order habitat selection in spotted hyaena movement, 2) interspecific interactions at shared food sources to understand the role of lion, Panthera leo, and spotted hyaenas dynamics in top-down pressure in carnivore structure, 3) territorial interactions when defending resources to understand spotted hyaena social dominance when occurring at high densities, 4) welfare considerations and allostatic load of spotted hyaenas, and additionally we provided insight into the social hierarchy disruptions which occur when removing the matriarch from a clan through an opportunistic record. By assessing the effects of socio-economic or biodiversity driven management regimes, this study provided novel accounts of social behaviour and responses of spotted hyaenas to pressures in fenced protected areas, highlighting the top-down pressure that lions have on multiple aspects of spotted hyaena functioning. Road networks and infrastructure in fenced protected areas were generally utilised by spotted hyaenas and despite high abundance, prey availability remained an important aspect of spotted hyaena ecology regardless of management regimes. Further, we showed that when food is abundant, spotted hyaenas are tolerant of subordinate carnivores, which emphasises their dynamic behavioural plasticity. We showed that spotted hyaenas gauge territorial responses according to the perceived threat and are less tolerant to familiar intruders than to unfamiliar individuals, which is an important inbreeding avoidance tactic that remains in place in fenced protected areas. And lastly, we showed that management regimes influence the adrenal function of spotted hyaenas, where fenced protected areas incentivised by wildlife photographic tourism may negatively affect species fitness through elevated epidandrosterone levels over time. However, spotted hyaenas appear to have adapted to elevated hormone levels, thus not affecting fecundity in fenced protected areas, resulting in high density populations. This study provides a holistic overview of the effects of management regimes on spotted hyaenas in fenced protected areas and provides insights into how spotted hyaenas adapt to pressures when occurring at high densities in these areas. This study contributes to the understanding of spotted hyaena ecology and the intrinsic effects on wildlife of different approaches to management regimes in fenced protected areas. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Solution of some cross-diffusion equations in biosciences using finite difference methods and artificial neural networks
- Authors: de Waal, Gysbert Nicolaas
- Date: 2024-12
- Subjects: Mathematics , Difference equations , Functional equations
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68829 , vital:77121
- Description: In this dissertation, three cross-diffusion models which require positivity-preserving solutions are solved using standard and nonstandard finite difference methods and physics-informed neural networks. The three models are a basic reaction-diffusion-chemotaxis model, a convective predator-prey pursuit and evasion model, and a two-dimensional Keller-Segel chemotaxis model. All three models involve systems of nonlinear coupled partial differential equations subject to some specified initial and boundary conditions for which no exact solution is known. It is not possible to obtain the stability region of the standard finite difference methods for the three models theoretically and therefore a range of values of temporal step size at a given spatial step size for reasonable solutions is obtained by running some numerical experiments. It is observed that the standard finite difference schemes are not always positivity-preserving, and this is why nonstandard finite difference schemes are necessary. Chapter 1 provides some background detail on partial differential equations, cross-diffusion equations, finite difference methods, and artificial neural networks. In Chapter 2, the cross-diffusion models considered in this dissertation are provided, namely a basic reaction-diffusion–chemotaxis model for two cases, a convective predator-prey pursuit and evasion model, and a two-dimensional Keller-Segel chemotaxis model for two cases. In Chapter 3, the basic reaction-diffusion–chemotaxis model is solved for the two cases using some standard and nonstandard finite difference schemes. It is determined that the standard methods give reasonable positivity-preserving numerical solutions if the temporal step size, 𝑘, is chosen such that 𝑘 ≤ 0.25 with the spatial step size, ℎ, fixed at ℎ = 1.0. Two nonstandard finite difference methods abbreviated as NSFD1 and NSFD2 are considered from Chapwanya et al. (2014). It is shown that NSFD1 preserves the positivity of the continuous model if the following criteria are satisfied: 𝜙(𝑘)[𝜓(ℎ)]2=12𝛾≤12𝜎+𝛽 and 𝛽≤𝜎. NSFD1 is modified to obtain NSFD2, which is positivity-preserving if 𝑅=𝜙(𝑘)[𝜓(ℎ)]2=12𝛾 and 2𝜎𝑅≤1, that is, 𝜎≤𝛾. In this work, it is shown that NSFD2 does not always achieve consistency, and it is proven that consistency can be achieved if 𝛽→0 and 𝑘ℎ2→0. Lastly, it is demonstrated that the numerical rate of convergence in time of the finite difference methods is approximately one for case 2 of the chemotaxis model. In Chapter 4, one standard and two nonstandard finite difference methods are constructed to solve the convective predator-prey model. Through some numerical experiments, it is observed that reasonable , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: de Waal, Gysbert Nicolaas
- Date: 2024-12
- Subjects: Mathematics , Difference equations , Functional equations
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68829 , vital:77121
