Molecular simulations of potential agents and targets of Alzheimer’s disease
- Authors: Joli, Luxolo
- Date: 2020
- Subjects: Alzheimer's disease -- Chemotherapy , Alzheimer's disease -- Treatment , Ligands (Biochemistry) , Proteins -- Chemistry , Molecular dynamics -- Simulation methods
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146411 , vital:38523
- Description: Alzheimer's Disease (AD) is a neurodegenerative brain disorder that was first discovered in 1901 by Dr Aloïs Alzheimer and was later reported publicly in 1906. The German doctor had a 51-yearold woman patient called Auguste Deter, who was suffering from a rare brain disorder with early signs of memory loss and cognition. Alzheimer's Disease is the most common type of dementia that affects people with the age of 65 years and older. There is no single known cause of Alzheimer’s disease however, amyloid β-peptide (Aβ1–40/42) was found to be at the centre of AD pathogenesis and this connection was referred as “amyloid hypothesis”. It is suspected that an accumulation of amyloid β-peptide is a major contributor to neuronal dysfunction and degeneration. Alzheimer’s disease is complex and therefore, currently there is no medication available that treats the disease. However, there are approaches that focus on helping people maintain mental function, manage behavioral symptoms, and slow down the symptoms of disease. According to South Africa’s 2011 census, there are approximately 2.2 million people in South Africa with some form of dementia and therefore there is a need to find a treatment for the disease. This study aims to find agents and targets of Alzheimer’s Disease by using different computational techniques such as molecular modelling. The study will use compounds from the South African Compounds Database (SANCDB) and the following therapeutic targets α-, β- and γ-secretase, acetylcholinesterase, tau protein and neprilysin. A successful High-throughput Virtual Screening (HTVS) study to determine lead compounds was performed using a computational program called KNIME. Molecular docking was achieved with GLIDE as it allows for exhaustive ligand flexibility. The docking calculations were carried out using the high level of precision XP (extra precision) for enhanced docking accuracy. The binding affinities (docking scores) for the best bound ligands obtained from docking were in the order of -5 kcal/mol or less. The ligandSANC00370 was the best binding ligand against the protein 1J1C_B and had the best binding energy of -13.94 kcal/mol compared to others. The receptor-ligand complexes were analyzed using the interaction diagrams obtained from the Discovery Studio Visualizer and Maestro programs. Molecular Dynamics simulations were performed on the complexes obtained from docking to help in optimizing their interactions. The simulations were performed using the Desmond tool with the OPLS3 force field. 100 ns simulations were performed for six systems with the best docking score results epresenting each of the therapeutic targets and for the other complex systems, 50 ns simulations were performed. The Desmond simulations were analyzed using the Simulations Interaction Diagrams such as PL-RMSD, L-RMSF, P-RMSF, L-Torsions, P-SSE, LP-Contacts and L-Properties. Maestro was used to visualize the stability of the ligands in the active site during the simulation. All 13 Desmond simulations were successful however, there were 9 simulations which produced satisfactory results while the others were nsatisfactory. Based on the molecular docking and Molecular Dynamics results of this study, 9 potential targets and 6 potential agents were obtained successfully and can be studied further as therapeutics for Alzheimer’s Disease.
- Full Text:
- Date Issued: 2020
- Authors: Joli, Luxolo
- Date: 2020
- Subjects: Alzheimer's disease -- Chemotherapy , Alzheimer's disease -- Treatment , Ligands (Biochemistry) , Proteins -- Chemistry , Molecular dynamics -- Simulation methods
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146411 , vital:38523
- Description: Alzheimer's Disease (AD) is a neurodegenerative brain disorder that was first discovered in 1901 by Dr Aloïs Alzheimer and was later reported publicly in 1906. The German doctor had a 51-yearold woman patient called Auguste Deter, who was suffering from a rare brain disorder with early signs of memory loss and cognition. Alzheimer's Disease is the most common type of dementia that affects people with the age of 65 years and older. There is no single known cause of Alzheimer’s disease however, amyloid β-peptide (Aβ1–40/42) was found to be at the centre of AD pathogenesis and this connection was referred as “amyloid hypothesis”. It is suspected that an accumulation of amyloid β-peptide is a major contributor to neuronal dysfunction and degeneration. Alzheimer’s disease is complex and therefore, currently there is no medication available that treats the disease. However, there are approaches that focus on helping people maintain mental function, manage behavioral symptoms, and slow down the symptoms of disease. According to South Africa’s 2011 census, there are approximately 2.2 million people in South Africa with some form of dementia and therefore there is a need to find a treatment for the disease. This study aims to find agents and targets of Alzheimer’s Disease by using different computational techniques such as molecular modelling. The study will use compounds from the South African Compounds Database (SANCDB) and the following therapeutic targets α-, β- and γ-secretase, acetylcholinesterase, tau protein and neprilysin. A successful High-throughput Virtual Screening (HTVS) study to determine lead compounds was performed using a computational program called KNIME. Molecular docking was achieved with GLIDE as it allows for exhaustive ligand flexibility. The docking calculations were carried out using the high level of precision XP (extra precision) for enhanced docking accuracy. The binding affinities (docking scores) for the best bound ligands obtained from docking were in the order of -5 kcal/mol or less. The ligandSANC00370 was the best binding ligand against the protein 1J1C_B and had the best binding energy of -13.94 kcal/mol compared to others. The receptor-ligand complexes were analyzed using the interaction diagrams obtained from the Discovery Studio Visualizer and Maestro programs. Molecular Dynamics simulations were performed on the complexes obtained from docking to help in optimizing their interactions. The simulations were performed using the Desmond tool with the OPLS3 force field. 100 ns simulations were performed for six systems with the best docking score results epresenting each of the therapeutic targets and for the other complex systems, 50 ns simulations were performed. The Desmond simulations were analyzed using the Simulations Interaction Diagrams such as PL-RMSD, L-RMSF, P-RMSF, L-Torsions, P-SSE, LP-Contacts and L-Properties. Maestro was used to visualize the stability of the ligands in the active site during the simulation. All 13 Desmond simulations were successful however, there were 9 simulations which produced satisfactory results while the others were nsatisfactory. Based on the molecular docking and Molecular Dynamics results of this study, 9 potential targets and 6 potential agents were obtained successfully and can be studied further as therapeutics for Alzheimer’s Disease.
- Full Text:
- Date Issued: 2020
Nutrient removal and biofuel potential of MaB-floc biomass from an integrated algal pond system treating domestic sewage
- Authors: Sibelo, Linda
- Date: 2020
- Subjects: Biomass energy , Waste products as fuel , Algal biofuels , Sewage -- Purification -- Nutrient removal
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/144955 , vital:38395
- Description: Integrated algal pond systems (IAPS) are a passive water treatment technology derived from the Oswald designed advanced integrated wastewater pond systems (AIWPS®) and effect wastewater treatment based on biological activity of microorganisms within the system, solar energy and gravity. The technology consists of an advanced facultative pond (AFP), a series of interconnected high rate algal oxidation ponds (HRAOP) and algal settling ponds. The symbiotic relationship between microalgae and bacteria facilitated by paddlewheel mixing of HRAOP results in the formation of biomass aggregates known as MaB-flocs. MaB-floc formation enhances nutrient abstraction, gravitational sedimentation and separation from water hence forming two product streams; recyclable water and biomass, both with valorisation potential. This work aimed to determine the suitability of MaB-floc biomass generated in the HRAOP of an IAPS treating domestic sewage as feedstock for biofuel production based on the content of carbohydrate and lipid. Nutrient removal efficiency, biomass productivity and bulk lipid and carbohydrate concentration were monitored for two consecutive three-month periods in the winter and summer seasons of 2018/19. Maximum removal efficiencies of nitrogen and phosphorus were determined as 71% and 75% respectively, demonstrating the efficiency of IAPS as a wastewater treatment technology. MaB-floc biomass productivity in winter and summer was 9.4 g/m2/d and 16.5 g/m2/d respectively indicating the heavy influence of seasonal temperature, possibly day length, and solar irradiation on biomass productivity in the HRAOP. Summer productivity was lower than the maximum theoretical productivity of 25 g/m2/d possibly due to photoinhibition of photosynthesis as well as grazing pressures caused by the proliferation of rotifers mainly of the Brachionus genus. MaB-floc biomass consistently contained higher amounts of carbohydrate than lipid despite the changes in species dominance from Scenedesmus sp. and Desmodesmus sp. in winter to Pediastrum sp. in summer. Variations in MaB-floc biomass carbohydrate content were linked to changes in nitrogen concentration, mainly in the form of nitrates. Lower nitrogen concentration significantly increased the carbohydrate content of MaB-floc biomass from 17.5 ± 0.15% to 33.5 ± 0.3 % recorded in summer. In winter, biomass carbohydrate increased from 18.3 ± 1.2% to 35.8 ± 0.3%.To induce accumulation of carbohydrates through nitrogen starvation, isolated microalgal species native to the HRAOPs of the IAPS at Institute for Environmental Biotechnology Rhodes University(EBRU) were used. The outcome from the laboratory studies showed that carbon partitioning within isolated strains could be altered from carbohydrate to lipid which is more energy-rich. Hence, exploring the biodiesel production option using HRAOP MaB-floc biomass, which had a lipid content ranging between 12.1 ± 0.64 % and 13.9 ± 0.5 %, would require a preconditioning step in the form of nitrogen starvation to enhance its lipid content. Overall, the outcome of outdoor monitoring studies on biomass biochemical composition indicated that HRAOPs operating under natural environmental conditions preferentially generated a biomass rich in carbohydrate. Therefore, anaerobic digestion may be a more viable option for HRAOP MaB-floc biomass because of the high carbohydrate levels ranging between 24.9 ± 0.6 % and 25.6 ± 1.3 % of the dry MaB-floc biomass weight. Despite the low biomass C/N ratio (7.1 to 7.8), the MaB-floc biomass can be anaerobically co-digested with a higher C/N ratio (24) substrate such as in-pond digester sludge, to improve methane yields calculated to be between 0.31 m3 CH4/ kg MaB-floc biomass and 0.33 m3 CH4/ kg MaB-floc biomass. Anaerobic digestion of biomass also produces CO2 which can be recovered and added to HRAOPs to enhance MaB-floc biomass productivity while lowering greenhouse gas emissions from a wastewater treatment plant. The digestate from the anaerobic process, which is rich in nitrogen and phosphorus can be used as a biofertiliser. Thus, a potential MaB-floc biomass biorefinery consisting of biogas and bio-fertiliser pathways can be established using IAPS treating sewage as the platform technology. IAPS is a system designed to operate in a way that is passive and without substantial environmental impact but technological innovations and a reduction in the size of the system are required to make the technology more acceptable.
