IL-4/ IL-13 directed microglial activation and differentiation in response to LPS-induced neuroinflammation
- Authors: Ackerdien, Shiraz
- Date: 2024-04
- Subjects: Inflammation , Inflammation -- Treatment , Anti-inflammatory agents
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63606 , vital:73554
- Description: Microglia activation is a common hallmark of neuroinflammation that occurs during pathogen invasion or lipopolysaccharide (LPS)-induced inflammation. A neuroinflammatory response is elicited by the release of proinflammatory cytokines which stimulates microglia in an autocrine manner to be polarized into classically activated, pro-inflammatory M1 cells. Prolonged exposure to the inflammatory response can have disastrous effects on the central nervous system (CNS). However, microglia can alternatively be polarized into the activated M2 anti-inflammatory phenotype, but the exact molecular mechanism mediating this phenotypic switch remains poorly understood. Studies have shown that interleukin (IL)-4 can induce the M2 phenotype and activate the signal transducer and activator of the transcription 6 (STAT6) signalling pathway that in turn provokes a beneficial Th2 immune response. Since IL-4 and IL-13 share a common IL-4 receptor alpha (IL-4Rα) chain, it is possible that alternative microglia differentiation and its anti-inflammatory action also involve IL-13. This study aimed to investigate how IL-13 and STAT6 signalling orchestrates the microglial response and differentiation associated with LPS-induced inflammation. Furthermore, the molecular mechanisms that relieve LPS-induced neuroinflammation and neural protection through IL-13-enhanced BDNF signalling were also investigated. C8-B4 microglial cells were induced with LPS to exhibit an M1 pro-inflammatory phenotype or stimulated with IL-4 and/or IL-13 to exhibit an M2 anti-inflammatory microglial phenotype. The cell viability following LPS, IL-4, and/ or IL-13 exposure was determined. The LPS-induced neuroinflammatory response and the anti-inflammatory response induced by IL-4 and IL-13 which promotes STAT-6 signalling were determined by measuring TNFα, IL-1β, and BDNF protein concentrations using ELISA assays. The polarising effects of LPS and IL-4/IL-13 cytokines were also examined via changes in the expression of Iba-1, CD206, CD86, and STAT-6 determined by immunofluorescence analysis. These changes were further investigated by quantifying the mRNA transcripts of TNFα, IL-1 β, Arg-1, CD206, IL-4R, and STAT-6 and BDNF using qRT-PCR. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Ackerdien, Shiraz
- Date: 2024-04
- Subjects: Inflammation , Inflammation -- Treatment , Anti-inflammatory agents
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63606 , vital:73554
- Description: Microglia activation is a common hallmark of neuroinflammation that occurs during pathogen invasion or lipopolysaccharide (LPS)-induced inflammation. A neuroinflammatory response is elicited by the release of proinflammatory cytokines which stimulates microglia in an autocrine manner to be polarized into classically activated, pro-inflammatory M1 cells. Prolonged exposure to the inflammatory response can have disastrous effects on the central nervous system (CNS). However, microglia can alternatively be polarized into the activated M2 anti-inflammatory phenotype, but the exact molecular mechanism mediating this phenotypic switch remains poorly understood. Studies have shown that interleukin (IL)-4 can induce the M2 phenotype and activate the signal transducer and activator of the transcription 6 (STAT6) signalling pathway that in turn provokes a beneficial Th2 immune response. Since IL-4 and IL-13 share a common IL-4 receptor alpha (IL-4Rα) chain, it is possible that alternative microglia differentiation and its anti-inflammatory action also involve IL-13. This study aimed to investigate how IL-13 and STAT6 signalling orchestrates the microglial response and differentiation associated with LPS-induced inflammation. Furthermore, the molecular mechanisms that relieve LPS-induced neuroinflammation and neural protection through IL-13-enhanced BDNF signalling were also investigated. C8-B4 microglial cells were induced with LPS to exhibit an M1 pro-inflammatory phenotype or stimulated with IL-4 and/or IL-13 to exhibit an M2 anti-inflammatory microglial phenotype. The cell viability following LPS, IL-4, and/ or IL-13 exposure was determined. The LPS-induced neuroinflammatory response and the anti-inflammatory response induced by IL-4 and IL-13 which promotes STAT-6 signalling were determined by measuring TNFα, IL-1β, and BDNF protein concentrations using ELISA assays. The polarising effects of LPS and IL-4/IL-13 cytokines were also examined via changes in the expression of Iba-1, CD206, CD86, and STAT-6 determined by immunofluorescence analysis. These changes were further investigated by quantifying the mRNA transcripts of TNFα, IL-1 β, Arg-1, CD206, IL-4R, and STAT-6 and BDNF using qRT-PCR. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Self-attentive vision in evolutionary robotics
- Authors: Botha, Bouwer
- Date: 2024-04
- Subjects: Evolutionary robotics , Robotics , Neural networks (Computer science)
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63628 , vital:73566
- Description: The autonomy of a robot refers to its ability to achieve a task in an environment with minimal human supervision. This may require autonomous solutions to be able to perceive their environment to inform their decisions. An inexpensive and highly informative way that robots can perceive the environment is through vision. The autonomy of a robot is reliant on the quality of the robotic controller. These controllers are the software interface between the robot and environment that determine the actions of the robot based on the perceived environment. Controllers are typically created using manual programming techniques, which become progressively more challenging with increasing complexity of both the robot and task. An alternative to manual programming is the use of machine learning techniques such as those used by Evolutionary Robotics (ER). ER is an area of research that investigates the automatic creation of controllers. Instead of manually programming a controller, an Evolutionary Algorithms can be used to evolve the controller through repeated interactions with the task environment. Employing the ER approach on camera-based controllers, however, has presented problems for conventional ER methods. Firstly, existing architectures that are capable of automatically processing images, have a large number of trained parameters. These architectures over-encumber the evolutionary process due to the large search space of possible configurations. Secondly, the evolution of complex controllers needs to be done in simulation, which requires either: (a) the construction of a photo-realistic virtual environment with accurate lighting, texturing and models or (b) potential reduction of the controller capability by simplifying the problem via image preprocessing. Any controller trained in simulation also raises the inherent concern of not being able to transfer to the real world. This study proposes a new technique for the evolution of camera-based controllers in ER, that aims to address the highlighted problems. The use of self-attention is proposed to facilitate the evolution of compact controllers that are able to evolve specialized sets of task-relevant features in unprocessed images by focussing on important image regions. Furthermore, a new neural network-based simulation approach, Generative Neuro-Augmented Vision (GNAV), is proposed to simplify simulation construction. GNAV makes use of random data collected in a simple virtual environment and the real world. A neural network is trained to overcome the visual discrepancies between these two environments. GNAV enables a controller to be trained in a simple simulated environment that appears similar to the real environment, while requiring minimal human supervision. The capabilities of the new technique were demonstrated using a series of real-world navigation tasks based on camera vision. Controllers utilizing the proposed self-attention mechanism were trained using GNAV and transferred to a real camera-equipped robot. The controllers were shown to be able to perform the same tasks in the real world. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Botha, Bouwer
- Date: 2024-04
- Subjects: Evolutionary robotics , Robotics , Neural networks (Computer science)
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63628 , vital:73566
- Description: The autonomy of a robot refers to its ability to achieve a task in an environment with minimal human supervision. This may require autonomous solutions to be able to perceive their environment to inform their decisions. An inexpensive and highly informative way that robots can perceive the environment is through vision. The autonomy of a robot is reliant on the quality of the robotic controller. These controllers are the software interface between the robot and environment that determine the actions of the robot based on the perceived environment. Controllers are typically created using manual programming techniques, which become progressively more challenging with increasing complexity of both the robot and task. An alternative to manual programming is the use of machine learning techniques such as those used by Evolutionary Robotics (ER). ER is an area of research that investigates the automatic creation of controllers. Instead of manually programming a controller, an Evolutionary Algorithms can be used to evolve the controller through repeated interactions with the task environment. Employing the ER approach on camera-based controllers, however, has presented problems for conventional ER methods. Firstly, existing architectures that are capable of automatically processing images, have a large number of trained parameters. These architectures over-encumber the evolutionary process due to the large search space of possible configurations. Secondly, the evolution of complex controllers needs to be done in simulation, which requires either: (a) the construction of a photo-realistic virtual environment with accurate lighting, texturing and models or (b) potential reduction of the controller capability by simplifying the problem via image preprocessing. Any controller trained in simulation also raises the inherent concern of not being able to transfer to the real world. This study proposes a new technique for the evolution of camera-based controllers in ER, that aims to address the highlighted problems. The use of self-attention is proposed to facilitate the evolution of compact controllers that are able to evolve specialized sets of task-relevant features in unprocessed images by focussing on important image regions. Furthermore, a new neural network-based simulation approach, Generative Neuro-Augmented Vision (GNAV), is proposed to simplify simulation construction. GNAV makes use of random data collected in a simple virtual environment and the real world. A neural network is trained to overcome the visual discrepancies between these two environments. GNAV enables a controller to be trained in a simple simulated environment that appears similar to the real environment, while requiring minimal human supervision. The capabilities of the new technique were demonstrated using a series of real-world navigation tasks based on camera vision. Controllers utilizing the proposed self-attention mechanism were trained using GNAV and transferred to a real camera-equipped robot. The controllers were shown to be able to perform the same tasks in the real world. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
Investigation of the host potential of compounds derived from tartaric acid, succinic acid and 1,4-cyclohexanedioic acid
- Authors: Adam, Muhammad Ameen
- Date: 2024-04
- Subjects: Chemical reactions , Chemistry, Organic , Bacteriology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63617 , vital:73562
- Description: The present investigation considered the host behaviour of three compounds, namely (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (H1), 1,1,4,4-tetraphenyl-1,4-butanediol (H2) and cyclohexane-1,4-diylbis(diphenylmethanol) (H3) in various guest mixtures. These host compounds were readily synthesized by means of Grignard addition reactions on the diesters of tartaric acid, succinic acid and 1,4-cyclohexanedioic acid. The guest mixtures included cyclopentanone, cyclohexanone, cycloheptanone and cyclooctanone, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, and pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine. Crystals of (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (H1) were grown from cyclopentanone (5-ONE), cyclohexanone (6-ONE), cycloheptanone (7-ONE) and cyclooctanone (8-ONE,) producing 1:1 host:guest complexes in each instance. Thermal analysis showed the thermal stabilities of these complexes to be in the order 6-ONE > 7-ONE > 8-ONE > 5-ONE which correlated exactly with results from binary guest/guest competition experiments, where 6-ONE was always preferred by H1, while 5-ONE was consistently disfavoured. Single crystal X-ray diffraction (SCXRD) analyses demonstrated that each guest compound was retained in the crystals by means of a hydrogen bond with an alcohol moiety of the host compound. Furthermore, preferred guests 6- and 7-ONE produced crystals with greater densities than guests less favoured (5- and 8-ONE). A conformational analysis of the guest geometries in the four complexes with H1 revealed that the low energy guest conformers were present. The host selectivity for 6- and 7-ONE was proposed to be due to the improved molecular packing in the crystals of the complexes containing these two guest compounds, observed from their higher crystal densities. Hirshfeld surface analyses were not useful in explaining the preference of H1 for 6-ONE relative to 7-ONE (these types of analyses were not possible for the 5-ONE and 8-ONE-containing inclusion compounds due to the nature and degree of disorder present in the guest molecules). H1 was also crystallized from γ-butyrolactone (GBL), 2-pyrrolidone (NP), N-methyl-2-pyrrolidone (NMP) and N-ethyl-2-pyrrolidone (NEP), and 1H-NMR spectroscopy revealed that all but GBL were included. The host compound was also presented with these guest solvents in various mixtures, and it was observed that NMP was an extremely favoured guest solvent, followed by NEP and NP, with GBL being consistently disfavoured in every experiment. It was therefore shown that in certain instances, H1 may serve as an alternative tool for separating some of these mixtures through host-guest chemistry strategies. The hydrogen bonding motifs present in each of the successfully formed complexes were extensively investigated through SCXRD analysis, as was the thermal behaviour of these complexes. In the latter instance, the peak temperature of the endotherm (from the DSC trace) representing the guest release was greater for the inclusion compound with favoured NMP (145.5 °C) relative to the complexes with NP (139.8 °C) and NEP (120.5 °C). Host compounds H2 and H3 were revealed to have the ability to include each of pyridine (PYR), 2-methylpyridine (2MP), 3-methylpyridine (3MP) and 4-methylpyridine (4MP). H2 displayed selective behaviour for 3MP and 4MP when presented with mixtures of these guest compounds, whilst H3 preferred PYR. In the latter case, this PYR-containing inclusion compound was also the more stable one (the guest release onset temperature was highest, Ton 66.0 °C). It was demonstrated that H2 has the ability to separate very many binary mixtures of these pyridines on a practical platform, since K (the selectivity coefficient) values were 10 or greater in many instances. However, unfortunately, the more difficult-to-separate mixtures containing 3MP and 4MP cannot be purified or separated by employing H2 and supramolecular chemistry strategies. H3 was also shown to be a likely candidate for binary guest separations in very many of the guest solutions considered here, where K was also 10 or greater, and even infinity in many cases. SCXRD demonstrated that 2MP, 3MP and 4MP were retained in the crystals of their complexes by means of classical hydrogen bonds with the host compound. Satisfyingly, this hydrogen bond between 2MP and H2 (3.0213(18) Å) was significantly longer than that between this host compound and both disorder components of 3MP (2.875(2) and 2.825(9) Å) and that between H2 and 4MP (2.8458(13) Å). This observation explains the affinity of H2 for both 3MP and 4MP, and why 2MP was disfavoured. The results of thermal experiments did not wholly concur with observations from the guest/guest competition experiments. Hirshfeld surface analyses were also conducted but were not entirely conclusive with respect to explaining the host selectivity behaviour. In the case of H3, SCXRD analyses revealed that favoured PYR experienced a classical hydrogen bond with the host compound that was statistically significantly shorter (2.795(2) Å, 165°) than those between the other guest compounds and H3. Additionally, this guest compound was the only one to be involved in a (host)C−H···π(guest) interaction (2.91 Å, 139°) and also a non-classical hydrogen bond with the host compound ((host)C−H···N−C(guest), 2.77 Å (144°)). Finally, Hirshfeld surface analyses showed also that preferred PYR experienced a greater percentage of C···H/H···C (33.1%) and H···N/N···H (11.1%) interactions compared with the complexes with 2MP, 3MP and 4MP. However, it is not clear whether these Hirshfeld observations explain the affinity of H3 for PYR. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Adam, Muhammad Ameen