- Description: In this dissertation, three cross-diffusion models which require positivity-preserving solutions are solved using standard and nonstandard finite difference methods and physics-informed neural networks. The three models are a basic reaction-diffusion-chemotaxis model, a convective predator-prey pursuit and evasion model, and a two-dimensional Keller-Segel chemotaxis model. All three models involve systems of nonlinear coupled partial differential equations subject to some specified initial and boundary conditions for which no exact solution is known. It is not possible to obtain the stability region of the standard finite difference methods for the three models theoretically and therefore a range of values of temporal step size at a given spatial step size for reasonable solutions is obtained by running some numerical experiments. It is observed that the standard finite difference schemes are not always positivity-preserving, and this is why nonstandard finite difference schemes are necessary. Chapter 1 provides some background detail on partial differential equations, cross-diffusion equations, finite difference methods, and artificial neural networks. In Chapter 2, the cross-diffusion models considered in this dissertation are provided, namely a basic reaction-diffusion–chemotaxis model for two cases, a convective predator-prey pursuit and evasion model, and a two-dimensional Keller-Segel chemotaxis model for two cases. In Chapter 3, the basic reaction-diffusion–chemotaxis model is solved for the two cases using some standard and nonstandard finite difference schemes. It is determined that the standard methods give reasonable positivity-preserving numerical solutions if the temporal step size, 𝑘, is chosen such that 𝑘 ≤ 0.25 with the spatial step size, ℎ, fixed at ℎ = 1.0. Two nonstandard finite difference methods abbreviated as NSFD1 and NSFD2 are considered from Chapwanya et al. (2014). It is shown that NSFD1 preserves the positivity of the continuous model if the following criteria are satisfied: 𝜙(𝑘)[𝜓(ℎ)]2=12𝛾≤12𝜎+𝛽 and 𝛽≤𝜎. NSFD1 is modified to obtain NSFD2, which is positivity-preserving if 𝑅=𝜙(𝑘)[𝜓(ℎ)]2=12𝛾 and 2𝜎𝑅≤1, that is, 𝜎≤𝛾. In this work, it is shown that NSFD2 does not always achieve consistency, and it is proven that consistency can be achieved if 𝛽→0 and 𝑘ℎ2→0. Lastly, it is demonstrated that the numerical rate of convergence in time of the finite difference methods is approximately one for case 2 of the chemotaxis model. In Chapter 4, one standard and two nonstandard finite difference methods are constructed to solve the convective predator-prey model. Through some numerical experiments, it is observed that reasonable , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-12
Student teacher's experiences of teaching mathematics using isiXhosa in foundation phase classrooms during teaching practice
- Bangiso, Innocentia Queen Zintle
- Authors: Bangiso, Innocentia Queen Zintle
- Date: 2024-12
- Subjects: Mathematics -- Study and teaching , Native language and education -- Africa , African languages -- Study and teaching
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68297 , vital:76972
- Description: In South Africa, learning in the Foundation Phase happens in a child’s home language, thus all eleven official languages, nine of them being African languages, must and are used as languages of teaching and learning in this phase. Teacher training, however, does not happen in all eleven official languages. The dominant language of training teachers across the country is English, even in classroom contexts where the language of learning and teaching may be an African language. This raises concerns about whether student teachers trained in English can translate mathematics content knowledge into an African language. This is particularly concerning given the country’s consistent underperformance in mathematics and literacy. Against this backdrop, this qualitative study aimed to explore Foundation Phase student teachers’ perspectives on their experiences of teaching mathematics using isiXhosa during teaching practice. The question that this study sought to answer was: what are student teachers’ perspectives on their experiences of teaching mathematics in isiXhosa during teaching practice? Drawing upon classroom observations and semi-structured individual interviews as the primary methods of data collection, the study explored the mediation of mathematics learning using isiXhosa, the pedagogical challenges encountered by student teachers, the strategies employed to address these challenges, and the influence of university training on their preparation. Findings reveal a significant discrepancy between the language of instruction used in university training which is English, and the language required for teaching practice which is isiXhosa. Student teachers expressed struggles in translating theoretical knowledge into practical application, leading to diminished confidence and pedagogical inefficacy. However, participants also demonstrated resilience through innovative strategies such as code-switching, visual aids, and collaborative learning approaches. The study highlights the urgent need for comprehensive language support and pedagogical training programmes to bridge the gap between theory and practice in isiXhosa-medium mathematics instruction. Recommendations are provided for educational institutions, especially the case study university, to enhance the preparation of student teachers and promote effective mathematics education in multilingual contexts. , Thesis (MEd) -- Faculty of Education, School of Primary School Education: Foundation Phase, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Bangiso, Innocentia Queen Zintle
- Date: 2024-12