- Full Text:
- Date Issued: 2020
- Authors: Sibelo, Linda
- Date: 2020
- Subjects: Biomass energy , Waste products as fuel , Algal biofuels , Sewage -- Purification -- Nutrient removal
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/144955 , vital:38395
- Description: Integrated algal pond systems (IAPS) are a passive water treatment technology derived from the Oswald designed advanced integrated wastewater pond systems (AIWPS®) and effect wastewater treatment based on biological activity of microorganisms within the system, solar energy and gravity. The technology consists of an advanced facultative pond (AFP), a series of interconnected high rate algal oxidation ponds (HRAOP) and algal settling ponds. The symbiotic relationship between microalgae and bacteria facilitated by paddlewheel mixing of HRAOP results in the formation of biomass aggregates known as MaB-flocs. MaB-floc formation enhances nutrient abstraction, gravitational sedimentation and separation from water hence forming two product streams; recyclable water and biomass, both with valorisation potential. This work aimed to determine the suitability of MaB-floc biomass generated in the HRAOP of an IAPS treating domestic sewage as feedstock for biofuel production based on the content of carbohydrate and lipid. Nutrient removal efficiency, biomass productivity and bulk lipid and carbohydrate concentration were monitored for two consecutive three-month periods in the winter and summer seasons of 2018/19. Maximum removal efficiencies of nitrogen and phosphorus were determined as 71% and 75% respectively, demonstrating the efficiency of IAPS as a wastewater treatment technology. MaB-floc biomass productivity in winter and summer was 9.4 g/m2/d and 16.5 g/m2/d respectively indicating the heavy influence of seasonal temperature, possibly day length, and solar irradiation on biomass productivity in the HRAOP. Summer productivity was lower than the maximum theoretical productivity of 25 g/m2/d possibly due to photoinhibition of photosynthesis as well as grazing pressures caused by the proliferation of rotifers mainly of the Brachionus genus. MaB-floc biomass consistently contained higher amounts of carbohydrate than lipid despite the changes in species dominance from Scenedesmus sp. and Desmodesmus sp. in winter to Pediastrum sp. in summer. Variations in MaB-floc biomass carbohydrate content were linked to changes in nitrogen concentration, mainly in the form of nitrates. Lower nitrogen concentration significantly increased the carbohydrate content of MaB-floc biomass from 17.5 ± 0.15% to 33.5 ± 0.3 % recorded in summer. In winter, biomass carbohydrate increased from 18.3 ± 1.2% to 35.8 ± 0.3%.To induce accumulation of carbohydrates through nitrogen starvation, isolated microalgal species native to the HRAOPs of the IAPS at Institute for Environmental Biotechnology Rhodes University(EBRU) were used. The outcome from the laboratory studies showed that carbon partitioning within isolated strains could be altered from carbohydrate to lipid which is more energy-rich. Hence, exploring the biodiesel production option using HRAOP MaB-floc biomass, which had a lipid content ranging between 12.1 ± 0.64 % and 13.9 ± 0.5 %, would require a preconditioning step in the form of nitrogen starvation to enhance its lipid content. Overall, the outcome of outdoor monitoring studies on biomass biochemical composition indicated that HRAOPs operating under natural environmental conditions preferentially generated a biomass rich in carbohydrate. Therefore, anaerobic digestion may be a more viable option for HRAOP MaB-floc biomass because of the high carbohydrate levels ranging between 24.9 ± 0.6 % and 25.6 ± 1.3 % of the dry MaB-floc biomass weight. Despite the low biomass C/N ratio (7.1 to 7.8), the MaB-floc biomass can be anaerobically co-digested with a higher C/N ratio (24) substrate such as in-pond digester sludge, to improve methane yields calculated to be between 0.31 m3 CH4/ kg MaB-floc biomass and 0.33 m3 CH4/ kg MaB-floc biomass. Anaerobic digestion of biomass also produces CO2 which can be recovered and added to HRAOPs to enhance MaB-floc biomass productivity while lowering greenhouse gas emissions from a wastewater treatment plant. The digestate from the anaerobic process, which is rich in nitrogen and phosphorus can be used as a biofertiliser. Thus, a potential MaB-floc biomass biorefinery consisting of biogas and bio-fertiliser pathways can be established using IAPS treating sewage as the platform technology. IAPS is a system designed to operate in a way that is passive and without substantial environmental impact but technological innovations and a reduction in the size of the system are required to make the technology more acceptable.
- Full Text:
- Date Issued: 2020
Observations of diffuse radio emission in the Abell 773 galaxy cluster
- Authors: Sichone, Gift L
- Date: 2020
- Subjects: Galaxies -- Clusters -- Observations , Radio astronomy -- Observations , Astrophysics -- South Africa , Westerbork Radio Telescope , A773 galaxy cluster , Astronomy -- Observations , Radio sources (Astronomy
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/144945 , vital:38394
- Description: In this thesis, we present 18 and 21 cm observations of the A773 galaxy cluster observed with the Westerbork radio telescope. The final 18 and 21 cm images achieve a noise level of 0.018 mJy beam‾ 1 and 0.025 mJy beam-1 respectively. After subtracting the compact sources, the low resolution images show evidence of a radio halo at 18 cm, whereas its presence is more uncertain in the low resolution 21 cm images due the presence of residual sidelobes from bright sources. In the joint analysis of both frequencies, the radio halo has a 5.37 arcmin2 area with a 6.76 mJy flux density. Further observations and analysis are, however, required to fully characterize its properties.
- Full Text:
- Date Issued: 2020
- Authors: Sichone, Gift L
- Date: 2020
- Subjects: Galaxies -- Clusters -- Observations , Radio astronomy -- Observations , Astrophysics -- South Africa , Westerbork Radio Telescope , A773 galaxy cluster , Astronomy -- Observations , Radio sources (Astronomy
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/144945 , vital:38394
- Description: In this thesis, we present 18 and 21 cm observations of the A773 galaxy cluster observed with the Westerbork radio telescope. The final 18 and 21 cm images achieve a noise level of 0.018 mJy beam‾ 1 and 0.025 mJy beam-1 respectively. After subtracting the compact sources, the low resolution images show evidence of a radio halo at 18 cm, whereas its presence is more uncertain in the low resolution 21 cm images due the presence of residual sidelobes from bright sources. In the joint analysis of both frequencies, the radio halo has a 5.37 arcmin2 area with a 6.76 mJy flux density. Further observations and analysis are, however, required to fully characterize its properties.
- Full Text:
- Date Issued: 2020
Observations of diffuse radio emission in the Perseus Galaxy Cluster
- Authors: Mungwariri, Clemence
- Date: 2020
- Subjects: Galaxies -- Clusters , Radio sources (Astronomy) , Radio interferometers , Perseus Galaxy Cluster , Diffuse radio emission
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/143325 , vital:38233
- Description: In this thesis we analysed Westerbork observations of the Perseus Galaxy Cluster at 1380 MHz. Observations consist of two different pointings, covering a total of ∼ 0.5 square degrees, one including the known mini halo and the source 3C 84, the other centred on the source 3C 83.1 B. We obtained images with 83 μJy beam⁻¹ and 240 μJy beam⁻¹ noise rms for the two pointings respectively. We achieved a 60000 : 1 dynamic range in the image containing the bright 3C 84 source. We imaged the mini halo surrounding 3C 84 at high sensitivity, measuring its diameter to be ∼140 kpc and its power 4 x 10²⁴ W Hz⁻¹. Its morphology agrees quite well with that observed at 240 MHz (e.g. Gendron-Marsolais et al., 2017). We measured the flux density of 3C 84 to be 20.5 ± 0.4 Jy at the 2007 epoch, consistent with a factor of ∼2 increase since the 1960s.
- Full Text:
- Date Issued: 2020
- Authors: Mungwariri, Clemence
- Date: 2020
- Subjects: Galaxies -- Clusters , Radio sources (Astronomy) , Radio interferometers , Perseus Galaxy Cluster , Diffuse radio emission
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/143325 , vital:38233
- Description: In this thesis we analysed Westerbork observations of the Perseus Galaxy Cluster at 1380 MHz. Observations consist of two different pointings, covering a total of ∼ 0.5 square degrees, one including the known mini halo and the source 3C 84, the other centred on the source 3C 83.1 B. We obtained images with 83 μJy beam⁻¹ and 240 μJy beam⁻¹ noise rms for the two pointings respectively. We achieved a 60000 : 1 dynamic range in the image containing the bright 3C 84 source. We imaged the mini halo surrounding 3C 84 at high sensitivity, measuring its diameter to be ∼140 kpc and its power 4 x 10²⁴ W Hz⁻¹. Its morphology agrees quite well with that observed at 240 MHz (e.g. Gendron-Marsolais et al., 2017). We measured the flux density of 3C 84 to be 20.5 ± 0.4 Jy at the 2007 epoch, consistent with a factor of ∼2 increase since the 1960s.
- Full Text:
- Date Issued: 2020
Performance of an integrated algal pond for treatment of domestic sewage: a process audit
- Authors: Dube, Anele
- Date: 2020
- Subjects: Water -- Purification , Sewage -- Purification -- Anaerobic treatment , Algae -- Biotechnology , Waste disposal -- South Africa , Integrated algae pond systems (IAPS)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167043 , vital:41432
- Description: Integrated algae pond systems (IAPS) are energy efficient, robust, passive systems that use the principles of fermentation, photosynthesis and microbial metabolism to remediate wastewater, producing a good quality effluent with reuse potential. In addition to the treatment of wastewater, IAPS have the ability to generate two additional product streams viz. biogas and biomass. The latter adds to the attractiveness of the system. However, the implementation of this technology, like many passive systems, has remained limited at a commercial scale, and the inclination is still towards grey technologies. The aim of this research was to investigate the capabilities and potential of a demonstration-scale IAPS and use results obtained to establish a process audit framework. The aspects considered for the audit included performance efficiency, effluent water quality, biomass composition, quantity and productivity within the ponds, and cost analysis of operation and maintenance over a 9-year period. Plant performance was closely monitored during the course of the study and this led to a review of previously adopted plant management strategies. Troubleshooting exercises were also carried out when plant performance declined. Results showed that IAPS efficiently reduced standard water parameters with the exception of pH, dissolved oxygen, and nitrate whose values increased from raw influent to final effluent. The following water quality parameters were established for the final effluent: total suspended solids 55 ± 7.1 mg. L-1 (n = 28); chemical oxygen demand 94.1 ± 10.6 mg. L-1 (n = 28) (after removal of algae); pH 9.9 ± 0.01 (n = 26); ammonium nitrogen 1.7 ± 0.3 mg. L-1 (n = 25); nitrate 3.3 ± 0.6 mg. L-1 (n = 25); ortho-phosphate 1.6 ± 0.2 mg. L-1 (n = 25); electrical conductivity 98.7 ± 2.0 mS m-1 (n = 26) and faecal coliforms (per 100 mL) 1482.6 ± 636.0 (n = 24). The final effluent measured consistently high chemical oxygen demand and total suspended solids, however close analysis showed that total suspended solids could be controlled by increasing the frequency of removal of settled biomass within the settling ponds. Biomass produced contained microalgae, bacteria, metazoa, and protozoa. The biomass productivity achieved was as high as 130.6 kg ha-1 d-1; however, about 33% was lost to the final effluent due to inadequate settling. Results obtained during the course of this study and outcomes of earlier work on IAPS are taken as the baseline to determine parameters needed for the development of the process audit framework. Techniques utilised to derive the blue print process audit protocol for IAPS included a turtle diagram, a flow diagram and a checklist. Attention to plant management proved vital in determining overall performance. Cost, including operating and maintenance, of treating water using the demonstration scale system on a per person equivalent per year basis was determined as ZAR 123.87 (where, ZAR to USD = 0.07).