- Date: 2024-04
- Subjects: Chemical reactions , Chemistry, Organic , Bacteriology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63617 , vital:73562
- Description: The present investigation considered the host behaviour of three compounds, namely (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (H1), 1,1,4,4-tetraphenyl-1,4-butanediol (H2) and cyclohexane-1,4-diylbis(diphenylmethanol) (H3) in various guest mixtures. These host compounds were readily synthesized by means of Grignard addition reactions on the diesters of tartaric acid, succinic acid and 1,4-cyclohexanedioic acid. The guest mixtures included cyclopentanone, cyclohexanone, cycloheptanone and cyclooctanone, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, and pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine. Crystals of (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (H1) were grown from cyclopentanone (5-ONE), cyclohexanone (6-ONE), cycloheptanone (7-ONE) and cyclooctanone (8-ONE,) producing 1:1 host:guest complexes in each instance. Thermal analysis showed the thermal stabilities of these complexes to be in the order 6-ONE > 7-ONE > 8-ONE > 5-ONE which correlated exactly with results from binary guest/guest competition experiments, where 6-ONE was always preferred by H1, while 5-ONE was consistently disfavoured. Single crystal X-ray diffraction (SCXRD) analyses demonstrated that each guest compound was retained in the crystals by means of a hydrogen bond with an alcohol moiety of the host compound. Furthermore, preferred guests 6- and 7-ONE produced crystals with greater densities than guests less favoured (5- and 8-ONE). A conformational analysis of the guest geometries in the four complexes with H1 revealed that the low energy guest conformers were present. The host selectivity for 6- and 7-ONE was proposed to be due to the improved molecular packing in the crystals of the complexes containing these two guest compounds, observed from their higher crystal densities. Hirshfeld surface analyses were not useful in explaining the preference of H1 for 6-ONE relative to 7-ONE (these types of analyses were not possible for the 5-ONE and 8-ONE-containing inclusion compounds due to the nature and degree of disorder present in the guest molecules). H1 was also crystallized from γ-butyrolactone (GBL), 2-pyrrolidone (NP), N-methyl-2-pyrrolidone (NMP) and N-ethyl-2-pyrrolidone (NEP), and 1H-NMR spectroscopy revealed that all but GBL were included. The host compound was also presented with these guest solvents in various mixtures, and it was observed that NMP was an extremely favoured guest solvent, followed by NEP and NP, with GBL being consistently disfavoured in every experiment. It was therefore shown that in certain instances, H1 may serve as an alternative tool for separating some of these mixtures through host-guest chemistry strategies. The hydrogen bonding motifs present in each of the successfully formed complexes were extensively investigated through SCXRD analysis, as was the thermal behaviour of these complexes. In the latter instance, the peak temperature of the endotherm (from the DSC trace) representing the guest release was greater for the inclusion compound with favoured NMP (145.5 °C) relative to the complexes with NP (139.8 °C) and NEP (120.5 °C). Host compounds H2 and H3 were revealed to have the ability to include each of pyridine (PYR), 2-methylpyridine (2MP), 3-methylpyridine (3MP) and 4-methylpyridine (4MP). H2 displayed selective behaviour for 3MP and 4MP when presented with mixtures of these guest compounds, whilst H3 preferred PYR. In the latter case, this PYR-containing inclusion compound was also the more stable one (the guest release onset temperature was highest, Ton 66.0 °C). It was demonstrated that H2 has the ability to separate very many binary mixtures of these pyridines on a practical platform, since K (the selectivity coefficient) values were 10 or greater in many instances. However, unfortunately, the more difficult-to-separate mixtures containing 3MP and 4MP cannot be purified or separated by employing H2 and supramolecular chemistry strategies. H3 was also shown to be a likely candidate for binary guest separations in very many of the guest solutions considered here, where K was also 10 or greater, and even infinity in many cases. SCXRD demonstrated that 2MP, 3MP and 4MP were retained in the crystals of their complexes by means of classical hydrogen bonds with the host compound. Satisfyingly, this hydrogen bond between 2MP and H2 (3.0213(18) Å) was significantly longer than that between this host compound and both disorder components of 3MP (2.875(2) and 2.825(9) Å) and that between H2 and 4MP (2.8458(13) Å). This observation explains the affinity of H2 for both 3MP and 4MP, and why 2MP was disfavoured. The results of thermal experiments did not wholly concur with observations from the guest/guest competition experiments. Hirshfeld surface analyses were also conducted but were not entirely conclusive with respect to explaining the host selectivity behaviour. In the case of H3, SCXRD analyses revealed that favoured PYR experienced a classical hydrogen bond with the host compound that was statistically significantly shorter (2.795(2) Å, 165°) than those between the other guest compounds and H3. Additionally, this guest compound was the only one to be involved in a (host)C−H···π(guest) interaction (2.91 Å, 139°) and also a non-classical hydrogen bond with the host compound ((host)C−H···N−C(guest), 2.77 Å (144°)). Finally, Hirshfeld surface analyses showed also that preferred PYR experienced a greater percentage of C···H/H···C (33.1%) and H···N/N···H (11.1%) interactions compared with the complexes with 2MP, 3MP and 4MP. However, it is not clear whether these Hirshfeld observations explain the affinity of H3 for PYR. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
An in vitro evaluation of the anti-breast cancer activity of Nigella sativa extracts and its bioactive compound in combination with curcumin
- Authors: Botha, Susanna Gertruida
- Date: 2024-04
- Subjects: Herbs -- Therapeutic use , Radiation-protective agents , Breast -- Cancer -- Treatment
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63639 , vital:73571
- Description: Breast cancer constitutes 23% of all cancers in South African females. Curcumin and Nigella sativa have anti-cancer, anti-metastatic and antioxidant-properties and may be effective against breast cancer. This study focused on the effect of N. sativa extracts or thymoquinone and curcumin, individually and in combination, on breast cancer cells. An MTT assay showed that curcumin reduced cell viability by 50% (IC50) at 18 ± 2.63 μg/mL and thymoquinone (TQ) at 5 ± 0.95 μg/mL against the MDA-MB-231 cells. The IC50 values for curcumin and TQ were 35 ± 6.98 μg/mL and 4 ± 0.96 μg/mL against the MCF-7 cells, respectively. The IC50 value for the NSBE was determined to be 350 ± 55 μg/mL. The IC50 value of NSAE did not fall within the selected concentration range. Synergism was noted for combinations of NSBE with curcumin, and combinations of TQ with curcumin, against both MCF-7 and MDA-MB-231 cells. Two synergistic combinations per treatment per cell line, as determined by the combination index analysis, were chosen for further investigation. The combinations and individual treatments tested against the MCF-10A cells, were not significant, except for NSBE80:CURC20 combination. Curcumin had the most significant anti-oxidant activity; however, no link was noted between the anti-oxidant activity and the cytotoxicity of the combinations. The combination treatments induced apoptosis more effectively than the individual treatments. Caspase-3 dependent apoptosis was noted for NSBE10:CURC90 and TQ80:CURC20 combinations against the MDA-MB-231 cells, and the TQ60:CURC40 combination against the MCF-7 cells. The individual and combined treatments effectively reduced MDA-MB-231 cell adhesion to fibronectin, but not all reduced the cell adhesion to laminin. Based on these results, the combinations of curcumin with TQ or NSBE, have promising anticancer benefits against breast cancer. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Botha, Susanna Gertruida
- Date: 2024-04
- Subjects: Herbs -- Therapeutic use , Radiation-protective agents , Breast -- Cancer -- Treatment
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63639 , vital:73571
- Description: Breast cancer constitutes 23% of all cancers in South African females. Curcumin and Nigella sativa have anti-cancer, anti-metastatic and antioxidant-properties and may be effective against breast cancer. This study focused on the effect of N. sativa extracts or thymoquinone and curcumin, individually and in combination, on breast cancer cells. An MTT assay showed that curcumin reduced cell viability by 50% (IC50) at 18 ± 2.63 μg/mL and thymoquinone (TQ) at 5 ± 0.95 μg/mL against the MDA-MB-231 cells. The IC50 values for curcumin and TQ were 35 ± 6.98 μg/mL and 4 ± 0.96 μg/mL against the MCF-7 cells, respectively. The IC50 value for the NSBE was determined to be 350 ± 55 μg/mL. The IC50 value of NSAE did not fall within the selected concentration range. Synergism was noted for combinations of NSBE with curcumin, and combinations of TQ with curcumin, against both MCF-7 and MDA-MB-231 cells. Two synergistic combinations per treatment per cell line, as determined by the combination index analysis, were chosen for further investigation. The combinations and individual treatments tested against the MCF-10A cells, were not significant, except for NSBE80:CURC20 combination. Curcumin had the most significant anti-oxidant activity; however, no link was noted between the anti-oxidant activity and the cytotoxicity of the combinations. The combination treatments induced apoptosis more effectively than the individual treatments. Caspase-3 dependent apoptosis was noted for NSBE10:CURC90 and TQ80:CURC20 combinations against the MDA-MB-231 cells, and the TQ60:CURC40 combination against the MCF-7 cells. The individual and combined treatments effectively reduced MDA-MB-231 cell adhesion to fibronectin, but not all reduced the cell adhesion to laminin. Based on these results, the combinations of curcumin with TQ or NSBE, have promising anticancer benefits against breast cancer. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
The Algoa Bay region groundwater cycle – linking source to coast
- Authors: Dodd, Carla
- Date: 2024-04
- Subjects: Ecohydrology , Hydrology , Groundwater -- Management
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63722 , vital:73592
- Description: Groundwater is a crucial component of freshwater supply globally, especially in water-scarce regions such as semi-arid climatic areas where surface water resources are climatically limited and further constrained during droughts. Groundwater resources are also important from an ecological perspective as they support numerous surface ecosystems including wetlands and rivers. Coastal groundwater discharge along the South African coast sustains supratidal spring-fed living microbialite ecosystems (SSLiME). These systems act as potential analogues for Earth’s earliest ecosystems and are therefore useful from a palaeoscientific and evolutionary perspective. The Southern Cape coast of South Africa is characterised by both fractured and intergranular aquifers and hosts the most extensive network of SSLiME reported globally. However, the region is frequently affected by water scarcity crises and consequently groundwater development and usage has increased. Yet, it is unclear to what extent coastal discharge is linked to inland aquifers and whether anthropogenic activities influence the quantity and quality of groundwater that flows into SSLiME. This thesis aims to assess the groundwater cycle of the Algoa Bay region along the Southern Cape coast by means of a multi-tracer study. Specifically, it endeavours to develop a better understanding of the hydrogeochemical connectivity between inland groundwater resources and coastal microbialite ecosystems. To achieve this, four groups of hydrochemical tracers were used: H- and O-isotope ratios, major cations and anions, organic micropollutants and macronutrients. Sampling strategies included monthly precipitation collection over twelve months (stable water isotopes), once-off groundwater collection from boreholes, inland springs and coastal discharge (all tracers). In addition, coastal groundwater discharge was sampled during a once-off repeat campaign (all tracers) and seasonally at selected sites (macronutrients). A local meteoric water line (LMWL) for the region was established and compared to the isotopic signature of groundwater. The results indicate that groundwater is likely recharged directly and with little evaporation. Furthermore, similarities in isotopic signatures between inland and coastal aquifer systems suggest some level of hydrogeological connectivity or similar environmental drivers of recharge, such as precipitation amount and moisture source. This is also supported by the physico-chemistry and major ionic composition of the groundwater samples. However, the major ion composition of groundwater is variable and, although it predominantly reflects the sodium-chloride nature of precipitation, lithological and spatial trends are apparent. For example, coastward trends such as increasing conductivity, calcium, total alkalinity, and nitrogen is evident. While isotopes and major ions inform on the environmental drivers and geogenic influence on groundwater recharge, the organic micropollutants and macronutrients provide insight into the nature of anthropogenic impacts on groundwater quality. Micropollutants quantified in the groundwater samples included artificial sweeteners, pharmaceuticals, a biocide, and an illicit drug. These compounds are mostly classed as wastewater indicators and indicate aquifer contamination from leaking reticulation systems and septic tanks. The highest concentrations are associated with the urban and coastal peri-urban areas, while groundwater from rural areas is often devoid of any micropollutants except sulfamic acid, which may be introduced during recharge from precipitation. Furthermore, the presence of selected compounds in groundwater discharge signifies that at least a component of the groundwater is derived from recent infiltration. Similarly, the macronutrient content of groundwater reflects the proximal land use. As such, coastal groundwater discharge sites adjacent to coastal villages reflect higher concentrations compared to rural sites. In addition, the nutrient load supplied to and discharged from SSLiME systems is quantified and the nutrient attenuation is estimated. This thesis contributes recent hydrogeochemical information for a structurally complex semi-arid area under both natural (drought conditions) and human (increased water use, degradation of aquifers) pressures. Collectively, the results indicate that coastal groundwater discharge is likely a mixture of both the intergranular and fractured aquifers and that anthropogenic activities in the hinterland is contaminating the groundwater. This study is an important addition to the baseline hydrological information available for the region and may be useful in terms of sustainable groundwater management strategies and development toward a socio-ecological optimum, especially as related to coastal microbialite system. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Dodd, Carla