- Subjects: Mathematics -- Study and teaching , Native language and education -- Africa , African languages -- Study and teaching
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/68297 , vital:76972
- Description: In South Africa, learning in the Foundation Phase happens in a child’s home language, thus all eleven official languages, nine of them being African languages, must and are used as languages of teaching and learning in this phase. Teacher training, however, does not happen in all eleven official languages. The dominant language of training teachers across the country is English, even in classroom contexts where the language of learning and teaching may be an African language. This raises concerns about whether student teachers trained in English can translate mathematics content knowledge into an African language. This is particularly concerning given the country’s consistent underperformance in mathematics and literacy. Against this backdrop, this qualitative study aimed to explore Foundation Phase student teachers’ perspectives on their experiences of teaching mathematics using isiXhosa during teaching practice. The question that this study sought to answer was: what are student teachers’ perspectives on their experiences of teaching mathematics in isiXhosa during teaching practice? Drawing upon classroom observations and semi-structured individual interviews as the primary methods of data collection, the study explored the mediation of mathematics learning using isiXhosa, the pedagogical challenges encountered by student teachers, the strategies employed to address these challenges, and the influence of university training on their preparation. Findings reveal a significant discrepancy between the language of instruction used in university training which is English, and the language required for teaching practice which is isiXhosa. Student teachers expressed struggles in translating theoretical knowledge into practical application, leading to diminished confidence and pedagogical inefficacy. However, participants also demonstrated resilience through innovative strategies such as code-switching, visual aids, and collaborative learning approaches. The study highlights the urgent need for comprehensive language support and pedagogical training programmes to bridge the gap between theory and practice in isiXhosa-medium mathematics instruction. Recommendations are provided for educational institutions, especially the case study university, to enhance the preparation of student teachers and promote effective mathematics education in multilingual contexts. , Thesis (MEd) -- Faculty of Education, School of Primary School Education: Foundation Phase, 2024
- Full Text:
- Date Issued: 2024-12
Studies on soil acidity management strategies for sustainable agriculture
- Authors: Swart, Nicolas
- Date: 2024-12
- Subjects: Soil acidity , Soil fertility , Sustainable agriculture
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69475 , vital:77260
- Description: Soil acidity is a widespread problem which reduces plant growth and yield. There are calls for alternative crop and soil management strategies that can be used by farmers to deal with soil acidification in a sustainable manner. Current literature suggests that the benefits of sustainable soil management systems on soil acidity are highly variable, and within the context of conservation agriculture (CA), farmers need recommendations for techniques to improve liming efficiency. Such techniques include acid resistant cultivars and soil amendments such as biochar. However, dedicated scientific research is still needed to increase our understanding of the benefits of integrating various sustainable agriculture approaches on reducing the acidity on cropped lands. A series of experiments were thus conducted to test whether the integration of reduced lime dosages with organic amendments such as biochar, along with acid resistant wheat cultivars could improve nutrient availability and reduce the harms of acidity on plant roots. It was hypothesised that if lower than recommended doses of lime are applied in combination with biochar and acid resistant cultivars, there will be significant improvement of nutrient availability, soil acidity amelioration benefits and crop growth. The first experiment was a 60–day incubation trial to examine the interaction effects of reduced lime application rates and black wattle (Acacia mearnsii) biochar on the acidity and plant nutrient availability of a sandy clay loam, acidic podzolic soil. The changes in pH water (pHw) across treatments were monitored at 10-day intervals over the incubation period. Additionally, the initial and final status of each treatment in terms of essential macro-and micronutrients, pH(KCl), extractable aluminium (ext Al), exchangeable acidity (EA) and acid saturation (AS) were also measured. The second experiment examined the genotype × biochar × lime interaction effects on wheat plant root growth in the acid soil. Soil incubation results showed that the interaction effect of lime rate and biochar was not significant (p>0.05) for any of the tested soil nutrient availability and soil acidity parameters, except for pHw. However, lime rate effects were significant (p<0.05) on AS, EA, pH(KCl) and ext Al. As lime rate increased, the acidity decreased. Increasing the lime application rate significantly (p<0.05) enhanced the cation exchange capacity (CEC), calcium (Ca), magnesium (Mg) and phosphorous (P), but decreased potassium (K) and sulphur (S). The availability of micro-nutrients namely copper (Cu), iron (Fe), manganese (Mn) and zinc (Zn) also decreased as the lime rate increased. Biochar effects on EA, AS, pH(KCl) and ext Al were not significant (p>0.05). However, the biochar significantly reduced the availability