- Full Text:
- Date Issued: 2020
- Authors: Dube, Anele
- Date: 2020
- Subjects: Water -- Purification , Sewage -- Purification -- Anaerobic treatment , Algae -- Biotechnology , Waste disposal -- South Africa , Integrated algae pond systems (IAPS)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167043 , vital:41432
- Description: Integrated algae pond systems (IAPS) are energy efficient, robust, passive systems that use the principles of fermentation, photosynthesis and microbial metabolism to remediate wastewater, producing a good quality effluent with reuse potential. In addition to the treatment of wastewater, IAPS have the ability to generate two additional product streams viz. biogas and biomass. The latter adds to the attractiveness of the system. However, the implementation of this technology, like many passive systems, has remained limited at a commercial scale, and the inclination is still towards grey technologies. The aim of this research was to investigate the capabilities and potential of a demonstration-scale IAPS and use results obtained to establish a process audit framework. The aspects considered for the audit included performance efficiency, effluent water quality, biomass composition, quantity and productivity within the ponds, and cost analysis of operation and maintenance over a 9-year period. Plant performance was closely monitored during the course of the study and this led to a review of previously adopted plant management strategies. Troubleshooting exercises were also carried out when plant performance declined. Results showed that IAPS efficiently reduced standard water parameters with the exception of pH, dissolved oxygen, and nitrate whose values increased from raw influent to final effluent. The following water quality parameters were established for the final effluent: total suspended solids 55 ± 7.1 mg. L-1 (n = 28); chemical oxygen demand 94.1 ± 10.6 mg. L-1 (n = 28) (after removal of algae); pH 9.9 ± 0.01 (n = 26); ammonium nitrogen 1.7 ± 0.3 mg. L-1 (n = 25); nitrate 3.3 ± 0.6 mg. L-1 (n = 25); ortho-phosphate 1.6 ± 0.2 mg. L-1 (n = 25); electrical conductivity 98.7 ± 2.0 mS m-1 (n = 26) and faecal coliforms (per 100 mL) 1482.6 ± 636.0 (n = 24). The final effluent measured consistently high chemical oxygen demand and total suspended solids, however close analysis showed that total suspended solids could be controlled by increasing the frequency of removal of settled biomass within the settling ponds. Biomass produced contained microalgae, bacteria, metazoa, and protozoa. The biomass productivity achieved was as high as 130.6 kg ha-1 d-1; however, about 33% was lost to the final effluent due to inadequate settling. Results obtained during the course of this study and outcomes of earlier work on IAPS are taken as the baseline to determine parameters needed for the development of the process audit framework. Techniques utilised to derive the blue print process audit protocol for IAPS included a turtle diagram, a flow diagram and a checklist. Attention to plant management proved vital in determining overall performance. Cost, including operating and maintenance, of treating water using the demonstration scale system on a per person equivalent per year basis was determined as ZAR 123.87 (where, ZAR to USD = 0.07).
- Full Text:
- Date Issued: 2020
Petrographic and geochemical characterisation of the hangingwall and the footwall rocks (the Dipeta and R.A.T. stratigraphic units) to the Kinsevere and Nambulwa copper ore deposits of the Lufilian Arc, southern Democratic Republic of Congo
- Authors: Nkulu, Robert Kankomba
- Date: 2020
- Subjects: Petrogenesis -- Congo (Democratic Republic) , Analytical geochemistry -- Congo (Democratic Republic) , Copper ores -- Congo (Democratic Republic) , Ore deposits -- Congo (Democratic Republic) , Katangan Sequence , Geological mapping -- Congo (Democratic Republic) , Central African Copperbelt (Congo and Zambia) , Lufilian Arc , Neoproterozoic Katangan R.A.T. (Roches Argilo Talqueuse) Subgroup , Dipeta Subgroup
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/142772 , vital:38115
- Description: The Kinsevere and Nambulwa copper deposits in the Democratic Republic of Congo (D.R.C.) are set in the eastern side of the Neoproterozoic Katanga Supergroup, forming the Lufilian Arc, resulting from a cratonic collision between the Congo and the Kalahari Cratons (ca.620-570_Ma). The Katanga Supergroup was deposited in an extensional rift setting with a sedimentary thickness succession ranging between 7 to 10 km, sub-divided into: − the Roan, the Nguba and the Kundelungu Groups. The stratigraphic column of the Roan Group consists of the R.A.T. (Roche Argilo Talqueuse), the Mines, the Dipeta and the Mwashya Subgroups. Three major deformation phases have been described characterised by complex multiphase tectonics related to a curved superposition of folded, thrust and sheared blocks. The rocks of the R.A.T., Mines and Dipeta Subgroups are recognised as blocks that occur within a stratiform to discordant and diapiritic megabreccia. The blocks were rafted upward with salt tectonics, resulting in the juxtaposition with the hangingwall and the footwall terranes. Therefore, in that context it has been found that the Dipeta may appear overlying the R.A.T. Subgroup through the unconformity decollement surface of heterogeneous breccia. The petrographic observations made of the R.A.T. and Dipeta samples indicates in both units the presence of detrital quartz and feldspar that have been altered and replaced by sericite and muscovite minerals. Gypsum is intimately associated with magnesite, showing an evaporitic environment domain, while magnesite is common as alteration phase both in the R.A.T. and Dipeta Subgroups. Pyrophyllite has been observed in the Dipeta, resulting from reaction of silica with the Kaolinite at low temperature. Accessory detrital minerals include zircon, as well as xenotime intergrown with altered Fe-Ti-oxide hematite, forming complex textures with disseminated Ti-oxides both in R.A.T. and Dipeta units. Major and trace element geochemistry indicates that the Dipeta is more dolomitic and magnesite while the R.A.T. is clay-rich. The Ti2O value of Dipeta and R.A.T samples is relatively low, ranging between 0.36 and 0.69 wt.% respectively, which suggest highly evolved felsic material in the protolith. This is consistent with interpretation based on the Al2O3/TiO2 ratio, which ranges between 18 and 23 for the R.A.T. and Dipeta respectively, indicating an intermediate to felsic granitoids as the protolith of R.A.T. and Dipeta siltstones. The Ti/Zr ratio of R.A.T. and Dipeta samples of less than 10, while, the higher La/Sc ratio of between 2.6 and 5.5 (for the R.A.T. and Dipeta respectively) indicate that both the R.A.T. and Dipeta are active continental and passive margin tectonic setting. Based on the geochemical variation with depth across the R.A.T. and Dipeta and their contact zone, a geochemical fingerprinting suggests that the ratio TiO2/Al2O3 appears to be useful and could be considered as a stratigraphic geochemical maker able to discriminate the R.A.T. and the Dipeta Subgroups during the geological mapping.
- Full Text:
- Date Issued: 2020
- Authors: Nkulu, Robert Kankomba
- Date: 2020
- Subjects: Petrogenesis -- Congo (Democratic Republic) , Analytical geochemistry -- Congo (Democratic Republic) , Copper ores -- Congo (Democratic Republic) , Ore deposits -- Congo (Democratic Republic) , Katangan Sequence , Geological mapping -- Congo (Democratic Republic) , Central African Copperbelt (Congo and Zambia) , Lufilian Arc , Neoproterozoic Katangan R.A.T. (Roches Argilo Talqueuse) Subgroup , Dipeta Subgroup
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/142772 , vital:38115
- Description: The Kinsevere and Nambulwa copper deposits in the Democratic Republic of Congo (D.R.C.) are set in the eastern side of the Neoproterozoic Katanga Supergroup, forming the Lufilian Arc, resulting from a cratonic collision between the Congo and the Kalahari Cratons (ca.620-570_Ma). The Katanga Supergroup was deposited in an extensional rift setting with a sedimentary thickness succession ranging between 7 to 10 km, sub-divided into: − the Roan, the Nguba and the Kundelungu Groups. The stratigraphic column of the Roan Group consists of the R.A.T. (Roche Argilo Talqueuse), the Mines, the Dipeta and the Mwashya Subgroups. Three major deformation phases have been described characterised by complex multiphase tectonics related to a curved superposition of folded, thrust and sheared blocks. The rocks of the R.A.T., Mines and Dipeta Subgroups are recognised as blocks that occur within a stratiform to discordant and diapiritic megabreccia. The blocks were rafted upward with salt tectonics, resulting in the juxtaposition with the hangingwall and the footwall terranes. Therefore, in that context it has been found that the Dipeta may appear overlying the R.A.T. Subgroup through the unconformity decollement surface of heterogeneous breccia. The petrographic observations made of the R.A.T. and Dipeta samples indicates in both units the presence of detrital quartz and feldspar that have been altered and replaced by sericite and muscovite minerals. Gypsum is intimately associated with magnesite, showing an evaporitic environment domain, while magnesite is common as alteration phase both in the R.A.T. and Dipeta Subgroups. Pyrophyllite has been observed in the Dipeta, resulting from reaction of silica with the Kaolinite at low temperature. Accessory detrital minerals include zircon, as well as xenotime intergrown with altered Fe-Ti-oxide hematite, forming complex textures with disseminated Ti-oxides both in R.A.T. and Dipeta units. Major and trace element geochemistry indicates that the Dipeta is more dolomitic and magnesite while the R.A.T. is clay-rich. The Ti2O value of Dipeta and R.A.T samples is relatively low, ranging between 0.36 and 0.69 wt.% respectively, which suggest highly evolved felsic material in the protolith. This is consistent with interpretation based on the Al2O3/TiO2 ratio, which ranges between 18 and 23 for the R.A.T. and Dipeta respectively, indicating an intermediate to felsic granitoids as the protolith of R.A.T. and Dipeta siltstones. The Ti/Zr ratio of R.A.T. and Dipeta samples of less than 10, while, the higher La/Sc ratio of between 2.6 and 5.5 (for the R.A.T. and Dipeta respectively) indicate that both the R.A.T. and Dipeta are active continental and passive margin tectonic setting. Based on the geochemical variation with depth across the R.A.T. and Dipeta and their contact zone, a geochemical fingerprinting suggests that the ratio TiO2/Al2O3 appears to be useful and could be considered as a stratigraphic geochemical maker able to discriminate the R.A.T. and the Dipeta Subgroups during the geological mapping.