- Date: 2024-04
- Subjects: Ecohydrology , Hydrology , Groundwater -- Management
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63722 , vital:73592
- Description: Groundwater is a crucial component of freshwater supply globally, especially in water-scarce regions such as semi-arid climatic areas where surface water resources are climatically limited and further constrained during droughts. Groundwater resources are also important from an ecological perspective as they support numerous surface ecosystems including wetlands and rivers. Coastal groundwater discharge along the South African coast sustains supratidal spring-fed living microbialite ecosystems (SSLiME). These systems act as potential analogues for Earth’s earliest ecosystems and are therefore useful from a palaeoscientific and evolutionary perspective. The Southern Cape coast of South Africa is characterised by both fractured and intergranular aquifers and hosts the most extensive network of SSLiME reported globally. However, the region is frequently affected by water scarcity crises and consequently groundwater development and usage has increased. Yet, it is unclear to what extent coastal discharge is linked to inland aquifers and whether anthropogenic activities influence the quantity and quality of groundwater that flows into SSLiME. This thesis aims to assess the groundwater cycle of the Algoa Bay region along the Southern Cape coast by means of a multi-tracer study. Specifically, it endeavours to develop a better understanding of the hydrogeochemical connectivity between inland groundwater resources and coastal microbialite ecosystems. To achieve this, four groups of hydrochemical tracers were used: H- and O-isotope ratios, major cations and anions, organic micropollutants and macronutrients. Sampling strategies included monthly precipitation collection over twelve months (stable water isotopes), once-off groundwater collection from boreholes, inland springs and coastal discharge (all tracers). In addition, coastal groundwater discharge was sampled during a once-off repeat campaign (all tracers) and seasonally at selected sites (macronutrients). A local meteoric water line (LMWL) for the region was established and compared to the isotopic signature of groundwater. The results indicate that groundwater is likely recharged directly and with little evaporation. Furthermore, similarities in isotopic signatures between inland and coastal aquifer systems suggest some level of hydrogeological connectivity or similar environmental drivers of recharge, such as precipitation amount and moisture source. This is also supported by the physico-chemistry and major ionic composition of the groundwater samples. However, the major ion composition of groundwater is variable and, although it predominantly reflects the sodium-chloride nature of precipitation, lithological and spatial trends are apparent. For example, coastward trends such as increasing conductivity, calcium, total alkalinity, and nitrogen is evident. While isotopes and major ions inform on the environmental drivers and geogenic influence on groundwater recharge, the organic micropollutants and macronutrients provide insight into the nature of anthropogenic impacts on groundwater quality. Micropollutants quantified in the groundwater samples included artificial sweeteners, pharmaceuticals, a biocide, and an illicit drug. These compounds are mostly classed as wastewater indicators and indicate aquifer contamination from leaking reticulation systems and septic tanks. The highest concentrations are associated with the urban and coastal peri-urban areas, while groundwater from rural areas is often devoid of any micropollutants except sulfamic acid, which may be introduced during recharge from precipitation. Furthermore, the presence of selected compounds in groundwater discharge signifies that at least a component of the groundwater is derived from recent infiltration. Similarly, the macronutrient content of groundwater reflects the proximal land use. As such, coastal groundwater discharge sites adjacent to coastal villages reflect higher concentrations compared to rural sites. In addition, the nutrient load supplied to and discharged from SSLiME systems is quantified and the nutrient attenuation is estimated. This thesis contributes recent hydrogeochemical information for a structurally complex semi-arid area under both natural (drought conditions) and human (increased water use, degradation of aquifers) pressures. Collectively, the results indicate that coastal groundwater discharge is likely a mixture of both the intergranular and fractured aquifers and that anthropogenic activities in the hinterland is contaminating the groundwater. This study is an important addition to the baseline hydrological information available for the region and may be useful in terms of sustainable groundwater management strategies and development toward a socio-ecological optimum, especially as related to coastal microbialite system. , Thesis (PhD) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
The Camdeboo-Mountain Zebra mega-reserve as an opportunity to protect viable populations of medium- to large-sized mammals
- Authors: Davis, Kristen
- Date: 2024-04
- Subjects: Mammals -- Ecology -- South Africa -- Eastern Cape , Conservation of natural resources -- South Africa -- Eastern Cape , Wildlife conservation -- South Africa -- Eastern Cape
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63711 , vital:73590
- Description: Conservation planning has focused extensively on representation of species in protected areas (PAs), rather than achieving the persistence of these species in PAs. Consequently, most PAs do not support viable populations of many species represented within them, particularly large mammals, resulting in extinction debt risks. The challenge is therefore to identify opportunities to achieve viable populations and to develop and implement conservation plans to achieve this, e.g., expand and connect existing PAs. A recent meta-analysis provides a minimum viable population (MVP) estimate of 5 000 individuals for mammals. This value was used as the target for modelling conservation opportunities for the South African endemic Cape mountain zebra (Equus zebra zebra), blesbok (Damaliscus pygargus phillipsi), black wildebeest (Connochaetes gnou) and co-existing medium- and large-sized mammal species. This study focused on the region between the Camdeboo and Mountain Zebra national parks (ca. 736 000 ha). Within the envisaged Camdeboo-Mountain Zebra (C-MZ) mega-reserve, a spreadsheet model was used to estimate potential herbivore population sizes, spatial requirement data were used to estimate potential omnivore and insectivore population sizes, and herbivore densities were used to estimate potential large carnivore population sizes. I show that 12 (the three endemic grazers and nine co-existing species) of the 28 modelled medium- and large-sized mammal species will potentially exceed 5 000 individuals, the MVP target, within the envisaged mega-reserve. The remaining 16 species show potential to reach substantial population sizes, however, will likely require ongoing metapopulation management. Using a conservation planning approach, I identify priority areas for the conservation of suitable habitat for Cape mountain zebra, blesbok, and black wildebeest within the envisaged mega-reserve, thus indirectly identifying priority areas for the conservation of these endemic species. I show that the potential incorporation of these priority areas within the envisaged mega-reserve will contribute considerably to the conservation of all focal species. In addition, the potential incorporation of these priority areas will contribute to PA expansion and significantly improve connectivity between existing PAs within the envisaged C-MZ mega-reserve. The importance of adequately-sized PAs to support viable populations of focal species is thus evident, and will ensure their long-term survival and ability to persist by allowing population and evolutionary scale processes. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Davis, Kristen
- Date: 2024-04
- Subjects: Mammals -- Ecology -- South Africa -- Eastern Cape , Conservation of natural resources -- South Africa -- Eastern Cape , Wildlife conservation -- South Africa -- Eastern Cape
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63711 , vital:73590
- Description: Conservation planning has focused extensively on representation of species in protected areas (PAs), rather than achieving the persistence of these species in PAs. Consequently, most PAs do not support viable populations of many species represented within them, particularly large mammals, resulting in extinction debt risks. The challenge is therefore to identify opportunities to achieve viable populations and to develop and implement conservation plans to achieve this, e.g., expand and connect existing PAs. A recent meta-analysis provides a minimum viable population (MVP) estimate of 5 000 individuals for mammals. This value was used as the target for modelling conservation opportunities for the South African endemic Cape mountain zebra (Equus zebra zebra), blesbok (Damaliscus pygargus phillipsi), black wildebeest (Connochaetes gnou) and co-existing medium- and large-sized mammal species. This study focused on the region between the Camdeboo and Mountain Zebra national parks (ca. 736 000 ha). Within the envisaged Camdeboo-Mountain Zebra (C-MZ) mega-reserve, a spreadsheet model was used to estimate potential herbivore population sizes, spatial requirement data were used to estimate potential omnivore and insectivore population sizes, and herbivore densities were used to estimate potential large carnivore population sizes. I show that 12 (the three endemic grazers and nine co-existing species) of the 28 modelled medium- and large-sized mammal species will potentially exceed 5 000 individuals, the MVP target, within the envisaged mega-reserve. The remaining 16 species show potential to reach substantial population sizes, however, will likely require ongoing metapopulation management. Using a conservation planning approach, I identify priority areas for the conservation of suitable habitat for Cape mountain zebra, blesbok, and black wildebeest within the envisaged mega-reserve, thus indirectly identifying priority areas for the conservation of these endemic species. I show that the potential incorporation of these priority areas within the envisaged mega-reserve will contribute considerably to the conservation of all focal species. In addition, the potential incorporation of these priority areas will contribute to PA expansion and significantly improve connectivity between existing PAs within the envisaged C-MZ mega-reserve. The importance of adequately-sized PAs to support viable populations of focal species is thus evident, and will ensure their long-term survival and ability to persist by allowing population and evolutionary scale processes. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Evaluating elephant, Loxodonta africana, space-use and elephant-linked vegetation change in Liwonde National Park, Malawi
- Authors: Evers, Emma Else Maria
- Date: 2024-04
- Subjects: Elephants -- Nutrition -- Malawi , Ecological heterogeneity , Vegetation and climate
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63744 , vital:73594
- Description: Heterogeneity, the spatio-temporal variation of abiotic and biotic factors, is a key concept that underpins many ecological phenomena and promotes biodiversity. Ecosystem engineers, such as African savanna elephants (hereafter elephant), Loxodonta africana, are organisms capable of affecting heterogeneity through the creation or modification of habitats. Thus, their impacts can have important consequences for ecosystem biodiversity, both positive and negative. Caughley’s “elephant problem” cautions that confined or compressed, growing elephant populations will inevitably lead to a loss of biodiversity. However, a shift in our understanding of elephants suggests that not all elephant impacts lead to negative biodiversity consequences, as long as there is a heterogeneous spread of elephant impacts that allows for spatio-temporal refuges promoting the persistence of both impact-tolerant and impact-intolerant species. To date, little empirical evidence is available in support of managing elephants under this paradigm and few studies are available that infer the consequences of the distribution of elephant impacts on biodiversity. In addition, most studies use parametric statistics that do not account for scale, spatial autocorrelation, or non-stationarity, leading to a misrepresentation of the underlying processes and patterns of drivers of elephant space-use and the consequences of their impacts on biodiversity. Here, I evaluate spatio-temporal patterns and drivers of elephant space-use, and how the distribution of their impacts affects biodiversity through vegetation changes, using a multi-scaled spatial approach, in Liwonde National Park, Malawi. My study demonstrates that elephant space-use in Liwonde is heterogeneous, leading to spatio-temporal variation in the distribution of their impacts, even in a small, fenced reserve. The importance of the drivers of this heterogeneous space-use varied based on the scale of analysis, water was generally important at larger scales while vegetation quality (indexed by NDVI) was more important at smaller scales. When examined using local models, my results suggest that relationships exhibit non-stationarity, what is important in one area of the park is not necessarily important in other areas. The spatio-temporal variation of the inferred impacts of elephants in Liwonde still allowed for spatio-temporal refuges to be created, no clear linear relationship was found between elephant return intervals and woody species structural and functional diversity (indexed by changes in tree cover and changes in annual regrowth using Normalized Difference Vegetation Index as a measure, respectively) throughout the park. My study provides support for adopting the heterogeneity paradigm for managing elephants and demonstrates that not all elephant impacts result in negative vegetation change. I also demonstrate the crucial implications of accounting for scale, non-stationarity, and spatial autocorrelation to evaluate how animals both respond to, and contribute to, environmental heterogeneity. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Evers, Emma Else Maria