of Ca and Mn but did not have a significant effecton all the other nutrients at the tested application rates. Unenriched biochar at 10 t ha-1 had an acidifying effect on the soil as it increased EA, when compared to enriched biochar. The significant (p <0.05) biochar × lime × time interaction effect on pHw showed that biochar applied without lime increased pHw, and the benefits were greatest at 10 t ha-1 biochar application rate. Similarly, lime applied without biochar also had a significant positive effect on pHw and the benefit increased at higher lime application rates. After 60 days of incubation, the lime applied at the highest rate of 5 t ha-1 without biochar (0 t ha-1 biochar) had the highest final pHw value. The 3-way interaction of lime, biochar and genotype was not significant (p>0.05). Koonap, the acid tolerant wheat variety outperformed the sensitive variety, Gariep under all treatments in the acid soil, as expected. There was, however, a significant (p<0.05) lime rate × biochar interaction. The highest application rates of lime (5 t ha-1) and biochar (10 t ha-1) were the best combination for root length for both the varieties. Overall, these results suggested a possible buffering effect of biochar at low lime application rates, thus limited benefits of combining reduced lime doses with biochar on reducing soil acidity or enhancing nutrient availability. The null hypothesis was thus rejected, and it was concluded that co-application of reduced lime rates and biochar will not significantly enhance benefits of liming. However, a positive interaction from co-application of biochar and lime on both pH and plant growth is possible at high application rates of both biochar and lime. , Thesis (MSc) -- Faculty of Science, School of Natural Resource Science and Management, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Swart, Nicolas
- Date: 2024-12
- Subjects: Soil acidity , Soil fertility , Sustainable agriculture
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69475 , vital:77260
- Description: Soil acidity is a widespread problem which reduces plant growth and yield. There are calls for alternative crop and soil management strategies that can be used by farmers to deal with soil acidification in a sustainable manner. Current literature suggests that the benefits of sustainable soil management systems on soil acidity are highly variable, and within the context of conservation agriculture (CA), farmers need recommendations for techniques to improve liming efficiency. Such techniques include acid resistant cultivars and soil amendments such as biochar. However, dedicated scientific research is still needed to increase our understanding of the benefits of integrating various sustainable agriculture approaches on reducing the acidity on cropped lands. A series of experiments were thus conducted to test whether the integration of reduced lime dosages with organic amendments such as biochar, along with acid resistant wheat cultivars could improve nutrient availability and reduce the harms of acidity on plant roots. It was hypothesised that if lower than recommended doses of lime are applied in combination with biochar and acid resistant cultivars, there will be significant improvement of nutrient availability, soil acidity amelioration benefits and crop growth. The first experiment was a 60–day incubation trial to examine the interaction effects of reduced lime application rates and black wattle (Acacia mearnsii) biochar on the acidity and plant nutrient availability of a sandy clay loam, acidic podzolic soil. The changes in pH water (pHw) across treatments were monitored at 10-day intervals over the incubation period. Additionally, the initial and final status of each treatment in terms of essential macro-and micronutrients, pH(KCl), extractable aluminium (ext Al), exchangeable acidity (EA) and acid saturation (AS) were also measured. The second experiment examined the genotype × biochar × lime interaction effects on wheat plant root growth in the acid soil. Soil incubation results showed that the interaction effect of lime rate and biochar was not significant (p>0.05) for any of the tested soil nutrient availability and soil acidity parameters, except for pHw. However, lime rate effects were significant (p<0.05) on AS, EA, pH(KCl) and ext Al. As lime rate increased, the acidity decreased. Increasing the lime application rate significantly (p<0.05) enhanced the cation exchange capacity (CEC), calcium (Ca), magnesium (Mg) and phosphorous (P), but decreased potassium (K) and sulphur (S). The availability of micro-nutrients namely copper (Cu), iron (Fe), manganese (Mn) and zinc (Zn) also decreased as the lime rate increased. Biochar effects on EA, AS, pH(KCl) and ext Al were not significant (p>0.05). However, the biochar significantly reduced the availability of Ca and Mn but did not have a significant effecton all the other nutrients at the tested application rates. Unenriched biochar at 10 t ha-1 had an acidifying effect on the soil as it increased EA, when compared to enriched biochar. The significant (p <0.05) biochar × lime × time interaction effect on pHw showed that biochar applied without lime increased pHw, and the benefits were greatest at 10 t ha-1 biochar application rate. Similarly, lime applied without biochar also had a significant positive effect on pHw and the benefit increased at higher lime application rates. After 60 days of incubation, the lime applied at the highest rate of 5 t ha-1 without biochar (0 t ha-1 biochar) had the highest final pHw value. The 3-way interaction of lime, biochar and genotype was not significant (p>0.05). Koonap, the acid tolerant wheat variety outperformed the sensitive variety, Gariep under all treatments in