- Full Text:
- Date Issued: 2020
Petrography, metamorphism, deformation and P-T conditions in the western arm of the Lufilian Arc - Zambezi, north-western Zambia
- Authors: Chilekwa, Mwango
- Date: 2020
- Subjects: Petrogenesis -- Zambia -- Zambezi District , Metamorphism (Geology) -- Zambia -- Zambezi District , Petrology -- Zambia -- Zambezi District , Formations (Geology) -- Zambia -- Zambezi District , Rock deformation -- Zambia -- Zambezi District , Lufilian Arc , Neoproterozoic Katangan R.A.T. (Roches Argilo Talqueuse) Subgroup
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/161971 , vital:40699
- Description: The Zambezi area in north-western Zambia is underlain by Neoproterozoic Katanga Supergroup and older, Archean to Mesoproterozoic Basement Supergroup rocks. The area lies within the Domes Region, which is a structural domain of the Lufilian Arc. The stratigraphic succession within Zambezi area is dominated by the Grand Conglomerate Formation (GC) and Mwashia Group which are the most extensive units, and the less abundant Lower and Upper Roan Groups of the Katanga Supergroup. They wrap around the domal Basement Supergroup units. The mineral assemblage of the Mwashia and the GC schists commonly contains garnet, anthophyllite and biotite. GC rocks show remnants of primary structures such as clasts and sedimentary features. Anthophyllite, garnet and biotite are the dominant Mg-Fe rich metamorphic minerals. However, these are iron rich for each mineral phase and has been attributed to iron rich protoliths. The earliest recognised deformation episode (D1) formed NE-SW S1 foliations within GC which is consistent with the regional structural trend in the western Lufilian Arc. S1 was later affected by D2 that generated downward facing F2 folds and S2 foliations. The other associated feature to D2 is garnet that grew as the result of pro-grade metamorphism. The D3 deformation fabric is not developed and did not affect much of the structural geometry of the Zambezi area. The peak assemblages of the Basement Supergroup and the Katanga Supergroup formed at mid-amphibolite facies conditions of 590 °C and 630 °C at an average pressure of 4.0 kbar. The Basement Supergroup has undergone retrograde metamorphism to greenschist facies condition indicated by presence of chlorite and also determined by biotite-anorthite isopleth in THERIAK DOMINO. At the eastern part of Zambezi area, the Katanga Supergroup rocks were retrogressed in the upper greenschist facies at about ~470°C and ~4.0 kbar due to isobaric cooling.
- Full Text:
- Date Issued: 2020
- Authors: Chilekwa, Mwango
- Date: 2020
- Subjects: Petrogenesis -- Zambia -- Zambezi District , Metamorphism (Geology) -- Zambia -- Zambezi District , Petrology -- Zambia -- Zambezi District , Formations (Geology) -- Zambia -- Zambezi District , Rock deformation -- Zambia -- Zambezi District , Lufilian Arc , Neoproterozoic Katangan R.A.T. (Roches Argilo Talqueuse) Subgroup
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/161971 , vital:40699
- Description: The Zambezi area in north-western Zambia is underlain by Neoproterozoic Katanga Supergroup and older, Archean to Mesoproterozoic Basement Supergroup rocks. The area lies within the Domes Region, which is a structural domain of the Lufilian Arc. The stratigraphic succession within Zambezi area is dominated by the Grand Conglomerate Formation (GC) and Mwashia Group which are the most extensive units, and the less abundant Lower and Upper Roan Groups of the Katanga Supergroup. They wrap around the domal Basement Supergroup units. The mineral assemblage of the Mwashia and the GC schists commonly contains garnet, anthophyllite and biotite. GC rocks show remnants of primary structures such as clasts and sedimentary features. Anthophyllite, garnet and biotite are the dominant Mg-Fe rich metamorphic minerals. However, these are iron rich for each mineral phase and has been attributed to iron rich protoliths. The earliest recognised deformation episode (D1) formed NE-SW S1 foliations within GC which is consistent with the regional structural trend in the western Lufilian Arc. S1 was later affected by D2 that generated downward facing F2 folds and S2 foliations. The other associated feature to D2 is garnet that grew as the result of pro-grade metamorphism. The D3 deformation fabric is not developed and did not affect much of the structural geometry of the Zambezi area. The peak assemblages of the Basement Supergroup and the Katanga Supergroup formed at mid-amphibolite facies conditions of 590 °C and 630 °C at an average pressure of 4.0 kbar. The Basement Supergroup has undergone retrograde metamorphism to greenschist facies condition indicated by presence of chlorite and also determined by biotite-anorthite isopleth in THERIAK DOMINO. At the eastern part of Zambezi area, the Katanga Supergroup rocks were retrogressed in the upper greenschist facies at about ~470°C and ~4.0 kbar due to isobaric cooling.
- Full Text:
- Date Issued: 2020
Photo-physicochemical characterization and in vitro Photodynamic Therapy Activity of Phthalocyanine-Graphene Quantum Dots Conjugates
- Authors: Nene, Lindokuhle Cindy
- Date: 2020
- Subjects: Photochemotherapy , Cancer -- Chemotherapy , Quantum dots , Graphene , Nanomedicine
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/140463 , vital:37891
- Description: This thesis reports on the preparation of several differently substituted Zn(II) phthalocyanine (Pc) complexes and their respective graphene quantum dots (GQDs) conjugates. In addition, Pc complexes substituted with biologically active molecules used in cancer therapeutics, namely: benzothiazole and morpholine, were also prepared and conjugated to GQDs. The photo-physicochemical properties were determined for both the complexes and their respective conjugates including the fluorescence/ triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pc complexes decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields. This is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of reduced actual number of Pc units provided in the conjugate for therapy. An increase in the efficacy upon quaternization was observed, and a relatively better performance was also observed for the cationic complex in combination with the biotin- functionalized GQDs, 7-GQDs-Biotin. Moreover, the cellular uptake of 7-GQDs-Biotin over 24 h was relatively high compared to complexes alone and other Pcs-GQDs conjugates.
- Full Text:
- Date Issued: 2020
- Authors: Nene, Lindokuhle Cindy
- Date: 2020
- Subjects: Photochemotherapy , Cancer -- Chemotherapy , Quantum dots , Graphene , Nanomedicine
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/140463 , vital:37891
- Description: This thesis reports on the preparation of several differently substituted Zn(II) phthalocyanine (Pc) complexes and their respective graphene quantum dots (GQDs) conjugates. In addition, Pc complexes substituted with biologically active molecules used in cancer therapeutics, namely: benzothiazole and morpholine, were also prepared and conjugated to GQDs. The photo-physicochemical properties were determined for both the complexes and their respective conjugates including the fluorescence/ triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pc complexes decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields. This is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of reduced actual number of Pc units provided in the conjugate for therapy. An increase in the efficacy upon quaternization was observed, and a relatively better performance was also observed for the cationic complex in combination with the biotin- functionalized GQDs, 7-GQDs-Biotin. Moreover, the cellular uptake of 7-GQDs-Biotin over 24 h was relatively high compared to complexes alone and other Pcs-GQDs conjugates.
- Full Text:
- Date Issued: 2020
Photocatalysis of 4-chloro and 4-nonylphenols using novel symmetric phthalocyanines and asymmetric porphyrin supported on polyacrylonitrite nanofibres
- Authors: Jones, Benjamin Martin
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Electrospinning , Porphyrins , Nanofibers , Photocatalysis , Photocatalysis -- Environmental aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164770 , vital:41163
- Description: This work explores the synthesis and characterisation of novel symmetrical phthalocyanines and novel asymmetric porphyrins that have been embedded or linked respectively,and electrospun into fibres for application in the photocatalysis of environmental pollutants. The phthalocyanines contain pyrrole moieties without hetero atom linkers to maintain a rigid structure. The porphyrin contains a carboxy moiety utilized to construct an amide bond between the complex and the polymer prior to the spinning process. The new compounds were characterized by elemental analyses, proton nuclear magnetic resonance (HNMR)Fourier-transform infrared spectroscopy (FTIR), MALDI-TOF and UV-vis spectroscopy. The general trends of fluorescence, triplet and singlet oxygen quantum yields are described as well as their appropriate lifetimes. The photocatalytic activity of phthalocyanine embedded fibres were compared against those that had been dyed. Unfortunately, during the degradation process, the dyed fibres leeched compound and the studies could not be continued. It was seen that the porphyrin fibres linked to the polymer showed the most efficient photocatalytic activity against 4-cholorphenol and 4-nonylphenol due to irradiation at lower wavelengths consequently having higher frequencies and transferring more energy.
- Full Text:
- Date Issued: 2020
- Authors: Jones, Benjamin Martin
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Electrospinning , Porphyrins , Nanofibers , Photocatalysis , Photocatalysis -- Environmental aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164770 , vital:41163
- Description: This work explores the synthesis and characterisation of novel symmetrical phthalocyanines and novel asymmetric porphyrins that have been embedded or linked respectively,and electrospun into fibres for application in the photocatalysis of environmental pollutants. The phthalocyanines contain pyrrole moieties without hetero atom linkers to maintain a rigid structure. The porphyrin contains a carboxy moiety utilized to construct an amide bond between the complex and the polymer prior to the spinning process. The new compounds were characterized by elemental analyses, proton nuclear magnetic resonance (HNMR)Fourier-transform infrared spectroscopy (FTIR), MALDI-TOF and UV-vis spectroscopy. The general trends of fluorescence, triplet and singlet oxygen quantum yields are described as well as their appropriate lifetimes. The photocatalytic activity of phthalocyanine embedded fibres were compared against those that had been dyed. Unfortunately, during the degradation process, the dyed fibres leeched compound and the studies could not be continued. It was seen that the porphyrin fibres linked to the polymer showed the most efficient photocatalytic activity against 4-cholorphenol and 4-nonylphenol due to irradiation at lower wavelengths consequently having higher frequencies and transferring more energy.
- Full Text:
- Date Issued: 2020
Prediction of mass spectra for natural products using an ab initio approach
- Authors: Novokoza, Yolanda
- Date: 2020
- Subjects: Molecular dynamics , Molecular dynamics -- Computer simulation , Mass spectroscopy , Electron impact ionization
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167166 , vital:41443
- Description: Mass spectrometry (MS) is a technique that measures the fragmentation of molecules, dependent on the molecule’s chemical composition and structure, by first introducing a charge on the molecules. The instrument records the mass to charge ratio, but the energy from the ionization process causes the molecule to fragment. The resultant mass spectrum is highly indicative of not only the molecule analyzed, but also its chemical composition. MS is used in research and industry for both routine and research purposes. One such way to ionize molecules for MS is by bombarding the molecule with electrons which is the basis of electron impact mass spectrometry (EIMS). Although EIMS is widely used, prediction of electron impact mass spectra from first principles is a challenging problem due to a need to accurately determine the probability of different fragmentation pathways of a molecule. Ab initio molecular dynamics based methods are able to explore in an automatic fashion the energetically available fragmentation paths thus give reaction mechanisms in an unbiased way. The mass spectra of five molecules have been explored in work-flows leading to the prediction of mass spectra. These molecules include three natural products alpha-hispanolol, PFB oxime derivative and boronolide (for which experimental mass spectra were not available) and two compounds from the NIST database (for which experimental mass spectra were available). For each of these systems many random conformations were generated using the RDKit library. To all conformations random velocities were applied to each atom. Ab initio molecular dynamics was performed on each conformer, using these initial random velocities using CP2K software, at DFTB+ level at a variety of highly raised temperatures (to accelerate the formation of fragments) Fragmentation was monitored by iterating through all bonds, and identifying bond breakages during dynamics. Graph theoretical packages were used then to track distinct fragments generated. For each of these fragments, charges were determined from Mulliken analysis for all atoms on the fragment from the QM calculations and sum of atomic spin densities per fragment was also plotted. The fragment with the greatest charge (corresponding to the formation of a cation fragment) was taken for plotting on the mass spectrum. Finally, from the mass of the fragment and its elemental composition, the isotopic distribution for the fragment was determined, and this distribution was included by addition in to the mass spectrum. For all trajectories, the sum of all isotopic distributions determined the final mass spectrum.