- Date: 2024-04
- Subjects: Elephants -- Nutrition -- Malawi , Ecological heterogeneity , Vegetation and climate
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63744 , vital:73594
- Description: Heterogeneity, the spatio-temporal variation of abiotic and biotic factors, is a key concept that underpins many ecological phenomena and promotes biodiversity. Ecosystem engineers, such as African savanna elephants (hereafter elephant), Loxodonta africana, are organisms capable of affecting heterogeneity through the creation or modification of habitats. Thus, their impacts can have important consequences for ecosystem biodiversity, both positive and negative. Caughley’s “elephant problem” cautions that confined or compressed, growing elephant populations will inevitably lead to a loss of biodiversity. However, a shift in our understanding of elephants suggests that not all elephant impacts lead to negative biodiversity consequences, as long as there is a heterogeneous spread of elephant impacts that allows for spatio-temporal refuges promoting the persistence of both impact-tolerant and impact-intolerant species. To date, little empirical evidence is available in support of managing elephants under this paradigm and few studies are available that infer the consequences of the distribution of elephant impacts on biodiversity. In addition, most studies use parametric statistics that do not account for scale, spatial autocorrelation, or non-stationarity, leading to a misrepresentation of the underlying processes and patterns of drivers of elephant space-use and the consequences of their impacts on biodiversity. Here, I evaluate spatio-temporal patterns and drivers of elephant space-use, and how the distribution of their impacts affects biodiversity through vegetation changes, using a multi-scaled spatial approach, in Liwonde National Park, Malawi. My study demonstrates that elephant space-use in Liwonde is heterogeneous, leading to spatio-temporal variation in the distribution of their impacts, even in a small, fenced reserve. The importance of the drivers of this heterogeneous space-use varied based on the scale of analysis, water was generally important at larger scales while vegetation quality (indexed by NDVI) was more important at smaller scales. When examined using local models, my results suggest that relationships exhibit non-stationarity, what is important in one area of the park is not necessarily important in other areas. The spatio-temporal variation of the inferred impacts of elephants in Liwonde still allowed for spatio-temporal refuges to be created, no clear linear relationship was found between elephant return intervals and woody species structural and functional diversity (indexed by changes in tree cover and changes in annual regrowth using Normalized Difference Vegetation Index as a measure, respectively) throughout the park. My study provides support for adopting the heterogeneity paradigm for managing elephants and demonstrates that not all elephant impacts result in negative vegetation change. I also demonstrate the crucial implications of accounting for scale, non-stationarity, and spatial autocorrelation to evaluate how animals both respond to, and contribute to, environmental heterogeneity. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Augmenting the Moore-Penrose generalised Inverse to train neural networks
- Authors: Fang, Bobby
- Date: 2024-04
- Subjects: Neural networks (Computer science) , Machine learning , Mathematical optimization -- Computer programs
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63755 , vital:73595
- Description: An Extreme Learning Machine (ELM) is a non-iterative and fast feedforward neural network training algorithm which uses the Moore-Penrose generalised inverse of a matrix to compute the weights of the output layer of the neural network, using a random initialisation for the hidden layer. While ELM has been used to train feedforward neural networks, the effectiveness of the MP generalised to train recurrent neural networks is yet to be investigated. The primary aim of this research was to investigate how biases in the output layer and the MP generalised inverse can be used to train recurrent neural networks. To accomplish this, the Bias Augmented ELM (BA-ELM), which concatenated the hidden layer output matrix with a ones-column vector to simulate the biases in the output layer, was proposed. A variety of datasets generated from optimisation test functions, as well as using real-world regression and classification datasets, were used to validate BA-ELM. The results showed in specific circumstances that BA-ELM was able to perform better than ELM. Following this, Recurrent ELM (R-ELM) was proposed which uses a recurrent hidden layer instead of a feedforward hidden layer. Recurrent neural networks also rely on having functional feedback connections in the recurrent layer. A hybrid training algorithm, Recurrent Hybrid ELM (R-HELM), was proposed, which uses a gradient-based algorithm to optimise the recurrent layer and the MP generalised inverse to compute the output weights. The evaluation of R-ELM and R-HELM algorithms were carried out using three different recurrent architectures on two recurrent tasks derived from the Susceptible- Exposed-Infected-Removed (SEIR) epidemiology model. Various training hyperparameters were evaluated through hyperparameter investigations to investigate their effectiveness on the hybrid training algorithm. With optimal hyperparameters, the hybrid training algorithm was able to achieve better performance than the conventional gradient-based algorithm. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Fang, Bobby
- Date: 2024-04
- Subjects: Neural networks (Computer science) , Machine learning , Mathematical optimization -- Computer programs
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63755 , vital:73595
- Description: An Extreme Learning Machine (ELM) is a non-iterative and fast feedforward neural network training algorithm which uses the Moore-Penrose generalised inverse of a matrix to compute the weights of the output layer of the neural network, using a random initialisation for the hidden layer. While ELM has been used to train feedforward neural networks, the effectiveness of the MP generalised to train recurrent neural networks is yet to be investigated. The primary aim of this research was to investigate how biases in the output layer and the MP generalised inverse can be used to train recurrent neural networks. To accomplish this, the Bias Augmented ELM (BA-ELM), which concatenated the hidden layer output matrix with a ones-column vector to simulate the biases in the output layer, was proposed. A variety of datasets generated from optimisation test functions, as well as using real-world regression and classification datasets, were used to validate BA-ELM. The results showed in specific circumstances that BA-ELM was able to perform better than ELM. Following this, Recurrent ELM (R-ELM) was proposed which uses a recurrent hidden layer instead of a feedforward hidden layer. Recurrent neural networks also rely on having functional feedback connections in the recurrent layer. A hybrid training algorithm, Recurrent Hybrid ELM (R-HELM), was proposed, which uses a gradient-based algorithm to optimise the recurrent layer and the MP generalised inverse to compute the output weights. The evaluation of R-ELM and R-HELM algorithms were carried out using three different recurrent architectures on two recurrent tasks derived from the Susceptible- Exposed-Infected-Removed (SEIR) epidemiology model. Various training hyperparameters were evaluated through hyperparameter investigations to investigate their effectiveness on the hybrid training algorithm. With optimal hyperparameters, the hybrid training algorithm was able to achieve better performance than the conventional gradient-based algorithm. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
The demographic-specific prey preferences of lions and cheetahs, and potential impacts on prey populations
- Authors: Dreyer, Nicola Bondi
- Date: 2024-04
- Subjects: Predation (Biology) , Animal populations , Animal ecology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63733 , vital:73593
- Description: Understanding prey selection offers predictive insights into predator-prey interactions, which can be extended to explore the impacts of predators on prey populations. Prey availability and vulnerability vary across species, demographic classes, body sizes, and seasons. Traditional prey selection models for large carnivores, based on estimates of prey body size, assume uniform vulnerability across prey demographic classes and seasons, failing to account for these variations. This study aims to contrast seasonal shifts in demographic-specific prey preferences between lions and cheetahs and examine the potential impact of their demographic-specific predation patterns on a range of prey species across a body size spectrum. It was predicted that cheetahs would shift their selection from adults and juveniles of smaller prey species in the dry season to neonates and juveniles of both smaller and larger prey species in the wet season, while lions would select adults irrespective of the season. Additionally, predation focusing on adults would have a greater impact on prey populations compared to predation focusing on non-adults. Furthermore, it was predicted that prey populations experiencing demographic-specific selection from both lions and cheetahs would be impacted more than species selected by only one predator. Degrees of preference (DOP) were estimated based on prey availability (camera traps) and prey use (GPS clusters) for lion and cheetah populations in Lapalala Wilderness Reserve. Generalized Additive Models for Location, Scale, and Shape (GAMLSS) were used to determine seasonal shifts in demographic-specific prey preferences. The seasonal-demographic specific predation patterns of lion and cheetah, along with prey vital rates extracted from the literature, were then used to model potential predation impacts on prey populations using both Leslie-Usher and Lefkovitch matrix models. Lions preferred larger adult prey such as blue wildebeest, eland, and buffalo, while cheetahs preferred smaller prey, particularly juveniles of small to intermediate-sized species like impala, kudu, blue wildebeest, and zebra. Both predators showed seasonal shifts in demographic-specific prey preferences, with lions selecting adult buffalo during the dry season and juvenile buffalo in the wet season, and cheetahs selecting juveniles in the dry season and neonates and juveniles during the wet season. Lions and cheetahs exerted the highest degree of top-down limitations on their preferred prey. Predation on adult prey had a greater effect on prey population growth rates than predation on non-adults, especially in the dry season. Intermediate-sized prey species experienced the highest predation pressures, while larger prey species were more affected than smaller ones, contrary to the size-nested predation hypothesis. My study represents a first effort in the southern hemisphere to model the demographic impacts of multiple predators on diverse prey species, incorporating seasonal and demographic-specific prey preferences. The findings emphasise the importance of incorporating prey demographics and seasonality in predator-prey studies as these refined studies have implications for the management and conservation of both predator and prey populations. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Dreyer, Nicola Bondi
- Date: 2024-04
- Subjects: Predation (Biology) , Animal populations , Animal ecology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63733 , vital:73593
- Description: Understanding prey selection offers predictive insights into predator-prey interactions, which can be extended to explore the impacts of predators on prey populations. Prey availability and vulnerability vary across species, demographic classes, body sizes, and seasons. Traditional prey selection models for large carnivores, based on estimates of prey body size, assume uniform vulnerability across prey demographic classes and seasons, failing to account for these variations. This study aims to contrast seasonal shifts in demographic-specific prey preferences between lions and cheetahs and examine the potential impact of their demographic-specific predation patterns on a range of prey species across a body size spectrum. It was predicted that cheetahs would shift their selection from adults and juveniles of smaller prey species in the dry season to neonates and juveniles of both smaller and larger prey species in the wet season, while lions would select adults irrespective of the season. Additionally, predation focusing on adults would have a greater impact on prey populations compared to predation focusing on non-adults. Furthermore, it was predicted that prey populations experiencing demographic-specific selection from both lions and cheetahs would be impacted more than species selected by only one predator. Degrees of preference (DOP) were estimated based on prey availability (camera traps) and prey use (GPS clusters) for lion and cheetah populations in Lapalala Wilderness Reserve. Generalized Additive Models for Location, Scale, and Shape (GAMLSS) were used to determine seasonal shifts in demographic-specific prey preferences. The seasonal-demographic specific predation patterns of lion and cheetah, along with prey vital rates extracted from the literature, were then used to model potential predation impacts on prey populations using both Leslie-Usher and Lefkovitch matrix models. Lions preferred larger adult prey such as blue wildebeest, eland, and buffalo, while cheetahs preferred smaller prey, particularly juveniles of small to intermediate-sized species like impala, kudu, blue wildebeest, and zebra. Both predators showed seasonal shifts in demographic-specific prey preferences, with lions selecting adult buffalo during the dry season and juvenile buffalo in the wet season, and cheetahs selecting juveniles in the dry season and neonates and juveniles during the wet season. Lions and cheetahs exerted the highest degree of top-down limitations on their preferred prey. Predation on adult prey had a greater effect on prey population growth rates than predation on non-adults, especially in the dry season. Intermediate-sized prey species experienced the highest predation pressures, while larger prey species were more affected than smaller ones, contrary to the size-nested predation hypothesis. My study represents a first effort in the southern hemisphere to model the demographic impacts of multiple predators on diverse prey species, incorporating seasonal and demographic-specific prey preferences. The findings emphasise the importance of incorporating prey demographics and seasonality in predator-prey studies as these refined studies have implications for the management and conservation of both predator and prey populations. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Lion and leopard diet and dispersal in human-dominated landscapes
