Finite precision arithmetic in Polyphase Filterbank implementations
- Authors: Myburgh, Talon
- Date: 2020
- Subjects: Radio interferometers , Interferometry , Radio telescopes , Gate array circuits , Floating-point arithmetic , Python (Computer program language) , Polyphase Filterbank , Finite precision arithmetic , MeerKAT
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146187 , vital:38503
- Description: The MeerKAT is the most sensitive radio telescope in its class, and it is important that systematic effects do not limit the dynamic range of the instrument, preventing this sensitivity from being harnessed for deep integrations. During commissioning, spurious artefacts were noted in the MeerKAT passband and the root cause was attributed to systematic errors in the digital signal path. Finite precision arithmetic used by the Polyphase Filterbank (PFB) was one of the main factors contributing to the spurious responses, together with bugs in the firmware. This thesis describes a software PFB simulator that was built to mimic the MeerKAT PFB and allow investigation into the origin and mitigation of the effects seen on the telescope. This simulator was used to investigate the effects in signal integrity of various rounding techniques, overflow strategies and dual polarisation processing in the PFB. Using the simulator to investigate a number of different signal levels, bit-width and algorithmic scenarios, it gave insight into how the periodic dips occurring in the MeerKAT passband were the result of the implementation using an inappropriate rounding strategy. It further indicated how to select the best strategy for preventing overflow while maintaining high quantization effciency in the FFT. This practice of simulating the design behaviour in the PFB independently of the tools used to design the DSP firmware, is a step towards an end-to-end simulation of the MeerKAT system (or any radio telescope using nite precision digital signal processing systems). This would be useful for design, diagnostics, signal analysis and prototyping of the overall instrument.
- Full Text:
- Date Issued: 2020
- Authors: Myburgh, Talon
- Date: 2020
- Subjects: Radio interferometers , Interferometry , Radio telescopes , Gate array circuits , Floating-point arithmetic , Python (Computer program language) , Polyphase Filterbank , Finite precision arithmetic , MeerKAT
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146187 , vital:38503
- Description: The MeerKAT is the most sensitive radio telescope in its class, and it is important that systematic effects do not limit the dynamic range of the instrument, preventing this sensitivity from being harnessed for deep integrations. During commissioning, spurious artefacts were noted in the MeerKAT passband and the root cause was attributed to systematic errors in the digital signal path. Finite precision arithmetic used by the Polyphase Filterbank (PFB) was one of the main factors contributing to the spurious responses, together with bugs in the firmware. This thesis describes a software PFB simulator that was built to mimic the MeerKAT PFB and allow investigation into the origin and mitigation of the effects seen on the telescope. This simulator was used to investigate the effects in signal integrity of various rounding techniques, overflow strategies and dual polarisation processing in the PFB. Using the simulator to investigate a number of different signal levels, bit-width and algorithmic scenarios, it gave insight into how the periodic dips occurring in the MeerKAT passband were the result of the implementation using an inappropriate rounding strategy. It further indicated how to select the best strategy for preventing overflow while maintaining high quantization effciency in the FFT. This practice of simulating the design behaviour in the PFB independently of the tools used to design the DSP firmware, is a step towards an end-to-end simulation of the MeerKAT system (or any radio telescope using nite precision digital signal processing systems). This would be useful for design, diagnostics, signal analysis and prototyping of the overall instrument.