- Full Text:
- Date Issued: 2020
- Authors: Novokoza, Yolanda
- Date: 2020
- Subjects: Molecular dynamics , Molecular dynamics -- Computer simulation , Mass spectroscopy , Electron impact ionization
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167166 , vital:41443
- Description: Mass spectrometry (MS) is a technique that measures the fragmentation of molecules, dependent on the molecule’s chemical composition and structure, by first introducing a charge on the molecules. The instrument records the mass to charge ratio, but the energy from the ionization process causes the molecule to fragment. The resultant mass spectrum is highly indicative of not only the molecule analyzed, but also its chemical composition. MS is used in research and industry for both routine and research purposes. One such way to ionize molecules for MS is by bombarding the molecule with electrons which is the basis of electron impact mass spectrometry (EIMS). Although EIMS is widely used, prediction of electron impact mass spectra from first principles is a challenging problem due to a need to accurately determine the probability of different fragmentation pathways of a molecule. Ab initio molecular dynamics based methods are able to explore in an automatic fashion the energetically available fragmentation paths thus give reaction mechanisms in an unbiased way. The mass spectra of five molecules have been explored in work-flows leading to the prediction of mass spectra. These molecules include three natural products alpha-hispanolol, PFB oxime derivative and boronolide (for which experimental mass spectra were not available) and two compounds from the NIST database (for which experimental mass spectra were available). For each of these systems many random conformations were generated using the RDKit library. To all conformations random velocities were applied to each atom. Ab initio molecular dynamics was performed on each conformer, using these initial random velocities using CP2K software, at DFTB+ level at a variety of highly raised temperatures (to accelerate the formation of fragments) Fragmentation was monitored by iterating through all bonds, and identifying bond breakages during dynamics. Graph theoretical packages were used then to track distinct fragments generated. For each of these fragments, charges were determined from Mulliken analysis for all atoms on the fragment from the QM calculations and sum of atomic spin densities per fragment was also plotted. The fragment with the greatest charge (corresponding to the formation of a cation fragment) was taken for plotting on the mass spectrum. Finally, from the mass of the fragment and its elemental composition, the isotopic distribution for the fragment was determined, and this distribution was included by addition in to the mass spectrum. For all trajectories, the sum of all isotopic distributions determined the final mass spectrum.
- Full Text:
- Date Issued: 2020
Production, purification and characterization of a multifunctional, thermostable and acido/alkaline stable putative xylanase from the psychrotrophic bacterium, Sphingomonas aerolata
- Authors: Mathibe, Brian Nkanyiso
- Date: 2020
- Subjects: Uncatalogued
- Language: English
- Type: thesis , text , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164478 , vital:41122
- Description: Thesis (MSc)--Rhodes University, Faculty of Science, Biochemistry and Microbiology, 2020
- Full Text:
- Date Issued: 2020
- Authors: Mathibe, Brian Nkanyiso
- Date: 2020
- Subjects: Uncatalogued
- Language: English
- Type: thesis , text , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164478 , vital:41122
- Description: Thesis (MSc)--Rhodes University, Faculty of Science, Biochemistry and Microbiology, 2020
- Full Text:
- Date Issued: 2020
Seasonal trends of rainfall intensity, ground cover and sediment dynamics in the Little Pot River and Gqukunqa River catchments, South Africa
- Authors: Herd-Hoare, Sean
- Date: 2020
- Subjects: Land degradation -- Control -- South Africa -- Eastern Cape , Vegetation mapping -- South Africa -- Eastern Cape , Rain and rainfall -- South Africa -- Eastern Cape , Gqukunqa River catchment (South Africa) , Little Pot River catchment (South Africa) , Tsitsa River catchment (South Africa)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146288 , vital:38512
- Description: Natural rangelands provide a variety of ecosystem services including livestock production which occurs on land under freehold land tenure and on land under communal tenure. There is an ongoing debate around the extent to which land degradation is occurring on these rangelands under different land management and land tenure systems and what the main degradation drivers are. Over-grazing, rainfall and soil type are key drivers of rangeland dynamics and the resultant sediment yield in the river systems, however, over-grazing is an outcome of land management while rainfall and soil type are natural drivers. This study explores the relationship between rainfall and daily sediment flux as well as the seasonal trends of vegetation cover and the study is part of a greater research effort called the Tsitsa Project which is based in the Tsitsa River catchment (near Maclear, Eastern Cape, South Africa). The Tsitsa Project aims at developing and managing both land and water in a sustainable way by improving the land, water and lives of people living in the Tsitsa River catchment. The restoration efforts of the Tstisa Project will aid in extending the lifespan of both the proposed dams on the Tsitsa River. The Tsitsa River catchment is characterised by grasslands, steep topography, highly erodible soils with many large gullies present and a very high sediment yield in the Tsitsa River which allowed for the exploration of some of the system drivers of sediment yield in this catchment. The study involved two sub-catchments of the Upper Tsitsa River catchment of different land management strategies: one dominated by commercial livestock farms (Little Pot River catchment) and one dominated by communal rangelands (Gqukunqa River catchment). The aim of this study was to determine the seasonal trends of rainfall intensity, ground cover and sediment dynamics in the Little Pot River and Gqukunqa River catchments. The purpose of the findings was to improve management strategies in degraded areas and catchments. In order to achieve this aim a variety of field and desktop methods were used. Field methods involved measuring variables including: vegetation biomass, vegetation cover, soil surface hardness, biocrust cover and slope angle for a range of Normalized Difference Vegetation Index (NDVI) values from the Sentinel-2A sensor. The study assessed the system response of the field variables in both catchments over one rainfall season (2018-2019). Desktop methods included various NDVI analyses as well as analyses of trends and relationships between vegetation dynamics, rainfall and sediment. The relationship between erosive rainfall events, daily rainfall, antecedent rainfall and daily sediment flux was explored over the time period of January 2016 to January 2019 and October 2015 to January 2019 for the Little Pot River catchment and the Gqukunqa River catchment respectively. NDVI was explored as a proxy for vegetation cover to extrapolate across the catchments and monitoring period. NDVI was found to have a weak positive relationship with vegetation cover and biomass (R2 values ranged from 0,04 to 0,525). Mean monthly catchment NDVI values, biomass and vegetation cover increased throughout the wet season of 2018-2019 in both catchments. Mean monthly NDVI values increased from 0,26 to 0,55 in the Little Pot River catchment and from 0,29 to 0,53 in the Gqukunqa River catchment over the course of the 2018-2019 wet season. NDVI, biomass and vegetation cover was found to be higher on south-facing slopes than north-facing slopes in both catchments for the majority of the wet season. The Gqukunqa River has significantly higher daily sediment fluxes than the Little Pot River despite similar NDVI and rainfall intensities which is owed to the dispersive soils in the Gqukunqa River catchment. Soil surface hardness results were inconclusive due to rainfall before or during every field trip which changed the properties of the soil. The largest erosive rainfall, daily rainfall and daily sediment events occurred from January to March each wet season in both catchments. Rainfall intensity and sediment fluxes were found to have a weak relationship, however, there was a stronger relationship found between antecedent rainfall and sediment flux. The larger daily sediment fluxes in each catchment often did not result from an erosive rainfall event on the same day but rather from multiple days of rainfall which can result in saturated soils and runoff leading to surface and sub-surface erosion. The possibility of sub-surface erosion via chemical processes contributing to the larger sediment events was also explored to explain the stronger relationship between antecedent rainfall and daily sediment flux.
- Full Text:
- Date Issued: 2020
- Authors: Herd-Hoare, Sean
- Date: 2020
- Subjects: Land degradation -- Control -- South Africa -- Eastern Cape , Vegetation mapping -- South Africa -- Eastern Cape , Rain and rainfall -- South Africa -- Eastern Cape , Gqukunqa River catchment (South Africa) , Little Pot River catchment (South Africa) , Tsitsa River catchment (South Africa)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146288 , vital:38512
- Description: Natural rangelands provide a variety of ecosystem services including livestock production which occurs on land under freehold land tenure and on land under communal tenure. There is an ongoing debate around the extent to which land degradation is occurring on these rangelands under different land management and land tenure systems and what the main degradation drivers are. Over-grazing, rainfall and soil type are key drivers of rangeland dynamics and the resultant sediment yield in the river systems, however, over-grazing is an outcome of land management while rainfall and soil type are natural drivers. This study explores the relationship between rainfall and daily sediment flux as well as the seasonal trends of vegetation cover and the study is part of a greater research effort called the Tsitsa Project which is based in the Tsitsa River catchment (near Maclear, Eastern Cape, South Africa). The Tsitsa Project aims at developing and managing both land and water in a sustainable way by improving the land, water and lives of people living in the Tsitsa River catchment. The restoration efforts of the Tstisa Project will aid in extending the lifespan of both the proposed dams on the Tsitsa River. The Tsitsa River catchment is characterised by grasslands, steep topography, highly erodible soils with many large gullies present and a very high sediment yield in the Tsitsa River which allowed for the exploration of some of the system drivers of sediment yield in this catchment. The study involved two sub-catchments of the Upper Tsitsa River catchment of different land management strategies: one dominated by commercial livestock farms (Little Pot River catchment) and one dominated by communal rangelands (Gqukunqa River catchment). The aim of this study was to determine the seasonal trends of rainfall intensity, ground cover and sediment dynamics in the Little Pot River and Gqukunqa River catchments. The purpose of the findings was to improve management strategies in degraded areas and catchments. In order to achieve this aim a variety of field and desktop methods were used. Field methods involved measuring variables including: vegetation biomass, vegetation cover, soil surface hardness, biocrust cover and slope angle for a range of Normalized Difference Vegetation Index (NDVI) values from the Sentinel-2A sensor. The study assessed the system response of the field variables in both catchments over one rainfall season (2018-2019). Desktop methods included various NDVI analyses as well as analyses of trends and relationships between vegetation dynamics, rainfall and sediment. The relationship between erosive rainfall events, daily rainfall, antecedent rainfall and daily sediment flux was explored over the time period of January 2016 to January 2019 and October 2015 to January 2019 for the Little Pot River catchment and the Gqukunqa River catchment respectively. NDVI was explored as a proxy for vegetation cover to extrapolate across the catchments and monitoring period. NDVI was found to have a weak positive relationship with vegetation cover and biomass (R2 values ranged from 0,04 to 0,525). Mean monthly catchment NDVI values, biomass and vegetation cover increased throughout the wet season of 2018-2019 in both catchments. Mean monthly NDVI values increased from 0,26 to 0,55 in the Little Pot River catchment and from 0,29 to 0,53 in the Gqukunqa River catchment over the course of the 2018-2019 wet season. NDVI, biomass and vegetation cover was found to be higher on south-facing slopes than north-facing slopes in both catchments for the majority of the wet season. The Gqukunqa River has significantly higher daily sediment fluxes than the Little Pot River despite similar NDVI and rainfall intensities which is owed to the dispersive soils in the Gqukunqa River catchment. Soil surface hardness results were inconclusive due to rainfall before or during every field trip which changed the properties of the soil. The largest erosive rainfall, daily rainfall and daily sediment events occurred from January to March each wet season in both catchments. Rainfall intensity and sediment fluxes were found to have a weak relationship, however, there was a stronger relationship found between antecedent rainfall and sediment flux. The larger daily sediment fluxes in each catchment often did not result from an erosive rainfall event on the same day but rather from multiple days of rainfall which can result in saturated soils and runoff leading to surface and sub-surface erosion. The possibility of sub-surface erosion via chemical processes contributing to the larger sediment events was also explored to explain the stronger relationship between antecedent rainfall and daily sediment flux.