- Authors: Forbes, Ryan Edward
- Date: 2024-04
- Subjects: Carnivora -- South Africa , Carnivorous animals -- Conservation , Carnivorous animals -- Ecology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63766 , vital:73596
- Description: Terrestrial carnivore population declines are driven by habitat loss and fragmentation, prey-depletion, persecution, and retaliatory killings. Population strongholds now centre on protected areas, that face increasing human pressure, resulting in population isolation, declining prey populations, and livestock intrusion. I therefore aimed to investigate dispersal and connectivity, and diets of lions (Panthera leo) and leopards (P. pardus) in response to human-use and wildlife density gradients in the Greater Limpopo Transfrontier Conservation Area (GLTCA). Firstly, I investigated dispersal and connectivity for these carnivores across the GLTCA, using single nucleotide polymorphisms. I present evidence that in the prey-depleted Mozambique portion of the GLTCA, lion and leopard dispersal distances are higher compared with the prey-abundant Kruger National Park (KNP). I also provide the first evidence for long-range dispersal in female lions. Despite evidence for connectivity occurring across the GLTCA, I recorded population structuring across the region for both carnivores, likely due to habitat fragmentation by human activities in the Mozambique portion of the GLTCA. I then assessed carnivore diet responses to prey depletion and livestock availability by comparing lion and leopard diets in the prey-abundant/livestock-absent KNP (South Africa), with the prey-depleted/livestock-abundant Limpopo National Park (LNP, Mozambique), using scat analyses. Lions and leopards downshifted their prey size selection in LNP relative to KNP. Despite both carnivores expanding their dietary niche breadths in LNP relative to KNP, diet overlap did not differ between sites. This suggests that even when prey is depleted, lions and leopards can partition food resources, which likely limits competition. Despite cattle (Bos taurus) being the most abundant ungulate in LNP, lions and leopards strongly avoided cattle, supporting the notion that carnivores can perceive the risk of hunting livestock and modulate their foraging behaviour to reduce human-carnivore conflict. Should my findings reflect general patterns in carnivore dispersal and diet responses to human-use and wildlife gradients, then carnivore conservation initiates across their range should focus on prey population rehabilitation, improved livestock husbandry practices, the establishment of effective dispersal corridors and improved human-tolerance towards large carnivores. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Forbes, Ryan Edward
- Date: 2024-04
- Subjects: Carnivora -- South Africa , Carnivorous animals -- Conservation , Carnivorous animals -- Ecology
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63766 , vital:73596
- Description: Terrestrial carnivore population declines are driven by habitat loss and fragmentation, prey-depletion, persecution, and retaliatory killings. Population strongholds now centre on protected areas, that face increasing human pressure, resulting in population isolation, declining prey populations, and livestock intrusion. I therefore aimed to investigate dispersal and connectivity, and diets of lions (Panthera leo) and leopards (P. pardus) in response to human-use and wildlife density gradients in the Greater Limpopo Transfrontier Conservation Area (GLTCA). Firstly, I investigated dispersal and connectivity for these carnivores across the GLTCA, using single nucleotide polymorphisms. I present evidence that in the prey-depleted Mozambique portion of the GLTCA, lion and leopard dispersal distances are higher compared with the prey-abundant Kruger National Park (KNP). I also provide the first evidence for long-range dispersal in female lions. Despite evidence for connectivity occurring across the GLTCA, I recorded population structuring across the region for both carnivores, likely due to habitat fragmentation by human activities in the Mozambique portion of the GLTCA. I then assessed carnivore diet responses to prey depletion and livestock availability by comparing lion and leopard diets in the prey-abundant/livestock-absent KNP (South Africa), with the prey-depleted/livestock-abundant Limpopo National Park (LNP, Mozambique), using scat analyses. Lions and leopards downshifted their prey size selection in LNP relative to KNP. Despite both carnivores expanding their dietary niche breadths in LNP relative to KNP, diet overlap did not differ between sites. This suggests that even when prey is depleted, lions and leopards can partition food resources, which likely limits competition. Despite cattle (Bos taurus) being the most abundant ungulate in LNP, lions and leopards strongly avoided cattle, supporting the notion that carnivores can perceive the risk of hunting livestock and modulate their foraging behaviour to reduce human-carnivore conflict. Should my findings reflect general patterns in carnivore dispersal and diet responses to human-use and wildlife gradients, then carnivore conservation initiates across their range should focus on prey population rehabilitation, improved livestock husbandry practices, the establishment of effective dispersal corridors and improved human-tolerance towards large carnivores. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Elephant impacts on plant diversity and structure in the Shamwari Private Game Reserve
- Authors: Halvey, Andrew Lloyd
- Date: 2024-04
- Subjects: Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape , Shamwari Game Reserve (South Africa)
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63777 , vital:73597
- Description: Many African landscapes rely on processes such as fire, tree-fall and drought in addition to herbivores to initiate change across the landscape. In the Eastern Cape, elephant have a significant impact on the community structure and diversity of the vegetation they live in. This is most likely the case for the Albany Valley Thicket and azonal riparian vegetation of Shamwari Private Game Reserve, where browsing animals, particularly megaherbivores like the black rhinoceros and elephant, are the main cause of defoliation. The presence of large herbivores creates challenges when it comes to long-term sustainability and biodiversity of the vegetation in Shamwari. Vegetation monitoring provides essential information for effective management of megaherbivores not only in Shamwari but in many other similar reserves. The aim of this study was to design a monitoring plan for the Albany Valley Thicket and riparian vegetation in Shamwari using available vegetation metrics. The vegetation was measured in permanent plots (90 m line intercept analysis per plot) in the Albany Valley Thicket and riparian vegetation of Shamwari. Plot selection was based on thicket structural integrity using NDVI score as a proxy. In all plots, thicket structure was assessed using canopy heights measured every 50 cm along the line. Detrended correspondence analysis of the species abundance data suggested three distinct structural and compositional vegetation states for thicket and riparian vegetation: dense, intermediate and open. Significant relationships between NDVI and vegetation structural metrics across the condition states indicated that NDVI could be used as a proxy for vegetation condition. Vegetation compositional metrics, however, were not always correlated to NDVI and determining species diversity for the vegetation presents additional information useful for monitoring. The monitoring recommended for the reserve is to evaluate vegetation structural integrity annually in summer using NDVI. Areas of change could then be measured for diversity as well as for change in the abundance of selected plant indicator species. This information should be used to initiate management actions if unwanted change has occurred. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Halvey, Andrew Lloyd
- Date: 2024-04
- Subjects: Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape , Shamwari Game Reserve (South Africa)
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63777 , vital:73597
- Description: Many African landscapes rely on processes such as fire, tree-fall and drought in addition to herbivores to initiate change across the landscape. In the Eastern Cape, elephant have a significant impact on the community structure and diversity of the vegetation they live in. This is most likely the case for the Albany Valley Thicket and azonal riparian vegetation of Shamwari Private Game Reserve, where browsing animals, particularly megaherbivores like the black rhinoceros and elephant, are the main cause of defoliation. The presence of large herbivores creates challenges when it comes to long-term sustainability and biodiversity of the vegetation in Shamwari. Vegetation monitoring provides essential information for effective management of megaherbivores not only in Shamwari but in many other similar reserves. The aim of this study was to design a monitoring plan for the Albany Valley Thicket and riparian vegetation in Shamwari using available vegetation metrics. The vegetation was measured in permanent plots (90 m line intercept analysis per plot) in the Albany Valley Thicket and riparian vegetation of Shamwari. Plot selection was based on thicket structural integrity using NDVI score as a proxy. In all plots, thicket structure was assessed using canopy heights measured every 50 cm along the line. Detrended correspondence analysis of the species abundance data suggested three distinct structural and compositional vegetation states for thicket and riparian vegetation: dense, intermediate and open. Significant relationships between NDVI and vegetation structural metrics across the condition states indicated that NDVI could be used as a proxy for vegetation condition. Vegetation compositional metrics, however, were not always correlated to NDVI and determining species diversity for the vegetation presents additional information useful for monitoring. The monitoring recommended for the reserve is to evaluate vegetation structural integrity annually in summer using NDVI. Areas of change could then be measured for diversity as well as for change in the abundance of selected plant indicator species. This information should be used to initiate management actions if unwanted change has occurred. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
A model for measuring and predicting stress for software developers using vital signs and activities
- Authors: Hibbers, Ilze
- Date: 2024-04
- Subjects: Machine learning , Neural networks (Computer science) , Computer software developers
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63799 , vital:73614
- Description: Occupational stress is a well-recognised issue that affects individuals in various professions and industries. Reducing occupational stress has multiple benefits, such as improving employee's health and performance. This study proposes a model to measure and predict occupational stress using data collected in a real IT office environment. Different data sources, such as questionnaires, application software (RescueTime) and Fitbit smartwatches were used for collecting heart rate (HR), facial emotions, computer interactions, and application usage. The results of the Demand Control Support and Effort and Reward questionnaires indicated that the participants experienced high social support and an average level of workload. Participants also reported their daily perceived stress and workload level using a 5- point score. The perceived stress of the participants was overall neutral. There was no correlation found between HR, interactions, fear, and meetings. K-means and Bernoulli algorithms were applied to the dataset and two well-separated clusters were formed. The centroids indicated that higher heart rates were grouped either with meetings or had a higher difference in the center point values for interactions. Silhouette scores and 5-fold-validation were used to measure the accuracy of the clusters. However, these clusters were unable to predict the daily reported stress levels. Calculations were done on the computer usage data to measure interaction speeds and time spent working, in meetings, or away from the computer. These calculations were used as input into a decision tree with the reported daily stress levels. The results of the tree helped to identify which patterns lead to stressful days. The results indicated that days with high time pressure led to more reported stress. A new, more general tree was developed, which was able to predict 82 per cent of the daily stress reported. The main discovery of the research was that stress does not have a straightforward connection with computer interactions, facial emotions, or meetings. High interactions sometimes lead to stress and other times do not. So, predicting stress involves finding patterns and how data from different data sources interact with each other. Future work will revolve around validating the model in more office environments around South Africa. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
A model for measuring and predicting stress for software developers using vital signs and activities
- Authors: Hibbers, Ilze
- Date: 2024-04
- Subjects: Machine learning , Neural networks (Computer science) , Computer software developers
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63799 , vital:73614
- Description: Occupational stress is a well-recognised issue that affects individuals in various professions and industries. Reducing occupational stress has multiple benefits, such as improving employee's health and performance. This study proposes a model to measure and predict occupational stress using data collected in a real IT office environment. Different data sources, such as questionnaires, application software (RescueTime) and Fitbit smartwatches were used for collecting heart rate (HR), facial emotions, computer interactions, and application usage. The results of the Demand Control Support and Effort and Reward questionnaires indicated that the participants experienced high social support and an average level of workload. Participants also reported their daily perceived stress and workload level using a 5- point score. The perceived stress of the participants was overall neutral. There was no correlation found between HR, interactions, fear, and meetings. K-means and Bernoulli algorithms were applied to the dataset and two well-separated clusters were formed. The centroids indicated that higher heart rates were grouped either with meetings or had a higher difference in the center point values for interactions. Silhouette scores and 5-fold-validation were used to measure the accuracy of the clusters. However, these clusters were unable to predict the daily reported stress levels. Calculations were done on the computer usage data to measure interaction speeds and time spent working, in meetings, or away from the computer. These calculations were used as input into a decision tree with the reported daily stress levels. The results of the tree helped to identify which patterns lead to stressful days. The results indicated that days with high time pressure led to more reported stress. A new, more general tree was developed, which was able to predict 82 per cent of the daily stress reported. The main discovery of the research was that stress does not have a straightforward connection with computer interactions, facial emotions, or meetings. High interactions sometimes lead to stress and other times do not. So, predicting stress involves finding patterns and how data from different data sources interact with each other. Future work will revolve around validating the model in more office environments around South Africa. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