the acid soil, as expected. There was, however, a significant (p<0.05) lime rate × biochar interaction. The highest application rates of lime (5 t ha-1) and biochar (10 t ha-1) were the best combination for root length for both the varieties. Overall, these results suggested a possible buffering effect of biochar at low lime application rates, thus limited benefits of combining reduced lime doses with biochar on reducing soil acidity or enhancing nutrient availability. The null hypothesis was thus rejected, and it was concluded that co-application of reduced lime rates and biochar will not significantly enhance benefits of liming. However, a positive interaction from co-application of biochar and lime on both pH and plant growth is possible at high application rates of both biochar and lime. , Thesis (MSc) -- Faculty of Science, School of Natural Resource Science and Management, 2024
- Full Text:
- Date Issued: 2024-12
Supramolecular chemistry considerations of fluorenyl-derived host compounds
- Authors: McFarlane, Duncan William
- Date: 2024-12
- Subjects: Supramolecular chemistry , Organic compounds , Chemistry, Organic
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69371 , vital:77227
- Description: This work examined various supramolecular aspects of 9-fluorenone-derived host compounds, namely 4,4’-(9-fluorenylidene)diphenol (H1), 9,9-(1,4-phenylene)bis(fluoren-9-ol) (H2), 9,9- (ethyne-1,2-diyl)bis(fluoren-9-ol) (H3) and 9,9-(biphenyl-4,4-diyl)bis(fluoren-9-ol) (H4). These compounds were successfully synthesized and then screened for their host ability for, and host behaviour in, various organic compounds. At the outset, molecular modelling calculations were carried out on each of the four host compounds. Various structural parameters and the geometries of the low energy conformers that were calculated were then compared with these aspects of the guest-free host molecules obtained from single crystal X-ray diffraction (SCXRD) analysis. The host behaviour of H1 was, furthermore, assessed in the presence of four alkylnitriles, namely acetonitrile (ACE), acrylonitrile (ACRY), propionitrile (PROP) and butyronitrile (BUT). All four guests complexed with H1 with 1:1 host:guest (H:G) ratios. From SCXRD analyses, each of the complexes crystallized in the monoclinic crystal system and the centrosymmetric space group P21/n, and the host packing was isostructural in each instance. The complexes were stabilized by a plethora of short inter- and intramolecular contacts. The thermal stabilities of the four complexes were also examined together with Hirshfeld surface considerations. Finally, lattice energy calculations were carried out and the results of these compared with the relative thermal stabilities of the four complexes. The compounds H2 and H3 were examined for their selectivity behaviour in mixtures of aniline, N-methylaniline and N,N’-dimethylaniline (ANI, NMA and DMA). Both host compounds were able to form complexes with ANI and DMA with various H:G ratios, while only H3 possessed enclathration ability for NMA (H:G 1:1). SCXRD analyses showed that all of the complexes were stabilized by means of classical (host)O‒H···N(guest) hydrogen bonds in addition to other short contacts. Equimolar binary guest competition experiments with H2 revealed an extremely high host selectivity for DMA (ANI/DMA and DMA/NMA experiments furnished crystals with > 91% DMA), while the experiment with all three anilines present also resulted in a complex with an , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: McFarlane, Duncan William
- Date: 2024-12
- Subjects: Supramolecular chemistry , Organic compounds , Chemistry, Organic
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69371 , vital:77227
- Description: This work examined various supramolecular aspects of 9-fluorenone-derived host compounds, namely 4,4’-(9-fluorenylidene)diphenol (H1), 9,9-(1,4-phenylene)bis(fluoren-9-ol) (H2), 9,9- (ethyne-1,2-diyl)bis(fluoren-9-ol) (H3) and 9,9-(biphenyl-4,4-diyl)bis(fluoren-9-ol) (H4). These compounds were successfully synthesized and then screened for their host ability for, and host behaviour in, various organic compounds. At the outset, molecular modelling calculations were carried out on each of the four host compounds. Various structural parameters and the geometries of the low energy conformers that were calculated were then compared with these aspects of the guest-free host molecules obtained from single crystal X-ray diffraction (SCXRD) analysis. The host behaviour of H1 was, furthermore, assessed in the presence of four alkylnitriles, namely acetonitrile (ACE), acrylonitrile (ACRY), propionitrile (PROP) and butyronitrile (BUT). All four guests complexed with H1 with 1:1 host:guest (H:G) ratios. From SCXRD analyses, each of the complexes crystallized in the monoclinic crystal system and the centrosymmetric space group P21/n, and the host packing was isostructural in each instance. The complexes were stabilized by a plethora of short inter- and intramolecular contacts. The thermal stabilities of the four complexes were also examined together with Hirshfeld surface considerations. Finally, lattice energy calculations were carried out and the results of these compared with the relative thermal stabilities of the four complexes. The compounds H2 and H3 were examined for their selectivity behaviour in mixtures of aniline, N-methylaniline and N,N’-dimethylaniline (ANI, NMA and DMA). Both host compounds were able to form complexes with ANI and DMA with various H:G ratios, while only H3 possessed enclathration ability for NMA (H:G 1:1). SCXRD analyses showed that all of the complexes were stabilized by means of classical (host)O‒H···N(guest) hydrogen bonds in addition to other short contacts. Equimolar binary guest competition experiments with H2 revealed an extremely high host selectivity for DMA (ANI/DMA and DMA/NMA experiments furnished crystals with > 91% DMA), while the experiment with all three anilines present also resulted in a complex with an , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Synthesis of two tartaric acid-derived host compounds and their behaviour in mixed pyridines and mixed heterocyclic guest compounds