- Full Text:
- Date Issued: 2020
Securing software development using developer access control
- Authors: Ongers, Grant
- Date: 2020
- Subjects: Computer software -- Development , Computers -- Access control , Computer security -- Software , Computer networks -- Security measures , Source code (Computer science) , Plug-ins (Computer programs) , Data encryption (Computer science) , Network Access Control , Data Loss Prevention , Google’s BeyondCorp , Confidentiality, Integrity and Availability (CIA) triad
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/149022 , vital:38796
- Description: This research is aimed at software development companies and highlights the unique information security concerns in the context of a non-malicious software developer’s work environment; and furthermore explores an application driven solution which focuses specifically on providing developer environments with access control for source code repositories. In order to achieve that, five goals were defined as discussed in section 1.3. The application designed to provide the developer environment with access control to source code repositories was modelled on lessons taken from the principles of Network Access Control (NAC), Data Loss Prevention (DLP), and Google’s BeyondCorp (GBC) for zero-trust end-user computing. The intention of this research is to provide software developers with maximum access to source code without compromising Confidentiality, as per the Confidentiality, Integrity and Availability (CIA) triad. Employing data gleaned from examining the characteristics of DLP, NAC, and Beyond- Corp—proof-of-concept code was developed to regulate access to the developer’s environment and source code. The system required sufficient flexibility to support the diversity of software development environments. In order to achieve this, a modular design was selected. The system comprised a client side agent and a plug-in-ready server component. The client side agent mounts and dismounts encrypted volumes containing source code. Furthermore, it provides the server with information of the client that is demanded by plug-ins. The server side service provided encryption keys to facilitate the mounting of the volumes and, through plug-ins, asked questions of the client agent to determine whether access should be granted. The solution was then tested with integration and system testing. There were plans to have it used by development teams who were then to be surveyed as to their view on the proof of concept but this proved impossible. The conclusion provides a basis by which organisations that develop software can better balance the two corners of the CIA triad most often in conflict: Confidentiality in terms of their source code against the Availability of the same to developers.
- Full Text:
- Date Issued: 2020
- Authors: Ongers, Grant
- Date: 2020
- Subjects: Computer software -- Development , Computers -- Access control , Computer security -- Software , Computer networks -- Security measures , Source code (Computer science) , Plug-ins (Computer programs) , Data encryption (Computer science) , Network Access Control , Data Loss Prevention , Google’s BeyondCorp , Confidentiality, Integrity and Availability (CIA) triad
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/149022 , vital:38796
- Description: This research is aimed at software development companies and highlights the unique information security concerns in the context of a non-malicious software developer’s work environment; and furthermore explores an application driven solution which focuses specifically on providing developer environments with access control for source code repositories. In order to achieve that, five goals were defined as discussed in section 1.3. The application designed to provide the developer environment with access control to source code repositories was modelled on lessons taken from the principles of Network Access Control (NAC), Data Loss Prevention (DLP), and Google’s BeyondCorp (GBC) for zero-trust end-user computing. The intention of this research is to provide software developers with maximum access to source code without compromising Confidentiality, as per the Confidentiality, Integrity and Availability (CIA) triad. Employing data gleaned from examining the characteristics of DLP, NAC, and Beyond- Corp—proof-of-concept code was developed to regulate access to the developer’s environment and source code. The system required sufficient flexibility to support the diversity of software development environments. In order to achieve this, a modular design was selected. The system comprised a client side agent and a plug-in-ready server component. The client side agent mounts and dismounts encrypted volumes containing source code. Furthermore, it provides the server with information of the client that is demanded by plug-ins. The server side service provided encryption keys to facilitate the mounting of the volumes and, through plug-ins, asked questions of the client agent to determine whether access should be granted. The solution was then tested with integration and system testing. There were plans to have it used by development teams who were then to be surveyed as to their view on the proof of concept but this proved impossible. The conclusion provides a basis by which organisations that develop software can better balance the two corners of the CIA triad most often in conflict: Confidentiality in terms of their source code against the Availability of the same to developers.
- Full Text:
- Date Issued: 2020
Sexual attraction and mating compatibility between Thaumatotibia leucotreta populations and implications for semiochemical dependent technologies
- Authors: Upfold, Jennifer Kate
- Date: 2020
- Subjects: Cryptophlebia leucotreta -- South Africa , Cryptophlebia leucotreta -- Reproduction , Citrus -- Disease and pests -- Control -- South Africa , Insect sterilization -- South Africa , Pheromones , Pheromone traps
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/148526 , vital:38747
- Description: False codling moth (FCM), Thaumatotibia leucotreta (Meyrick), is the most important pest for the cultivation of citrus in South Africa. False codling moth is indigenous to southern Africa and is a regulated pest of many international markets for phytosanitary concerns. Considerable research efforts have been invested in the past decades to develop semiochemcial technologies, such as monitoring with sex pheromones, attract-and-kill, mating disruption and the sterile insect technique. One of the potential obstacles identified with semiochemical control is the differences in the ratio of the compounds comprising the sex pheromone at different geographical locations, resulting in what is known as regional attraction. This has been identified in FCM populations from three different countries, however, regional attraction within South African FCM populations was unknown. Therefore, the study assessed the genetic integrity of five laboratory-reared FCM populations originating from geographically isolated populations in South Africa using the AFLP technique in order to assess regional attractiveness within the country. The results found isolated populations from Addo, Citrusdal, Marble Hall, Nelspruit and a fifth group found to be closely related to Addo and Citrusdal called the ‘Old’ colony. These five genetically isolated populations as well as a population from Xsit (Pty) Ltd, used for the sterile insect technique (SIT), were used in regional attractiveness trials. Males were significantly (P = <0.05) more attracted to females originating from the same population. No significant attraction could be determined from the sterile males, as the recapture rates in the trap were too low. Furthermore, regional attractiveness was assessed through choice/ no-choice mating compatibility trials. Significant sexual isolation (ISI) occurred between mating combinations Addo × Nelspruit (ISI = 0,13; t2 = 6.23; p = 0.02), Addo × Marble Hall (ISI = 0,11; t2 = 4.72; p = 0.04), Citrusdal × Nelspruit (ISI = 0,11; t2 = 4.95; p = 0.04), and Citrusdal × Marble Hall (ISI = 0,12; t2 = 4.31; p = 0.04). In these combinations, Addo and Citrusdal males were found to have outcompeted Nelspruit and Marble Hall males for more mating events. Significant sexual isolation was also recorded for Sterile × Marble Hall (ISI = 0.12; t2 = 4.98; p =0.01) and Sterile × Citrusdal (ISI = 0.13; t2 = 3.96; p = 0.01) populations. The male relative performance index was significant in both combinations, indicating that non-sterile laboratory males outcompeted the sterile males in these two combinations. When given no choice, evaluated as spermatophore transfer/ female/ 48h, all males (including sterile) were successful in transferring spermatophores to all FCM populations, with no significant differences. These results indicate that there may be incipient pre-isolation mechanisms affected by local natural selection, resulting in localised sexual attraction via differences in the sex pheromone ratios. These findings provide important information for semiochemical technologies and the implication of these results with regard to monitoring with sex pheromones, attract-and-kill, mating disruption and sterile insect technique are discussed.
- Full Text:
- Date Issued: 2020
- Authors: Upfold, Jennifer Kate
- Date: 2020
- Subjects: Cryptophlebia leucotreta -- South Africa , Cryptophlebia leucotreta -- Reproduction , Citrus -- Disease and pests -- Control -- South Africa , Insect sterilization -- South Africa , Pheromones , Pheromone traps
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/148526 , vital:38747
- Description: False codling moth (FCM), Thaumatotibia leucotreta (Meyrick), is the most important pest for the cultivation of citrus in South Africa. False codling moth is indigenous to southern Africa and is a regulated pest of many international markets for phytosanitary concerns. Considerable research efforts have been invested in the past decades to develop semiochemcial technologies, such as monitoring with sex pheromones, attract-and-kill, mating disruption and the sterile insect technique. One of the potential obstacles identified with semiochemical control is the differences in the ratio of the compounds comprising the sex pheromone at different geographical locations, resulting in what is known as regional attraction. This has been identified in FCM populations from three different countries, however, regional attraction within South African FCM populations was unknown. Therefore, the study assessed the genetic integrity of five laboratory-reared FCM populations originating from geographically isolated populations in South Africa using the AFLP technique in order to assess regional attractiveness within the country. The results found isolated populations from Addo, Citrusdal, Marble Hall, Nelspruit and a fifth group found to be closely related to Addo and Citrusdal called the ‘Old’ colony. These five genetically isolated populations as well as a population from Xsit (Pty) Ltd, used for the sterile insect technique (SIT), were used in regional attractiveness trials. Males were significantly (P = <0.05) more attracted to females originating from the same population. No significant attraction could be determined from the sterile males, as the recapture rates in the trap were too low. Furthermore, regional attractiveness was assessed through choice/ no-choice mating compatibility trials. Significant sexual isolation (ISI) occurred between mating combinations Addo × Nelspruit (ISI = 0,13; t2 = 6.23; p = 0.02), Addo × Marble Hall (ISI = 0,11; t2 = 4.72; p = 0.04), Citrusdal × Nelspruit (ISI = 0,11; t2 = 4.95; p = 0.04), and Citrusdal × Marble Hall (ISI = 0,12; t2 = 4.31; p = 0.04). In these combinations, Addo and Citrusdal males were found to have outcompeted Nelspruit and Marble Hall males for more mating events. Significant sexual isolation was also recorded for Sterile × Marble Hall (ISI = 0.12; t2 = 4.98; p =0.01) and Sterile × Citrusdal (ISI = 0.13; t2 = 3.96; p = 0.01) populations. The male relative performance index was significant in both combinations, indicating that non-sterile laboratory males outcompeted the sterile males in these two combinations. When given no choice, evaluated as spermatophore transfer/ female/ 48h, all males (including sterile) were successful in transferring spermatophores to all FCM populations, with no significant differences. These results indicate that there may be incipient pre-isolation mechanisms affected by local natural selection, resulting in localised sexual attraction via differences in the sex pheromone ratios. These findings provide important information for semiochemical technologies and the implication of these results with regard to monitoring with sex pheromones, attract-and-kill, mating disruption and sterile insect technique are discussed.