A methodology for modernising legacy web applications: subtitle if needed. If no subtitle follow instructions in manual
- Authors: Malgraff, Maxine
- Date: 2024-04
- Subjects: Management information systems , Information technology , Application software -- Development
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64148 , vital:73657
- Description: One problem faced in the Information Systems domain is that of poorly maintained, poorly documented, and/or unmanageable systems, known as Legacy Information Systems (LISs). As a result of the everchanging web development landscape, web applications have also become susceptible to the challenges faced in keeping up with technological advances, and older applications are starting to display the characteristics of becoming Legacy Web Applications (LWAs). As retaining business process support and meeting business requirements is often necessary, one method of recovering vital LWAs is to modernise them. System modernisation aims to recover business knowledge and provide an enhanced system that overcomes the problems plagued by LISs. When planning to modernise an LWA, guidance and support are essential to ensure that the modernisation exercise is performed efficiently and effectively. Modernisation methodologies can provide this required guidance and support as they provide models, tools and techniques that serve as guiding principles for the modernisation process. Although many modernisation methodologies exist, very few offer a comprehensive approach to modernisation that provides guidelines for each modernisation phase, tools to assist in the modernisation and techniques that can be used throughout. Existing methodologies also do not cater for cases that include both the LWA and migration to modernised web-specific environments. This research study aimed to investigate modernisation methodologies and identify which methodologies, or parts thereof, could be adapted for modernising LWAs. Existing methodologies were analysed and compared using the definition of a methodology, as well as other factors that improve the modernisation process. Modernisation case studies were reviewed to identify lessons learned from these studies so that these could be considered when planning an LWA modernisation. The ARTIST methodology was the most comprehensive modernisation methodology identified from those researched and was selected as the most appropriate methodology for modernising an LWA. ARTIST was modified to the mARTIST methodology to cater for web-based environments.mARTIST was used to modernise an existing LWA, called OldMax, at an automotive manufacturer, anonymously referred to as AutoCo, to determine its ability to support the modernisation of LWAs. Additional tools and evaluation methods were also investigated and used in place of those recommended by ARTIST, where deemed appropriate for the modernisation of OldMax. Limitations set by AutoCo on the hosting and technical environments for the modernised application also required ARTIST to be adapted to better suit the use case. The steps taken during this modernisation were documented and reported on to highlight the effectiveness of mARTIST and the tools used. The result of this modernisation was that the modernised web application, ModMax, was evaluated to determine the success of the modernisation. The modernisation of OldMax to ModMax, using the mARTIST methodology, was found to be successful based on the criteria set by the ARTIST methodology. Based on this, mARTIST can successfully be used for the modernisation of LWAs. To support future modernisations, an evaluation method for determining technical feasibility was developed for LWA, and alternate tools that could be used throughout modernisation exercises were recommended. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Malgraff, Maxine
- Date: 2024-04
- Subjects: Management information systems , Information technology , Application software -- Development
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64148 , vital:73657
- Description: One problem faced in the Information Systems domain is that of poorly maintained, poorly documented, and/or unmanageable systems, known as Legacy Information Systems (LISs). As a result of the everchanging web development landscape, web applications have also become susceptible to the challenges faced in keeping up with technological advances, and older applications are starting to display the characteristics of becoming Legacy Web Applications (LWAs). As retaining business process support and meeting business requirements is often necessary, one method of recovering vital LWAs is to modernise them. System modernisation aims to recover business knowledge and provide an enhanced system that overcomes the problems plagued by LISs. When planning to modernise an LWA, guidance and support are essential to ensure that the modernisation exercise is performed efficiently and effectively. Modernisation methodologies can provide this required guidance and support as they provide models, tools and techniques that serve as guiding principles for the modernisation process. Although many modernisation methodologies exist, very few offer a comprehensive approach to modernisation that provides guidelines for each modernisation phase, tools to assist in the modernisation and techniques that can be used throughout. Existing methodologies also do not cater for cases that include both the LWA and migration to modernised web-specific environments. This research study aimed to investigate modernisation methodologies and identify which methodologies, or parts thereof, could be adapted for modernising LWAs. Existing methodologies were analysed and compared using the definition of a methodology, as well as other factors that improve the modernisation process. Modernisation case studies were reviewed to identify lessons learned from these studies so that these could be considered when planning an LWA modernisation. The ARTIST methodology was the most comprehensive modernisation methodology identified from those researched and was selected as the most appropriate methodology for modernising an LWA. ARTIST was modified to the mARTIST methodology to cater for web-based environments.mARTIST was used to modernise an existing LWA, called OldMax, at an automotive manufacturer, anonymously referred to as AutoCo, to determine its ability to support the modernisation of LWAs. Additional tools and evaluation methods were also investigated and used in place of those recommended by ARTIST, where deemed appropriate for the modernisation of OldMax. Limitations set by AutoCo on the hosting and technical environments for the modernised application also required ARTIST to be adapted to better suit the use case. The steps taken during this modernisation were documented and reported on to highlight the effectiveness of mARTIST and the tools used. The result of this modernisation was that the modernised web application, ModMax, was evaluated to determine the success of the modernisation. The modernisation of OldMax to ModMax, using the mARTIST methodology, was found to be successful based on the criteria set by the ARTIST methodology. Based on this, mARTIST can successfully be used for the modernisation of LWAs. To support future modernisations, an evaluation method for determining technical feasibility was developed for LWA, and alternate tools that could be used throughout modernisation exercises were recommended. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
Development of a numerical geohydrological model for a fractured rock aquifer in the Karoo, near Sutherland, South Africa
- Authors: Maqhubela, Akhona
- Date: 2024-04
- Subjects: Hydrogeology -- South Africa -- Northern Cape , Groundwater -- South Africa -- North Cape -- Management , Evapotranspiration
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64164 , vital:73658
- Description: The regional scale method in groundwater storage observation introduces uncertainties that hinder the evaluation of the remaining lifespan of depleted aquifers. The scarcity of precipitation data presents significant global challenge, especially in semi-arid regions. This study constructs a regional numerical hydrogeological model that identifies the potential impacts of climate change on the water balance for the South African Gravimetric Observation Station in Sutherland. The purpose of this study is to understand mechanisms controlling groundwater in the fractured rock aquifer. The climate data from the Weather forecast data over the last ten years was collected from the South African Weather Service. and groundwater levels data assessed the potential impacts of climate change on water balance components, especially precipitation and evapotranspiration. Precipitation is the primary recharge parameter in this study and had the highest level recorded in winter, with May having the highest precipitation rates of 24,62mm. The instrument conducted two profile investigations in a single day to detect geological abnormalities at various depths, achieving an impressive accuracy of up to 0.001 mV. The fact that groundwater flows from regions of higher hydraulic heads to areas of lower hydraulic charges, confirms that riverbeds in Sutherland act as preferential conduits for subsurface recharge. The profile and processed geophysical maps show low chances of getting groundwater in this observed area due to extensively great depth, approximately 150 – 210 m. The river package from MODFLOW model shows little inflow to the study nearby well locations. These model results showed a negative difference between water flowing in and out of the system of about -7m3 between 2002 and 2020. Groundwater flows faster at borehole five, where the hydraulic conductivity is large. The resulting regional hydrogeological model offered valuable insights into how climate change might influence the distribution and accessibility of groundwater resources. In the context of Sutherland, a negative groundwater budget value signaled that groundwater extraction or consumption surpassed the natural replenishment or recharge of the aquifer. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Maqhubela, Akhona
- Date: 2024-04
- Subjects: Hydrogeology -- South Africa -- Northern Cape , Groundwater -- South Africa -- North Cape -- Management , Evapotranspiration
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64164 , vital:73658
- Description: The regional scale method in groundwater storage observation introduces uncertainties that hinder the evaluation of the remaining lifespan of depleted aquifers. The scarcity of precipitation data presents significant global challenge, especially in semi-arid regions. This study constructs a regional numerical hydrogeological model that identifies the potential impacts of climate change on the water balance for the South African Gravimetric Observation Station in Sutherland. The purpose of this study is to understand mechanisms controlling groundwater in the fractured rock aquifer. The climate data from the Weather forecast data over the last ten years was collected from the South African Weather Service. and groundwater levels data assessed the potential impacts of climate change on water balance components, especially precipitation and evapotranspiration. Precipitation is the primary recharge parameter in this study and had the highest level recorded in winter, with May having the highest precipitation rates of 24,62mm. The instrument conducted two profile investigations in a single day to detect geological abnormalities at various depths, achieving an impressive accuracy of up to 0.001 mV. The fact that groundwater flows from regions of higher hydraulic heads to areas of lower hydraulic charges, confirms that riverbeds in Sutherland act as preferential conduits for subsurface recharge. The profile and processed geophysical maps show low chances of getting groundwater in this observed area due to extensively great depth, approximately 150 – 210 m. The river package from MODFLOW model shows little inflow to the study nearby well locations. These model results showed a negative difference between water flowing in and out of the system of about -7m3 between 2002 and 2020. Groundwater flows faster at borehole five, where the hydraulic conductivity is large. The resulting regional hydrogeological model offered valuable insights into how climate change might influence the distribution and accessibility of groundwater resources. In the context of Sutherland, a negative groundwater budget value signaled that groundwater extraction or consumption surpassed the natural replenishment or recharge of the aquifer. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
The on-demand continuous flow generation, separation, and utilization of monosilane gas, a feedstock for solar-grade silicon
- Authors: Mathe, Francis Matota
- Date: 2024-04
- Subjects: Chemistry, Organic , Chemistry , Silicon -- Synthesis
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/64179 , vital:73660
- Description: This research is dedicated to the development of a continuous flow process for the production and utilization of monosilane gas. The utilization of continuous flow techniques was instrumental in addressing the challenges and conditions associated with the handling of monosilane gas. Furthermore, the integration of Process Analytical Technologies (PAT) facilitated in-process monitoring and analysis. Chapter one of this research provides an extensive background and literature review encompassing the purification methods of silicon, the latest advancements in the direct synthesis of alkoxysilanes, current synthesis methods for monosilane, the various applications of monosilane, as well as the utilization of continuous flow technology and process analytical technologies. In chapter two, a detailed account of the experimental procedures employed in this research is presented. Chapter three delves into the results derived from each section of the research. The first section discusses an attempt to upscale the continuous flow synthesis of triethoxysilane, based on previous group research. Process Analytical Technologies (PAT), specifically thermocouples, were utilized in this endeavor. The study revealed temperature inconsistencies along the packed bed reactor, which had a notable impact on the reaction capabilities. The subsequent section explores the continuous flow synthesis of monosilane from triethoxysilane. A Design of Experiment (DoE) approach was employed to identify the optimal reaction conditions and compare the effectiveness of two catalysts. The study determined that Amberlyst-A26 emerged as the superior catalyst, offering stability and reasonable conversions over a 24-hour period. In a residence time of 6 minutes and at a temperature of 55 °C, the maximum triethoxysilane conversion of 100% was achieved. PAT, particularly inline FT-IR, was instrumental in monitoring catalyst activity, while continuous flow gas separation techniques facilitated the separation of monosilane. The research also demonstrated further applications of continuous flow techniques in the synthesis of monosilane from tetraethoxysilane and magnesium silicide. The former aimed to , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Mathe, Francis Matota