- Authors: Recchia, Daniella Loridana
- Date: 2024-12
- Subjects: Compounds -- guest/host , Chemistry, Organic , Chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69441 , vital:77256
- Description: The host compounds (4R,5R)-bis(diphenylhydroxymethyl)-2-spiro-1’-cyclopentane-1,3-dioxolane (TADDOL5) and (4R,5R)-bis(diphenylhydroxymethyl)-2-spiro-1’-cyclohexane-1,3-dioxolane (TADDOL6) were successfully synthesized after initially reacting diethyl tartrate with either 1,1-dimethoxycyclopentane or 1,1-dimethoxycyclohexane to afford the intermediates diethyl 2-spiro-1’-cyclopentane-1,3-dioxolan-4,5-dicarboxylate or diethyl 2-spiro-1’-cyclohexane-1,3-dioxolan-4,5-dicarboxylate. These were then each subjected to a Grignard addition reaction with PhMgBr to furnish TADDOL5 and TADDOL6 in reasonably high yields (77 and 80%, respectively). Computational calculations were performed on TADDOL5 and TADDOL6 using the software programs Avogadro and ORCA. The optimised geometries of these host molecules were obtained using the MMFF94 force field in Avogadro, while ORCA was used to perform the computational modelling at the BLYP level using the 6-31G*, 6-31G**, 6-311G* and 6-311G** basis sets and, also, the B3LYP functional (with the same basis sets) to obtain the three lowest energy conformers. The final geometries of each conformer for both TADDOL5 and TADDOL6 at the B3LYP 6-311G* level were overlaid with the molecules obtained from their crystal structures. Significantly different geometries were thus noted for the calculated conformers compared with the guest-free TADDOL5 and TADDOL6 structures obtained from the SCXRD experiments. When TADDOL5 was crystallized independently from each of PYR, 2MP, 3MP and 4MP, 1:1 H:G inclusion complexes formed in each instance. This host compound was then investigated for its host separation ability of mixed pyridines through supramolecular chemistry protocols. These mixed guest experiments revealed that TADDOL5 possessed a notable selectivity towards 3MP and PYR (in the absence of 3MP) followed by 4MP and 2MP, and it was shown that TADDOL5 is a suitable host candidate for the separation of many of the mixed pyridines employed here. The results of the SCXRD analyses indicated that the only significant (host)π···π(guest) stacking interaction present was between TADDOL5 and the most favoured guest species PYR and 3MP. Furthermore, significantly shorter (host)O‒H···N(guest) hydrogen bonds were also observed in the complexes formed between this host compound and 3MP and PYR compared with these bonds involving disfavoured 4MP and 2MP. Hirshfeld surface considerations provided an explanation for the affinity of TADDOL5 for PYR (but not 3MP), while thermal analyses successfully explained this affinity: the 3MP-containing complex with the most preferred guest species was the most thermally stable one, followed by TADDOL5·PYR, as obtained through a consideration of the Ton values (the temperature at which the guest release event initiated) of the four complexes. As with TADDOL5, TADDOL6 formed 1:1 H:G inclusion compounds with each of the four pyridines. TADDOL6 was, furthermore, also assessed for its separation ability for mixed pyridines, and these guest competition experiments showed that the selectivity of TADDOL6 was for PYR and 3MP (in the absence of PYR), followed by 4MP and 2MP. (Interestingly, TADDOL5 preferred 3MP and then PYR, while both host compounds disfavoured 4MP and 2MP.) The results obtained in this work indicated that TADDOL6 may also serve as an efficient host candidate for the separation of many of these pyridyl solutions. SCXRD experiments demonstrated that the only significant (host)π···π(guest) stacking interactions were those between TADDOL6 and preferred PYR and 3MP, as was the case for TADDOL5. These experiments also revealed that the strongest (host)O‒H···N(guest) hydrogen bonds were between TADDOL6 and these favoured guest species. A consideration of Hirshfeld surfaces and quantification of the (guest)N···H(host) intermolecular interactions correlated with the host selectivity order, as did thermal analyses, where the Ton values confirmed that the thermal stabilities of these complexes decreased in the guest order PYR > 3MP > 4MP > 2MP. The behaviour of TADDOL5 was further investigated in guest compounds DIO, PYR, PIP and MOR. Each guest solvent formed 1:1 H:G inclusion complexes with the host species, with the exception of DIO, which formed a 2:1 H:G complex. Mixed guest experiments revealed a clear preference for PIP and MOR, while PYR and DIO were less favoured. The host selectivity was demonstrated to be in the order PIP > MOR > PYR > DIO. SCXRD experiments showed that TADDOL5 formed a much shorter (and more linear) (host)O‒H···N(guest) hydrogen bond with the most favoured guest, PIP, compared to those involving MOR and PYR. A (host)O‒H···O(guest) hydrogen bond was also observed in the DIO-containing inclusion complex. A consideration of the Hirshfeld surface interactions was not useful in explaining the host selectivity order for these heterocyclic guests, but thermal analyses confirmed that the most stable complex was the one with favoured PIP, followed by those with PYR, MOR and DIO. TADDOL6, on the other hand, formed 1:1 H:G inclusion compounds with all four of the heterocyclic guest solvents. Experiments in mixed guests showed that the selectivity of this host compound for these guests was in the order PYR > PIP > MOR > DIO, which differed from the TADDOL5 (which favoured PIP and then MOR). Interestingly, the strongest classical hydrogen bond was not formed with the most favoured guest PYR, but with PIP instead (this bond with TADDOL5 was also strongest with PIP, but PIP was favoured in that work). Hirshfeld surface investigations again were not useful in understanding the host selectivity behaviour. However, thermal analyses agreed with the observations made in the mixed guest experiments: the most stable complex was with PYR (favoured) and the least stable one was with DIO (least preferred). , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Recchia, Daniella Loridana