- Full Text:
- Date Issued: 2020
Structure and interaction studies of beta-amyloid in the search for new lead compounds for the treatment of Alzheimer’s disease
- Authors: Mtini, Onke
- Date: 2020
- Subjects: Alzheimer's disease -- Chemotherapy , Alzheimer's disease -- Treatment , Amyloid beta-protein , Oxidative stress , Protein binding , South African Natural Compounds Database
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167574 , vital:41493
- Description: Alzheimer’s disease (AD) is the most devastating neurodegenerative disorder that effects the aging population worldwide. In this study three hypotheses of AD are explored, the β-amyloid cascade hypothesis, the β-amyloid metal binding hypothesis and the oxidative stress hypothesis are explored. In the first case compounds from the South African Natural Compounds Database (SANCDB) are docked to models of β-amyloid fibrils and the properties of these fibrils under pulling simulations are compared to a known small molecule disruptor of β-amyloid, wgx-50. In these simulations SANCDB compounds are identified that disrupt β-amyloid in a similar manner to wgx-50. In these simulations the disruption to the free energy of binding of chains to the fibrils is quantified. For metal binding and oxidative stress hypotheses, problems in simulation arise due to only fragments of β-amyloid being present in the Research Collaboratory for Structural Bioinformatics protein data bank (RCSB PDB), as determined from NMR experiments. In this work, β-amyloid is set up under periodic boundary conditions to simulate a fibril under reasonable computational time. Within these periodic boundary conditions, β-amyloid has been solvated in copper and zinc rich environments and diffusion of these metals around the fibrils has been explored. The localization of these metals (in simulation only using van der Waal’s and electrostatic terms) around the fibril has led us to explore other possible metal binding sites. Metal bound to the infinite fibril has been optimized at the QM/MM level and some of the reactive oxygen species in the presence of the fibril are quantified.
- Full Text:
- Date Issued: 2020
- Authors: Mtini, Onke
- Date: 2020
- Subjects: Alzheimer's disease -- Chemotherapy , Alzheimer's disease -- Treatment , Amyloid beta-protein , Oxidative stress , Protein binding , South African Natural Compounds Database
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167574 , vital:41493
- Description: Alzheimer’s disease (AD) is the most devastating neurodegenerative disorder that effects the aging population worldwide. In this study three hypotheses of AD are explored, the β-amyloid cascade hypothesis, the β-amyloid metal binding hypothesis and the oxidative stress hypothesis are explored. In the first case compounds from the South African Natural Compounds Database (SANCDB) are docked to models of β-amyloid fibrils and the properties of these fibrils under pulling simulations are compared to a known small molecule disruptor of β-amyloid, wgx-50. In these simulations SANCDB compounds are identified that disrupt β-amyloid in a similar manner to wgx-50. In these simulations the disruption to the free energy of binding of chains to the fibrils is quantified. For metal binding and oxidative stress hypotheses, problems in simulation arise due to only fragments of β-amyloid being present in the Research Collaboratory for Structural Bioinformatics protein data bank (RCSB PDB), as determined from NMR experiments. In this work, β-amyloid is set up under periodic boundary conditions to simulate a fibril under reasonable computational time. Within these periodic boundary conditions, β-amyloid has been solvated in copper and zinc rich environments and diffusion of these metals around the fibrils has been explored. The localization of these metals (in simulation only using van der Waal’s and electrostatic terms) around the fibril has led us to explore other possible metal binding sites. Metal bound to the infinite fibril has been optimized at the QM/MM level and some of the reactive oxygen species in the presence of the fibril are quantified.
- Full Text:
- Date Issued: 2020
Symmetry and asymmetry in electrocatalysis: enhancing the electrocatalytic activity of phthalocyanines through synergy with doped graphene quantum dots
- Nkhahle, Reitumetse Precious
- Authors: Nkhahle, Reitumetse Precious
- Date: 2020
- Subjects: Phthalocyanines , Quantum dots , Graphene
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117585 , vital:34529
- Description: An exploration on the enhancement of the electrocatalytic activity of phthalocyanines (Pcs) through coupling with a series of graphene quantum dots (GQDs) is undertaken. The preliminary studies using symmetrical Pcs, a cobalt and an iron chloride tetra substituted diethylaminophenoxy Pc (complexes 1 and 2), for the electro-oxidation of nitrite revealed through the various sequential modifications that doped GQDs fare better than their pristine counterparts with respect to improving the electrocatalytic behaviour of Pcs, in particular, the nitrogen-doped GQDs (NGQDs). Following up on this, a series of asymmetric Pc complexes; 2,9,16-tris-(4-tert-butylphenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (3), 2,9,16-tris-(4-tert-butylphenoxy) mono aminophenoxy phthalocyanato cobalt (II) (4), 2,9,16-tris-(3-diethylamino)phenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (5) and 2,9,16-tris-(3-diethylamino)phenoxy) mono aminophenoxy phthalocyanato cobalt (II) (6) was prepared in which push-pull systems were compared to other asymmetric complexes that lack this effect towards the electrocatalytic sensing of hydrazine. All asymmetric complexes (3-6) were π-stacked to the NGQDs while those with an NH2 group (4 and 6), were also covalently linked to the NGQDs. These complexes and their corresponding conjugates were characterized accordingly and applied as electrocatalysts in the oxidation of hydrazine. The electrochemical studies revealed that π π stacking yields better responses (higher sensitivities and lower limits of detection) than covalent linking because there are less forces acting on the graphene network. Covalent linking introduces both tensile and compressive forces which in turn results in an increase in the ID/IG ratio and that is unfavourable for electrocatalysis. In comparing the electrodes composed of the π-stacked conjugates to those altered through sequential modifications, despite the conditions not being the same, it can be inferred that the magnitude of the electrostatic forces between the Pcs and the GQDs also plays a significant role in electrocatalysis. The π-stacked conjugates, owing to the manner in which they were prepared, have stronger electrostatic forces acting between the Pc and GQDs hence they were able to elicit a better electrochemical response than the sequentially modified electrodes. In addition to that, it appears that asymmetric Pcs are better electrocatalysts in comparison to the symmetric Pcs.
- Full Text:
- Date Issued: 2020
- Authors: Nkhahle, Reitumetse Precious
- Date: 2020
- Subjects: Phthalocyanines , Quantum dots , Graphene
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117585 , vital:34529
- Description: An exploration on the enhancement of the electrocatalytic activity of phthalocyanines (Pcs) through coupling with a series of graphene quantum dots (GQDs) is undertaken. The preliminary studies using symmetrical Pcs, a cobalt and an iron chloride tetra substituted diethylaminophenoxy Pc (complexes 1 and 2), for the electro-oxidation of nitrite revealed through the various sequential modifications that doped GQDs fare better than their pristine counterparts with respect to improving the electrocatalytic behaviour of Pcs, in particular, the nitrogen-doped GQDs (NGQDs). Following up on this, a series of asymmetric Pc complexes; 2,9,16-tris-(4-tert-butylphenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (3), 2,9,16-tris-(4-tert-butylphenoxy) mono aminophenoxy phthalocyanato cobalt (II) (4), 2,9,16-tris-(3-diethylamino)phenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (5) and 2,9,16-tris-(3-diethylamino)phenoxy) mono aminophenoxy phthalocyanato cobalt (II) (6) was prepared in which push-pull systems were compared to other asymmetric complexes that lack this effect towards the electrocatalytic sensing of hydrazine. All asymmetric complexes (3-6) were π-stacked to the NGQDs while those with an NH2 group (4 and 6), were also covalently linked to the NGQDs. These complexes and their corresponding conjugates were characterized accordingly and applied as electrocatalysts in the oxidation of hydrazine. The electrochemical studies revealed that π π stacking yields better responses (higher sensitivities and lower limits of detection) than covalent linking because there are less forces acting on the graphene network. Covalent linking introduces both tensile and compressive forces which in turn results in an increase in the ID/IG ratio and that is unfavourable for electrocatalysis. In comparing the electrodes composed of the π-stacked conjugates to those altered through sequential modifications, despite the conditions not being the same, it can be inferred that the magnitude of the electrostatic forces between the Pcs and the GQDs also plays a significant role in electrocatalysis. The π-stacked conjugates, owing to the manner in which they were prepared, have stronger electrostatic forces acting between the Pc and GQDs hence they were able to elicit a better electrochemical response than the sequentially modified electrodes. In addition to that, it appears that asymmetric Pcs are better electrocatalysts in comparison to the symmetric Pcs.
- Full Text:
- Date Issued: 2020
Synthesis, photophysicochemical properties and photodynamic therapy activities of indium and zinc phthalocyanines when incorporated into Pluronic polymer micelles
- Authors: Motloung, Banele Mike
- Date: 2020
- Subjects: Indium , Zinc , Phthalocyanines , Polymers , Photochemotherapy , Micelles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167529 , vital:41489
- Description: This thesis reports on the syntheses, photophysicochemical properties and photodynamic therapy activities of symmetrical metallophthalocyanines (MPcs) when alone or when incorporated into Pluronic polymer micelles. The Pcs contain either zinc or indium as central metals and have phenyldiazenylphenoxy, pyridine-2-yloxy and benzo[d]thiazol-2-ylthio as ring substituents. Spectroscopic and microscopic techniques were used to confirm the formation MPcs with micelles. The photophysics and photochemistry of the Pcs were assessed when alone and with micelles. All the studied Pcs showed good photophysicochemical behavior with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yields. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy atom effect obtained from the former. The in vitro dark cytotoxicity and photodynamic therapy of the Pc complexes and conjugates against MCF7 cells was tested. All studied Pc complexes alone and with micelles showed minimum dark toxicity making them applicable for PDT. All complexes displayed good phototoxicity < 50% cell viability (except for complex 2 > 50% cell viability) at concentrations ≤100 μg/mL, however the conjugates showed < 45% cell viability at concentrations ≤ 100 μg/mL, probably due to the small micellar size and EPR effect. The findings from this work show the importance of incorporating photosensitizers such as phthalocyanines into Pluronic polymers micelles and making them water soluble and ultimately improving their photodynamic effect.
- Full Text:
- Date Issued: 2020
- Authors: Motloung, Banele Mike
- Date: 2020
- Subjects: Indium , Zinc , Phthalocyanines , Polymers , Photochemotherapy , Micelles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167529 , vital:41489
- Description: This thesis reports on the syntheses, photophysicochemical properties and photodynamic therapy activities of symmetrical metallophthalocyanines (MPcs) when alone or when incorporated into Pluronic polymer micelles. The Pcs contain either zinc or indium as central metals and have phenyldiazenylphenoxy, pyridine-2-yloxy and benzo[d]thiazol-2-ylthio as ring substituents. Spectroscopic and microscopic techniques were used to confirm the formation MPcs with micelles. The photophysics and photochemistry of the Pcs were assessed when alone and with micelles. All the studied Pcs showed good photophysicochemical behavior with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yields. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy atom effect obtained from the former. The in vitro dark cytotoxicity and photodynamic therapy of the Pc complexes and conjugates against MCF7 cells was tested. All studied Pc complexes alone and with micelles showed minimum dark toxicity making them applicable for PDT. All complexes displayed good phototoxicity < 50% cell viability (except for complex 2 > 50% cell viability) at concentrations ≤100 μg/mL, however the conjugates showed < 45% cell viability at concentrations ≤ 100 μg/mL, probably due to the small micellar size and EPR effect. The findings from this work show the importance of incorporating photosensitizers such as phthalocyanines into Pluronic polymers micelles and making them water soluble and ultimately improving their photodynamic effect.