- Date: 2024-04
- Subjects: Chemistry, Organic , Chemistry , Silicon -- Synthesis
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/64179 , vital:73660
- Description: This research is dedicated to the development of a continuous flow process for the production and utilization of monosilane gas. The utilization of continuous flow techniques was instrumental in addressing the challenges and conditions associated with the handling of monosilane gas. Furthermore, the integration of Process Analytical Technologies (PAT) facilitated in-process monitoring and analysis. Chapter one of this research provides an extensive background and literature review encompassing the purification methods of silicon, the latest advancements in the direct synthesis of alkoxysilanes, current synthesis methods for monosilane, the various applications of monosilane, as well as the utilization of continuous flow technology and process analytical technologies. In chapter two, a detailed account of the experimental procedures employed in this research is presented. Chapter three delves into the results derived from each section of the research. The first section discusses an attempt to upscale the continuous flow synthesis of triethoxysilane, based on previous group research. Process Analytical Technologies (PAT), specifically thermocouples, were utilized in this endeavor. The study revealed temperature inconsistencies along the packed bed reactor, which had a notable impact on the reaction capabilities. The subsequent section explores the continuous flow synthesis of monosilane from triethoxysilane. A Design of Experiment (DoE) approach was employed to identify the optimal reaction conditions and compare the effectiveness of two catalysts. The study determined that Amberlyst-A26 emerged as the superior catalyst, offering stability and reasonable conversions over a 24-hour period. In a residence time of 6 minutes and at a temperature of 55 °C, the maximum triethoxysilane conversion of 100% was achieved. PAT, particularly inline FT-IR, was instrumental in monitoring catalyst activity, while continuous flow gas separation techniques facilitated the separation of monosilane. The research also demonstrated further applications of continuous flow techniques in the synthesis of monosilane from tetraethoxysilane and magnesium silicide. The former aimed to , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Statistical learning methods for photovoltaic energy output prediction
- Authors: Magaya, Aphiwe
- Date: 2024-04
- Subjects: Photovoltaic power generation , Mathematical statistics , Statistics
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64138 , vital:73656
- Description: Predicting solar energy accurately is important for the integration of more renewable energy into the grid, which can help to alleviate the energy demand on traditional coal-powered sources in South Africa. This study aims to assess several statistical learning models to predict the energy output of a 1MW photovoltaic system installed on the Nelson Mandela University South Campus in Gqeberha. Weather data (including temperature, wind speed, wind direction, precipitation, air pressure, and humidity) and solar irradiance data (including global horizontal radiation, diffuse radiation, and direct radiation) are used to predict the energy output of this system using Artificial Neural Networks (ANN), Support Vector Machines (SVM), Multiple Linear Regression (MLR), and Regression Trees (RT). The performance of each of the models was compared and the results indicated that the ANN model performed best. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Magaya, Aphiwe
- Date: 2024-04
- Subjects: Photovoltaic power generation , Mathematical statistics , Statistics
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64138 , vital:73656
- Description: Predicting solar energy accurately is important for the integration of more renewable energy into the grid, which can help to alleviate the energy demand on traditional coal-powered sources in South Africa. This study aims to assess several statistical learning models to predict the energy output of a 1MW photovoltaic system installed on the Nelson Mandela University South Campus in Gqeberha. Weather data (including temperature, wind speed, wind direction, precipitation, air pressure, and humidity) and solar irradiance data (including global horizontal radiation, diffuse radiation, and direct radiation) are used to predict the energy output of this system using Artificial Neural Networks (ANN), Support Vector Machines (SVM), Multiple Linear Regression (MLR), and Regression Trees (RT). The performance of each of the models was compared and the results indicated that the ANN model performed best. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2024
- Full Text:
- Date Issued: 2024-04
The host potential of wheel-and-axle polyaromatic compounds
- Authors: Vorgers, Jarryd Allister
- Date: 2024-04
- Subjects: Supramolecular chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64426 , vital:73704
- Description: In this work, wheel-and-axle compounds 1,4-phenylene-bis(diphenylmethanol) (H1), 1,4-phenylene-bis(di-p-tolylmethanol) (H2) and 1,4-phenylene-bis(di-p-fluorophenylmethanol) (H3) were investigated for their host behaviour in various pyridyl and heterocyclic guest mixtures. These host compounds were readily synthesized by means of Grignard addition reactions on dimethyl terephthalate, employing the aryl halides bromobenzene for H1 (73% yield), p-bromotoluene for H2 (69%) and p-bromofluorobenzene for H3 (70%). Molecular modelling calculations demonstrated that the various C-C-C angles differed between the computed low energy host conformers and those in the host molecules from their PYR-containing crystal structures. However, specified ‘torsion’ angles were in close agreement. Compound 1,4-phenylene-bis(diphenylmethanol) (H1) possessed the ability to form 1:2 host-guest (H:G) complexes with each of pyridine (PYR) and 2-, 3- and 4-methylpyridine (2MP, 3MP and 4MP). Furthermore, H1 showed preferential behaviour towards PYR and 4MP when presented with various mixtures of these four pyridines. Due to the high selectivity coefficients calculated in many instances (the selectivity coefficient, K, is a measure of the selectivity of a host compound for one particular guest in a mixture), it was demonstrated that H1 would be suitable for separations/purifications for many of the mixtures investigated in this work through host-guest chemistry strategies. (These pyridines are difficult to separate by means of the more conventional fractional distillations because of very similar boiling points.) Single crystal X-ray diffraction (SCXRD) analyses revealed that 4MP and 3MP experienced hydrogen bonds with the host molecule which were similar in distance, while the hydrogen bond distance between H1 and 4MP was shorter than that between H1 and 2MP. Furthermore, the hydrogen bond angles in complexes with the preferred PYR and 4MP guest species were more linear than in those having 2MP and 3MP. Additionally, preferred PYR and 4MP experienced significant π‧‧‧π contacts with nearby guest molecules, while disfavoured 2MP and 3MP did not interact in this fashion. Hirshfeld surface analyses demonstrated that PYR and 4MP (favoured) were involved in a greater percentage of (guest)N‧‧H(host) , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Vorgers, Jarryd Allister
- Date: 2024-04
- Subjects: Supramolecular chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64426 , vital:73704
- Description: In this work, wheel-and-axle compounds 1,4-phenylene-bis(diphenylmethanol) (H1), 1,4-phenylene-bis(di-p-tolylmethanol) (H2) and 1,4-phenylene-bis(di-p-fluorophenylmethanol) (H3) were investigated for their host behaviour in various pyridyl and heterocyclic guest mixtures. These host compounds were readily synthesized by means of Grignard addition reactions on dimethyl terephthalate, employing the aryl halides bromobenzene for H1 (73% yield), p-bromotoluene for H2 (69%) and p-bromofluorobenzene for H3 (70%). Molecular modelling calculations demonstrated that the various C-C-C angles differed between the computed low energy host conformers and those in the host molecules from their PYR-containing crystal structures. However, specified ‘torsion’ angles were in close agreement. Compound 1,4-phenylene-bis(diphenylmethanol) (H1) possessed the ability to form 1:2 host-guest (H:G) complexes with each of pyridine (PYR) and 2-, 3- and 4-methylpyridine (2MP, 3MP and 4MP). Furthermore, H1 showed preferential behaviour towards PYR and 4MP when presented with various mixtures of these four pyridines. Due to the high selectivity coefficients calculated in many instances (the selectivity coefficient, K, is a measure of the selectivity of a host compound for one particular guest in a mixture), it was demonstrated that H1 would be suitable for separations/purifications for many of the mixtures investigated in this work through host-guest chemistry strategies. (These pyridines are difficult to separate by means of the more conventional fractional distillations because of very similar boiling points.) Single crystal X-ray diffraction (SCXRD) analyses revealed that 4MP and 3MP experienced hydrogen bonds with the host molecule which were similar in distance, while the hydrogen bond distance between H1 and 4MP was shorter than that between H1 and 2MP. Furthermore, the hydrogen bond angles in complexes with the preferred PYR and 4MP guest species were more linear than in those having 2MP and 3MP. Additionally, preferred PYR and 4MP experienced significant π‧‧‧π contacts with nearby guest molecules, while disfavoured 2MP and 3MP did not interact in this fashion. Hirshfeld surface analyses demonstrated that PYR and 4MP (favoured) were involved in a greater percentage of (guest)N‧‧H(host) , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Trophic ecology and breeding success of Brown Skuas (Catharacta antarctica)
- Authors: Walker, Tegan
- Date: 2024-04
- Subjects: Birds -- Conservation , Birds -- Ecology , Birds -- Behavior -- Evolution
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64437 , vital:73710
- Description: Invasive species can impact island ecosystem processes by altering species interactions through direct competition for the same resources or by predation on insular species. Seabirds on sub-Antarctic islands are naïve to any new predators and are most at risk of local extirpation. Successful eradications of invasive mammals have yielded positive ecological responses from several seabird species. On sub-Antarctic Marion Island, populations of burrowing petrels, largely targeted by Feral Cats Felis catus, have indicated slow recovery despite the successful eradication of cats in the early 1990s. House Mice Mus musculus, have since proliferated on Marion Island, aided by a warmer climate, and are severely impacting several defenceless populations of burrowing petrels. In this thesis, I investigated the contemporary breeding productivity and diet of Brown Skuas Catharacta antarctica. At Marion Island, Brown Skua breeding productivity was associated to diet, which varied between years. Skuas feeding mostly on burrowing petrels exhibited higher breeding success than pairs mostly feeding on penguins. Higher contributions of burrowing petrels were seen in the contemporary diet of skuas compared to previous diet work. The importance of penguin prey compared to their 1980 and 2010/11 diet, was largely reduced during the 2021/22 and 2022/23 breeding seasons (53 and 51%, respectively) despite a historically high dependence on this prey (78% in 1980 and 67% in 2010/11). Penguin populations have been decreasing at the island and this may be reflected in the current skua diet. Breeding productivity was not influenced by the other factors tested, i.e. weather data (daily minimum, average and maximum air temperature; daily minimum, average, maximum wind speed; daily precipitation), distance to closest penguin colony, species of penguin or number of conspecifics in a 100 m radius around the nest. Brown Skuas breeding on Marion, Gough and Mayes islands were also used as biosamplers of burrowing petrels. These birds form a large part of the skua diet and are reflected in regurgitated skua pellets. Temporal comparisons for Marion Island indicated significant changes in burrowing petrel composition since the 1980s. Blue Petrels Halobaena caerulea and Salvin’s Prions Pachyptila salvini remained the highest contributors of skua pellets, but their proportions differed with three-fold increase in Blue Petrel and 25% decrease in Salvin’s Prion remains compared to previous studies. Further, my study indicated that smaller species of burrowing petrels such as the storm-petrels and diving petrels may be returning to Marion Island, 30 years after the eradication of cats. Pellet analyses at Marion, Gough and Mayes islands also indicated that skua diet may underrepresent larger species of petrels and soft-bodied prey. Despite these limitations, skua diet can indicate the presence of burrowing petrels during summer months, more so at Marion and Mayes islands than Gough Island, where pellet collection is difficult due to dense vegetation. Prey remains, such as wings in middens, may be a more appropriate method to investigate skua diet at Gough Island. Dominant burrowing petrels indicated by pellets at each island generally reflected the most abundant breeding species; Blue Petrels and Salvin’s Prions at Marion Island, Great Shearwaters Puffinus gravis and prion Pachyptila spp. at Gough Island, and Blue Petrels and Slender-billed Prions Pachyptila belcheri at Mayes Island. Pellets provide a non-invasive method for studying species of burrowing petrels that are challenging to monitor. This method is appropriate for studies conducted during summer months, while other studies (e.g., observations, camera traps, acoustic recordings and genetics) may be more reflective of the presence of burrowing species that breed in winter or could be used in combination with skua pellets during summer months. Population monitoring is an important part of conservation as it provides insights into population change. This thesis adds to the baseline data in terms of breeding productivity and updated trophic ecology of Brown Skuas, which will be used to inform the recovery of burrowing petrels once mice have been eradicated from Marion Island. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Walker, Tegan
- Date: 2024-04
- Subjects: Birds -- Conservation , Birds -- Ecology , Birds -- Behavior -- Evolution
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64437 , vital:73710