- Date: 2024-12
- Subjects: Compounds -- guest/host , Chemistry, Organic , Chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69441 , vital:77256
- Description: The host compounds (4R,5R)-bis(diphenylhydroxymethyl)-2-spiro-1’-cyclopentane-1,3-dioxolane (TADDOL5) and (4R,5R)-bis(diphenylhydroxymethyl)-2-spiro-1’-cyclohexane-1,3-dioxolane (TADDOL6) were successfully synthesized after initially reacting diethyl tartrate with either 1,1-dimethoxycyclopentane or 1,1-dimethoxycyclohexane to afford the intermediates diethyl 2-spiro-1’-cyclopentane-1,3-dioxolan-4,5-dicarboxylate or diethyl 2-spiro-1’-cyclohexane-1,3-dioxolan-4,5-dicarboxylate. These were then each subjected to a Grignard addition reaction with PhMgBr to furnish TADDOL5 and TADDOL6 in reasonably high yields (77 and 80%, respectively). Computational calculations were performed on TADDOL5 and TADDOL6 using the software programs Avogadro and ORCA. The optimised geometries of these host molecules were obtained using the MMFF94 force field in Avogadro, while ORCA was used to perform the computational modelling at the BLYP level using the 6-31G*, 6-31G**, 6-311G* and 6-311G** basis sets and, also, the B3LYP functional (with the same basis sets) to obtain the three lowest energy conformers. The final geometries of each conformer for both TADDOL5 and TADDOL6 at the B3LYP 6-311G* level were overlaid with the molecules obtained from their crystal structures. Significantly different geometries were thus noted for the calculated conformers compared with the guest-free TADDOL5 and TADDOL6 structures obtained from the SCXRD experiments. When TADDOL5 was crystallized independently from each of PYR, 2MP, 3MP and 4MP, 1:1 H:G inclusion complexes formed in each instance. This host compound was then investigated for its host separation ability of mixed pyridines through supramolecular chemistry protocols. These mixed guest experiments revealed that TADDOL5 possessed a notable selectivity towards 3MP and PYR (in the absence of 3MP) followed by 4MP and 2MP, and it was shown that TADDOL5 is a suitable host candidate for the separation of many of the mixed pyridines employed here. The results of the SCXRD analyses indicated that the only significant (host)π···π(guest) stacking interaction present was between TADDOL5 and the most favoured guest species PYR and 3MP. Furthermore, significantly shorter (host)O‒H···N(guest) hydrogen bonds were also observed in the complexes formed between this host compound and 3MP and PYR compared with these bonds involving disfavoured 4MP and 2MP. Hirshfeld surface considerations provided an explanation for the affinity of TADDOL5 for PYR (but not 3MP), while thermal analyses successfully explained this affinity: the 3MP-containing complex with the most preferred guest species was the most thermally stable one, followed by TADDOL5·PYR, as obtained through a consideration of the Ton values (the temperature at which the guest release event initiated) of the four complexes. As with TADDOL5, TADDOL6 formed 1:1 H:G inclusion compounds with each of the four pyridines. TADDOL6 was, furthermore, also assessed for its separation ability for mixed pyridines, and these guest competition experiments showed that the selectivity of TADDOL6 was for PYR and 3MP (in the absence of PYR), followed by 4MP and 2MP. (Interestingly, TADDOL5 preferred 3MP and then PYR, while both host compounds disfavoured 4MP and 2MP.) The results obtained in this work indicated that TADDOL6 may also serve as an efficient host candidate for the separation of many of these pyridyl solutions. SCXRD experiments demonstrated that the only significant (host)π···π(guest) stacking interactions were those between TADDOL6 and preferred PYR and 3MP, as was the case for TADDOL5. These experiments also revealed that the strongest (host)O‒H···N(guest) hydrogen bonds were between TADDOL6 and these favoured guest species. A consideration of Hirshfeld surfaces and quantification of the (guest)N···H(host) intermolecular interactions correlated with the host selectivity order, as did thermal analyses, where the Ton values confirmed that the thermal stabilities of these complexes decreased in the guest order PYR > 3MP > 4MP > 2MP. The behaviour of TADDOL5 was further investigated in guest compounds DIO, PYR, PIP and MOR. Each guest solvent formed 1:1 H:G inclusion complexes with the host species, with the exception of DIO, which formed a 2:1 H:G complex. Mixed guest experiments revealed a clear preference for PIP and MOR, while PYR and DIO were less favoured. The host selectivity was demonstrated to be in the order PIP > MOR > PYR > DIO. SCXRD experiments showed that TADDOL5 formed a much shorter (and more linear) (host)O‒H···N(guest) hydrogen bond with the most favoured guest, PIP, compared to those involving MOR and PYR. A (host)O‒H···O(guest) hydrogen bond was also observed in the DIO-containing inclusion complex. A consideration of the Hirshfeld surface