- Full Text:
- Date Issued: 2020
System analysis of fatigue in pilots and co-pilots executing short-hall flight operations
- Authors: Bennett, Cleo Taylor
- Date: 2020
- Subjects: Air pilots -- Health and hygiene , Fatigue , Work environment -- Psychological aspects , Work environment -- Physiological aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146622 , vital:38543
- Description: Background: This study was conducted as part of Denel’s South African Regional Aircraft (SARA) development project. Regional aircraft have a maximum flight time of 60 minutes. Hence, the study focuses on matters pertaining to the short-haul flight context. Pilot fatigue has been recognised as a safety concern in the aviation industry. It impacts on pilot performance across the board, not least in the short-haul context. However, the specific factors that lead to pilot fatigue in short-haul operations have not been well researched. Research Aim: To identify and examine the factors which influence pilot/co-pilot fatigue in short-haul aviation contexts. Method: Fatigue is multifaceted, and has multiple definitions and descriptions. It is acknowledged as a complex phenomenon, the development of which is dynamically influenced by various factors. Thus, a systems approach based on the work system model by Smith and Carayon-Sainfort (1989) was adopted for this study. A systems analysis was conducted in two parts: 1) a literature analysis, and 2) expert interviews. Results: Both the literature analysis and the interviews indicated that pilot fatigue in short-haul flight operations represent composite system outcomes influenced by various factors. The factors identified were structured (systematised) into categories, namely organizational factors, task-related factors, environmental factors, factors linked to technology and tools, and non-work-related factors specific to the individual pilot. An example of a task-related factor would be the performance by pilots of multiple take-offs and landings; organizational factors include work time arrangements and duty scheduling (e.g. unpredictable schedule, early starts/late finishes, number of flight sectors in a shift, extended working hours, numerous consecutive work days, standby duties, flight, duty and rest limitations (regulations and guidelines); and short turnaround periods); environmental factors might include the small pressurised cockpit environment, movement restriction, very low humidity, low air pressure, vibrations, high noise levels, low light intensity light, and inclement weather); there are many examples of how tools and technology utilized by pilots might affect their fatigue levels; and finally, pilot-specific non-work-related factors would include things like the pilot’s age, health (lifestyle), family stress, work experience and sleep environment. All of these factors were identified during the literature analysis and have a significant bearing on how fatigue could present in short-haul pilots/co-pilots. Other important fatigue-related factors revealed during the expert interviews included, organizational culture, time management, health implications of fatigue, and management of fatigue. Conclusions: Pilot fatigue is a complex and multi-factorial physiological condition. There are many interacting components which contribute to pilot fatigue in short-haul operations. These should be viewed from an integrated perspective and holistic, systems-based approaches should be taken to manage these issues, particularly in the context of short-haul operations. This would optimize pilot performance and well-being and, most importantly, improve the safety of the work environment to enhance overall operation safety. Limitations: The study does not quantify the contributions made to pilot fatigue by the various factors explored. Therefore, care needs to be taken when designing and implementing interventions based on this research.
- Full Text:
- Date Issued: 2020
- Authors: Bennett, Cleo Taylor
- Date: 2020
- Subjects: Air pilots -- Health and hygiene , Fatigue , Work environment -- Psychological aspects , Work environment -- Physiological aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146622 , vital:38543
- Description: Background: This study was conducted as part of Denel’s South African Regional Aircraft (SARA) development project. Regional aircraft have a maximum flight time of 60 minutes. Hence, the study focuses on matters pertaining to the short-haul flight context. Pilot fatigue has been recognised as a safety concern in the aviation industry. It impacts on pilot performance across the board, not least in the short-haul context. However, the specific factors that lead to pilot fatigue in short-haul operations have not been well researched. Research Aim: To identify and examine the factors which influence pilot/co-pilot fatigue in short-haul aviation contexts. Method: Fatigue is multifaceted, and has multiple definitions and descriptions. It is acknowledged as a complex phenomenon, the development of which is dynamically influenced by various factors. Thus, a systems approach based on the work system model by Smith and Carayon-Sainfort (1989) was adopted for this study. A systems analysis was conducted in two parts: 1) a literature analysis, and 2) expert interviews. Results: Both the literature analysis and the interviews indicated that pilot fatigue in short-haul flight operations represent composite system outcomes influenced by various factors. The factors identified were structured (systematised) into categories, namely organizational factors, task-related factors, environmental factors, factors linked to technology and tools, and non-work-related factors specific to the individual pilot. An example of a task-related factor would be the performance by pilots of multiple take-offs and landings; organizational factors include work time arrangements and duty scheduling (e.g. unpredictable schedule, early starts/late finishes, number of flight sectors in a shift, extended working hours, numerous consecutive work days, standby duties, flight, duty and rest limitations (regulations and guidelines); and short turnaround periods); environmental factors might include the small pressurised cockpit environment, movement restriction, very low humidity, low air pressure, vibrations, high noise levels, low light intensity light, and inclement weather); there are many examples of how tools and technology utilized by pilots might affect their fatigue levels; and finally, pilot-specific non-work-related factors would include things like the pilot’s age, health (lifestyle), family stress, work experience and sleep environment. All of these factors were identified during the literature analysis and have a significant bearing on how fatigue could present in short-haul pilots/co-pilots. Other important fatigue-related factors revealed during the expert interviews included, organizational culture, time management, health implications of fatigue, and management of fatigue. Conclusions: Pilot fatigue is a complex and multi-factorial physiological condition. There are many interacting components which contribute to pilot fatigue in short-haul operations. These should be viewed from an integrated perspective and holistic, systems-based approaches should be taken to manage these issues, particularly in the context of short-haul operations. This would optimize pilot performance and well-being and, most importantly, improve the safety of the work environment to enhance overall operation safety. Limitations: The study does not quantify the contributions made to pilot fatigue by the various factors explored. Therefore, care needs to be taken when designing and implementing interventions based on this research.
- Full Text:
- Date Issued: 2020
Taxonomic revision of the Natal mountain catfish, Amphilius natalensis (Siluriformes, Amphiliidae) in southern Africa
- Mazungula, Daniel Nkosinathi
- Authors: Mazungula, Daniel Nkosinathi
- Date: 2020
- Subjects: Uncatalogued
- Language: English
- Type: thesis , text , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164490 , vital:41123
- Description: Thesis (MSc)--Rhodes University, Department of Ichthyology and Fisheries Science, 2020
- Full Text:
- Date Issued: 2020
- Authors: Mazungula, Daniel Nkosinathi
- Date: 2020
- Subjects: Uncatalogued
- Language: English
- Type: thesis , text , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164490 , vital:41123
- Description: Thesis (MSc)--Rhodes University, Department of Ichthyology and Fisheries Science, 2020
- Full Text:
- Date Issued: 2020
Technology in conservation: towards a system for in-field drone detection of invasive vegetation
- James, Katherine Margaret Frances
- Authors: James, Katherine Margaret Frances
- Date: 2020
- Subjects: Drone aircraft in remote sensing , Neural networks (Computer science) , Drone aircraft in remote sensing -- Case studies , Machine learning , Computer vision , Environmental monitoring -- Remote sensing , Invasive plants -- Monitoring
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/143408 , vital:38244
- Description: Remote sensing can assist in monitoring the spread of invasive vegetation. The adoption of camera-carrying unmanned aerial vehicles, commonly referred to as drones, as remote sensing tools has yielded images of higher spatial resolution than traditional techniques. Drones also have the potential to interact with the environment through the delivery of bio-control or herbicide, as seen with their adoption in precision agriculture. Unlike in agricultural applications, however, invasive plants do not have a predictable position relative to each other within the environment. To facilitate the adoption of drones as an environmental monitoring and management tool, drones need to be able to intelligently distinguish between invasive and non-invasive vegetation on the fly. In this thesis, we present the augmentation of a commercially available drone with a deep machine learning model to investigate the viability of differentiating between an invasive shrub and other vegetation. As a case study, this was applied to the shrub genus Hakea, originating in Australia and invasive in several countries including South Africa. However, for this research, the methodology is important, rather than the chosen target plant. A dataset was collected using the available drone and manually annotated to facilitate the supervised training of the model. Two approaches were explored, namely, classification and semantic segmentation. For each of these, several models were trained and evaluated to find the optimal one. The chosen model was then interfaced with the drone via an Android application on a mobile device and its performance was preliminarily evaluated in the field. Based on these findings, refinements were made and thereafter a thorough field evaluation was performed to determine the best conditions for model operation. Results from the classification task show that deep learning models are capable of distinguishing between target and other shrubs in ideal candidate windows. However, classification in this manner is restricted by the proposal of such candidate windows. End-to-end image segmentation using deep learning overcomes this problem, classifying the image in a pixel-wise manner. Furthermore, the use of appropriate loss functions was found to improve model performance. Field tests show that illumination and shadow pose challenges to the model, but that good recall can be achieved when the conditions are ideal. False positive detection remains an issue that could be improved. This approach shows the potential for drones as an environmental monitoring and management tool when coupled with deep machine learning techniques and outlines potential problems that may be encountered.
- Full Text:
- Date Issued: 2020
- Authors: James, Katherine Margaret Frances
- Date: 2020
- Subjects: Drone aircraft in remote sensing , Neural networks (Computer science) , Drone aircraft in remote sensing -- Case studies , Machine learning , Computer vision , Environmental monitoring -- Remote sensing , Invasive plants -- Monitoring
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/143408 , vital:38244
- Description: Remote sensing can assist in monitoring the spread of invasive vegetation. The adoption of camera-carrying unmanned aerial vehicles, commonly referred to as drones, as remote sensing tools has yielded images of higher spatial resolution than traditional techniques. Drones also have the potential to interact with the environment through the delivery of bio-control or herbicide, as seen with their adoption in precision agriculture. Unlike in agricultural applications, however, invasive plants do not have a predictable position relative to each other within the environment. To facilitate the adoption of drones as an environmental monitoring and management tool, drones need to be able to intelligently distinguish between invasive and non-invasive vegetation on the fly. In this thesis, we present the augmentation of a commercially available drone with a deep machine learning model to investigate the viability of differentiating between an invasive shrub and other vegetation. As a case study, this was applied to the shrub genus Hakea, originating in Australia and invasive in several countries including South Africa. However, for this research, the methodology is important, rather than the chosen target plant. A dataset was collected using the available drone and manually annotated to facilitate the supervised training of the model. Two approaches were explored, namely, classification and semantic segmentation. For each of these, several models were trained and evaluated to find the optimal one. The chosen model was then interfaced with the drone via an Android application on a mobile device and its performance was preliminarily evaluated in the field. Based on these findings, refinements were made and thereafter a thorough field evaluation was performed to determine the best conditions for model operation. Results from the classification task show that deep learning models are capable of distinguishing between target and other shrubs in ideal candidate windows. However, classification in this manner is restricted by the proposal of such candidate windows. End-to-end image segmentation using deep learning overcomes this problem, classifying the image in a pixel-wise manner. Furthermore, the use of appropriate loss functions was found to improve model performance. Field tests show that illumination and shadow pose challenges to the model, but that good recall can be achieved when the conditions are ideal. False positive detection remains an issue that could be improved. This approach shows the potential for drones as an environmental monitoring and management tool when coupled with deep machine learning techniques and outlines potential problems that may be encountered.
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- Date Issued: 2020