- Description: Invasive species can impact island ecosystem processes by altering species interactions through direct competition for the same resources or by predation on insular species. Seabirds on sub-Antarctic islands are naïve to any new predators and are most at risk of local extirpation. Successful eradications of invasive mammals have yielded positive ecological responses from several seabird species. On sub-Antarctic Marion Island, populations of burrowing petrels, largely targeted by Feral Cats Felis catus, have indicated slow recovery despite the successful eradication of cats in the early 1990s. House Mice Mus musculus, have since proliferated on Marion Island, aided by a warmer climate, and are severely impacting several defenceless populations of burrowing petrels. In this thesis, I investigated the contemporary breeding productivity and diet of Brown Skuas Catharacta antarctica. At Marion Island, Brown Skua breeding productivity was associated to diet, which varied between years. Skuas feeding mostly on burrowing petrels exhibited higher breeding success than pairs mostly feeding on penguins. Higher contributions of burrowing petrels were seen in the contemporary diet of skuas compared to previous diet work. The importance of penguin prey compared to their 1980 and 2010/11 diet, was largely reduced during the 2021/22 and 2022/23 breeding seasons (53 and 51%, respectively) despite a historically high dependence on this prey (78% in 1980 and 67% in 2010/11). Penguin populations have been decreasing at the island and this may be reflected in the current skua diet. Breeding productivity was not influenced by the other factors tested, i.e. weather data (daily minimum, average and maximum air temperature; daily minimum, average, maximum wind speed; daily precipitation), distance to closest penguin colony, species of penguin or number of conspecifics in a 100 m radius around the nest. Brown Skuas breeding on Marion, Gough and Mayes islands were also used as biosamplers of burrowing petrels. These birds form a large part of the skua diet and are reflected in regurgitated skua pellets. Temporal comparisons for Marion Island indicated significant changes in burrowing petrel composition since the 1980s. Blue Petrels Halobaena caerulea and Salvin’s Prions Pachyptila salvini remained the highest contributors of skua pellets, but their proportions differed with three-fold increase in Blue Petrel and 25% decrease in Salvin’s Prion remains compared to previous studies. Further, my study indicated that smaller species of burrowing petrels such as the storm-petrels and diving petrels may be returning to Marion Island, 30 years after the eradication of cats. Pellet analyses at Marion, Gough and Mayes islands also indicated that skua diet may underrepresent larger species of petrels and soft-bodied prey. Despite these limitations, skua diet can indicate the presence of burrowing petrels during summer months, more so at Marion and Mayes islands than Gough Island, where pellet collection is difficult due to dense vegetation. Prey remains, such as wings in middens, may be a more appropriate method to investigate skua diet at Gough Island. Dominant burrowing petrels indicated by pellets at each island generally reflected the most abundant breeding species; Blue Petrels and Salvin’s Prions at Marion Island, Great Shearwaters Puffinus gravis and prion Pachyptila spp. at Gough Island, and Blue Petrels and Slender-billed Prions Pachyptila belcheri at Mayes Island. Pellets provide a non-invasive method for studying species of burrowing petrels that are challenging to monitor. This method is appropriate for studies conducted during summer months, while other studies (e.g., observations, camera traps, acoustic recordings and genetics) may be more reflective of the presence of burrowing species that breed in winter or could be used in combination with skua pellets during summer months. Population monitoring is an important part of conservation as it provides insights into population change. This thesis adds to the baseline data in terms of breeding productivity and updated trophic ecology of Brown Skuas, which will be used to inform the recovery of burrowing petrels once mice have been eradicated from Marion Island. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Evaluation of road surface distresses using GPS and GIS techniques: a case study of the City of Johannesburg, South Africa
- Authors: Tsedu, Rinae
- Date: 2024-04
- Subjects: Global Positioning System South Africa -- Johannesburg , Navigation -- Technological innovations , Geographic information systems -- South Africa -- Johannesburg
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64401 , vital:73695
- Description: Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Tsedu, Rinae
- Date: 2024-04
- Subjects: Global Positioning System South Africa -- Johannesburg , Navigation -- Technological innovations , Geographic information systems -- South Africa -- Johannesburg
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64401 , vital:73695
- Description: Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Synthesis and applications of hydroxyl-functionalized chemosensors for selective detection of ions in aqueous systems
- Authors: Hamukoshi, Simeon Shiweda
- Date: 2024-04
- Subjects: Molecular recognition , Solution (Chemistry) , Water chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63787 , vital:73613
- Description: Fluorescent molecular chemosensors are crucial tools for monitoring toxic metal ions and environmental compounds that pose risks to both humans and wildlife. Continuous sensing is essential for early detection, and chemosensors offer a sensitive and straightforward approach by detecting challenging analyte’s through optical absorption and fluorescence. Current detection methods, such as flame photometry and mass spectrometry, can be expensive, destructive, and impractical for continuous monitoring. Consequently, fluorescent-based methods present a promising, simple, and highly sensitive alternative for chemical recognition and monitoring. In this project, we successfully synthesized ten highly selective small hydroxyl containing molecule fluorescent and colorimetric sensors; Oxime Dye (OD), Small Sensor 1 (SS1), Small Sensor 2 (SS2), Quinoline Dye 1 (QD1), Quinoline Dye 2 (QD2), Quinoline Dye 3 (QD3), Coumarin Dye 1 (CD1), Coumarin Dye 2 (CD2), Naphthalene Dye 1 (ND1), Naphthalene Dye 2 (ND2). These chemosensors contained benzothiazole, naphthalene, quinoline, and coumarin fluorophores. These sensors facilitate both quantitative and qualitative assessment of cationic and anionic species in aqueous organic media. The chemosensors were synthesized using modified Schiff base, azo dye, and oxime-based reactions, enhancing binding and selectivity with analyte’s. They exhibited selectivity towards various metal ions (Cu2+, Fe2+, Ni2+, and Hg2+) and anions (hydroxyl and cyanate), characterized by distinct absorption bands and significant fluorescent quenching and enhancement. While some sensors were selective towards both cations and anions, others exclusively targeted cations, showing lower selectivity or sensitivity towards anions upon further testing. Conversely, certain sensors were selective towards anions, demonstrating reduced sensitivity or selectivity towards the tested cations. The oxime-based chemosensor, OD, was obtained through an oxime-based reaction. The sensor demonstrates remarkable selectivity for Cu2+ and cyanate ions. During titration experiments, the interaction of Cu2+ with OD resulted in a noticeable fluorescence quenching effect, while the presence of OCN ions led to fluorescence enhancement. These distinct behaviors strongly suggest the formation of specific 1:1 complexes between OD and Cu2+ or OCN ions, a conclusion supported by detailed analysis using the Jobs plot technique. In addition to the fluorescence studies, investigations into the influence of pH on the sensor OD, as well as its complexes with Cu2+ and OCN, were conducted to determine the optimum pH conditions for their operation. Moreover, reversible behavior of the complexes was explored in the presence of EDTA, revealing that only the OD-OCN complex displayed reversibility. Furthermore, molecular modeling studies were performed to validate the binding units and calculate the energy differences between the sensor and its respective complexes. Additionally, four chemosensors (SS1, SS2, CD2, and QD2) were synthesized and characterized using Schiff-based reactions, showcasing their unique absorption behaviors. SS1 and SS2, characterized by benzothiazole fluorophores, demonstrated high sensitivity to hydroxyl anions. Jobs plot studies revealed a stable 1:1 binding stoichiometry. Chemosensor CD2, incorporating a coumarin fluorophore, was structurally confirmed but showed no significant spectral changes when screened with various ions. Chemosensor QD2 exhibited remarkable selectivity for Fe2+ ions, and stable 1:1 complexes were confirmed. Further molecular modeling studies were conducted to identify potential binding sites. Furthermore, five chemosensors (CD1, CD3, QD1, ND1, and ND2) were synthesized and characterized using azo dye reactions, revealing their unique absorption behaviors. Chemosensor CD1 showed high selectivity towards Hg2+ under both absorption and emission spectroscopy. Job's plot studies confirmed a stable 1:1 complex formation. The presence of competing cations did not affect complex formation, emphasizing its stability and selectivity. Another coumarin-containing dye chemosensor, CD3, was synthesized as a novel chemosensor. In the presence of TBA anionic solutions, CD3 exhibited strong absorption bands and selectivity for OH- ions, forming a stable complex with them. Quantitative studies, including the determination of LOD and LOQ, were also conducted. The binding stoichiometry of 1:1 between CD3 and OH- was established through Job's plot analysis. Lastly, two naphthalene dyes were synthesized. However, they did not exhibit selectivity towards cations or anions. Interestingly, their absorption spectra were affected by the change in solvent system, a concept worth exploring in future work. Chemosensor ND1 and ND2 did not show any cation or anion selectivity. However, they demonstrated different spectra and colour responses to cations and anions in different water-DMSO solvent systems. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Hamukoshi, Simeon Shiweda
- Date: 2024-04
- Subjects: Molecular recognition , Solution (Chemistry) , Water chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63787 , vital:73613
- Description: Fluorescent molecular chemosensors are crucial tools for monitoring toxic metal ions and environmental compounds that pose risks to both humans and wildlife. Continuous sensing is essential for early detection, and chemosensors offer a sensitive and straightforward approach by detecting challenging analyte’s through optical absorption and fluorescence. Current detection methods, such as flame photometry and mass spectrometry, can be expensive, destructive, and impractical for continuous monitoring. Consequently, fluorescent-based methods present a promising, simple, and highly sensitive alternative for chemical recognition and monitoring. In this project, we successfully synthesized ten highly selective small hydroxyl containing molecule fluorescent and colorimetric sensors; Oxime Dye (OD), Small Sensor 1 (SS1), Small Sensor 2 (SS2), Quinoline Dye 1 (QD1), Quinoline Dye 2 (QD2), Quinoline Dye 3 (QD3), Coumarin Dye 1 (CD1), Coumarin Dye 2 (CD2), Naphthalene Dye 1 (ND1), Naphthalene Dye 2 (ND2). These chemosensors contained benzothiazole, naphthalene, quinoline, and coumarin fluorophores. These sensors facilitate both quantitative and qualitative assessment of cationic and anionic species in aqueous organic media. The chemosensors were synthesized using modified Schiff base, azo dye, and oxime-based reactions, enhancing binding and selectivity with analyte’s. They exhibited selectivity towards various metal ions (Cu2+, Fe2+, Ni2+, and Hg2+) and anions (hydroxyl and cyanate), characterized by distinct absorption bands and significant fluorescent quenching and enhancement. While some sensors were selective towards both cations and anions, others exclusively targeted cations, showing lower selectivity or sensitivity towards anions upon further testing. Conversely, certain sensors were selective towards anions, demonstrating reduced sensitivity or selectivity towards the tested cations. The oxime-based chemosensor, OD, was obtained through an oxime-based reaction. The sensor demonstrates remarkable selectivity for Cu2+ and cyanate ions. During titration experiments, the interaction of Cu2+ with OD resulted in a noticeable fluorescence quenching effect, while the presence of OCN ions led to fluorescence enhancement. These distinct behaviors strongly suggest the formation of specific 1:1 complexes between OD and Cu2+ or OCN ions, a conclusion supported by detailed analysis using the Jobs plot technique. In addition to the fluorescence studies, investigations into the influence of pH on the sensor OD, as well as its complexes with Cu2+ and OCN, were conducted to determine the optimum pH conditions for their operation. Moreover, reversible behavior of the complexes was explored in the presence of EDTA, revealing that only the OD-OCN complex displayed reversibility. Furthermore, molecular modeling studies were performed to validate the binding units and calculate the energy differences between the sensor and its respective complexes. Additionally, four chemosensors (SS1, SS2, CD2, and QD2) were synthesized and characterized using Schiff-based reactions, showcasing their unique absorption behaviors. SS1 and SS2, characterized by benzothiazole fluorophores, demonstrated high sensitivity to hydroxyl anions. Jobs plot studies revealed a stable 1:1 binding stoichiometry. Chemosensor CD2, incorporating a coumarin fluorophore, was structurally confirmed but showed no significant spectral changes when screened with various ions. Chemosensor QD2 exhibited remarkable selectivity for Fe2+ ions, and stable 1:1 complexes were confirmed. Further molecular modeling studies were conducted to identify potential binding sites. Furthermore, five chemosensors (CD1, CD3, QD1, ND1, and ND2) were synthesized and characterized using azo dye reactions, revealing their unique absorption behaviors. Chemosensor CD1 showed high selectivity towards Hg2+ under both absorption and emission spectroscopy. Job's plot studies confirmed a stable 1:1 complex formation. The presence of competing cations did not affect complex formation, emphasizing its stability and selectivity. Another coumarin-containing dye chemosensor, CD3, was synthesized as a novel chemosensor. In the presence of TBA anionic solutions, CD3 exhibited strong absorption bands and selectivity for OH- ions, forming a stable complex with them. Quantitative studies, including the determination of LOD and LOQ, were also conducted. The binding stoichiometry of 1:1 between CD3 and OH- was established through Job's plot analysis. Lastly, two naphthalene dyes were synthesized. However, they did not exhibit selectivity towards cations or anions. Interestingly, their absorption spectra were affected by the change in solvent system, a concept worth exploring in future work. Chemosensor ND1 and ND2 did not show any cation or anion selectivity. However, they demonstrated different spectra and colour responses to cations and anions in different water-DMSO solvent systems. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04