interactions was not useful in explaining the host selectivity order for these heterocyclic guests, but thermal analyses confirmed that the most stable complex was the one with favoured PIP, followed by those with PYR, MOR and DIO. TADDOL6, on the other hand, formed 1:1 H:G inclusion compounds with all four of the heterocyclic guest solvents. Experiments in mixed guests showed that the selectivity of this host compound for these guests was in the order PYR > PIP > MOR > DIO, which differed from the TADDOL5 (which favoured PIP and then MOR). Interestingly, the strongest classical hydrogen bond was not formed with the most favoured guest PYR, but with PIP instead (this bond with TADDOL5 was also strongest with PIP, but PIP was favoured in that work). Hirshfeld surface investigations again were not useful in understanding the host selectivity behaviour. However, thermal analyses agreed with the observations made in the mixed guest experiments: the most stable complex was with PYR (favoured) and the least stable one was with DIO (least preferred). , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
Synthesis, X-Ray characterization, spectroscopic and Hirshfeld surface analysis of dimeric metal centers featuring phenacyl-esters
- Authors: Qomfo, Vuyiseka
- Date: 2024-12
- Subjects: Spectrum analysis , Spectroscopic imaging , Diagnostic imaging -- Digital techniques
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69426 , vital:77254
- Description: In this study, the synthesis and characterization of carboxylate paddlewheel copper complexes were investigated and reported. The complexes consist of O-, and N- donor ligands which coordinated in the apical positions of the copper (II) paddlewheel complexes. The primary focus was the investigation of the influence of the incoming substituents on the structure; more especially with regards to the spectral properties and thermal properties of the synthesized compounds. Synthesized complexes ranged from simple mononuclear complexes and dinuclear dimers to supramolecular 1D networks and a tetranuclear copper (II) compound. Characterization of complexes was done using analytical, and spectroscopic techniques such as single crystal diffraction studies, FT-IR spectroscopy, thermal analysis and Hirshfeld surface analysis. Structural analysis of the mononuclear complex obtained in the reaction of the Cu2(o-CH3-PhCO2)4(THF)2 with the ligand ,2-oxo-phenylethylnicotinate, revealed a square-planar geometry. The series of dinuclear paddlewheel complexes obtained with ligands (L = THF (1), C4H8O (2), C14H11NO3 (3)) revealed a square pyramidal geometry with the methyl-substituted phenyl carboxylate groups bridging the two copper atoms in the syn-syn coordination mode. Extended supramolecular complexes were synthesized via the reaction of three synthesized structurally bifunctional organic ligands and the tetrakis(μ-carboxylato-O,O)dicopper(II) core. Two of the six reactions synthesized successfully to form paddlewheel cage type structures; resulting in dinuclear paddlewheel complexes with four carboxylate ligands occupying the equatorial positions and the bifunctional ligands coordinating in the apical positions. Four of the nine reactions produced mononuclear copper complexes. Due to the inconsistent power supply because of load-shedding, the other three crystals synthesized could not be confirmed by single-crystal diffraction before the submission of this thesis. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12
- Authors: Qomfo, Vuyiseka
- Date: 2024-12
- Subjects: Spectrum analysis , Spectroscopic imaging , Diagnostic imaging -- Digital techniques
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/69426 , vital:77254
- Description: In this study, the synthesis and characterization of carboxylate paddlewheel copper complexes were investigated and reported. The complexes consist of O-, and N- donor ligands which coordinated in the apical positions of the copper (II) paddlewheel complexes. The primary focus was the investigation of the influence of the incoming substituents on the structure; more especially with regards to the spectral properties and thermal properties of the synthesized compounds. Synthesized complexes ranged from simple mononuclear complexes and dinuclear dimers to supramolecular 1D networks and a tetranuclear copper (II) compound. Characterization of complexes was done using analytical, and spectroscopic techniques such as single crystal diffraction studies, FT-IR spectroscopy, thermal analysis and Hirshfeld surface analysis. Structural analysis of the mononuclear complex obtained in the reaction of the Cu2(o-CH3-PhCO2)4(THF)2 with the ligand ,2-oxo-phenylethylnicotinate, revealed a square-planar geometry. The series of dinuclear paddlewheel complexes obtained with ligands (L = THF (1), C4H8O (2), C14H11NO3 (3)) revealed a square pyramidal geometry with the methyl-substituted phenyl carboxylate groups bridging the two copper atoms in the syn-syn coordination mode. Extended supramolecular complexes were synthesized via the reaction of three synthesized structurally bifunctional organic ligands and the tetrakis(μ-carboxylato-O,O)dicopper(II) core. Two of the six reactions synthesized successfully to form paddlewheel cage type structures; resulting in dinuclear paddlewheel complexes with four carboxylate ligands occupying the equatorial positions and the bifunctional ligands coordinating in the apical positions. Four of the nine reactions produced mononuclear copper complexes. Due to the inconsistent power supply because of load-shedding, the other three crystals synthesized could not be confirmed by single-crystal diffraction before the submission of this thesis. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-12