- Full Text:
- Date Issued: 2020
Formulation and evaluation of liposomal films for buccal delivery of antiretroviral drug
- Authors: Okafor, Nnamdi Ikemefuna
- Date: 2020
- Subjects: Liposomes , Highly active antiretroviral therapy , Antiretroviral agents , HIV infections -- Prevention
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117161 , vital:34485
- Description: The human immune deficiency virus (HIV) infection has been ranked as one of the most devastating microbial infections in the world. This status is a result of the HIV rapid genetic variation, which limits discovery of a vaccine. Use application of antiretroviral therapy (ARVT) in treatment of the disease caused by the HIV infection (known as acquired immunodeficiency syndrome, HIV-AIDS) is frequently compromised by several factors such as the low bioavailability and severe adverse effects associated with the existing antiretroviral drugs (ARVDs). This underlines the need for controlling the pharmacokinetics profiles of ARVD using effective vehicles that can modify drug biodistribution. The same is true for many other conditions, where delivery systems can determine the success or failure of treatment by controlling pharmacokinetic and dynamic properties. The mucosal linings of the oral cavities in addition offer adorable route of administration for systematic drug delivery, improving drug therapeutic performance and often preferred by clinicians and patients. Liposomes are tiny spherical sacs of phospholipid molecules enclosing water droplets, formed (artificially) to carry drugs or other substances into the tissues by crossing and targeting to specific organelles. This work therefore focused on preparation of liposomes and liposomal buccal films (BFs) for potential buccal delivery of efavirenz, an ARVD model endowed with poor solubility and several side effects. The liposomes were prepared by thin film hydration method using crude soybean lecithin (CL) and cholesterol. Efavirenz loaded liposomes were evaluated for particle size, Zeta potential (ZP), morphology, encapsulation efficiency (EE%) and release kinetics studies. The physiochemical properties of the liposomes were also evaluated using Differential Scanning Calorimetry (DSC), X-ray diffraction (XRD), energy dispersity spectroscopy (EDS), and Fourier transform infrared (FTIR), while the formulation with the best encapsulation efficiency was used as the solvent medium for the buccal film formation. The buccal films were prepared using solvent casting method, where the liposomal suspension was used as the dispersing medium. The films were optimized for physical properties (thickness, weight variation and folding endurance) using digital Vernier calliper and digital weighing balance. The physiochemical properties of the selected BFs films made of Carbopol (CP) and its combination with Pluronic F127 (PF127) were further characterized using XRD, DSC, FTIR, Transmission Electron Microscopy (TEM), EDS and Scanning Electron Microscopy (SEM). The permeation study of the selected BFs was investigated using Franz diffusion cell. The BFs composed of CP alone or its combination with PF127 demonstrated much better bio-adhesive properties than the films made of other polymers (like Hydroxyl propyl methyl cellulose, HPMC) alone or in combination with PF127. The developed liposome formulation showed high encapsulation 98.8 ± 0.01 % in CL to cholesterol mass ratio of 1:1 and total lipid to drug mass ratio of 2:1. The average particle size 104.82 ± 2.29 nm and Zeta potential -50.33 ± 0.95 mV of these liposomes were found to be attractive for targeted delivery to the HIV infected cells. The CP based BFs (without and with PF127) exhibited good film thickness 0.88 ± 0.10 and 0.76 ± 0.14 mm, with weight uniformity 68.22 ± 1.04 and 86.28 ± 2. 16 mg, satisfactory flexibility values 258 and 321, and slightly acidic pH 6.43 ± 0.76 and 6.32 ± 0.01. The swelling percentage was found to be 50 % for CP film alone and 78 % for CP film with PF127. The cumulative amount of drug that permeated through the buccal epithelium over 24 hours was about 66 % from CP film alone and 75 % from CP film with PF127. Since no evidence of the liposomal encapsulation of EFV have been reported to our knowledge, we find the insights from the present study valuable as a set of preliminary data to encourage further investigations of the encapsulation and delivery of EFV like antiretrovirals for enhanced solubility, site targeting and prolonged release using crude soybean lecithin and mucoadhesive polymers, which holds some added economical values as naturally occurring lipid and polymeric mixtures as a promising delivery systems for buccal delivery of ARVDs.
- Full Text:
- Date Issued: 2020
- Authors: Okafor, Nnamdi Ikemefuna
- Date: 2020
- Subjects: Liposomes , Highly active antiretroviral therapy , Antiretroviral agents , HIV infections -- Prevention
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117161 , vital:34485
- Description: The human immune deficiency virus (HIV) infection has been ranked as one of the most devastating microbial infections in the world. This status is a result of the HIV rapid genetic variation, which limits discovery of a vaccine. Use application of antiretroviral therapy (ARVT) in treatment of the disease caused by the HIV infection (known as acquired immunodeficiency syndrome, HIV-AIDS) is frequently compromised by several factors such as the low bioavailability and severe adverse effects associated with the existing antiretroviral drugs (ARVDs). This underlines the need for controlling the pharmacokinetics profiles of ARVD using effective vehicles that can modify drug biodistribution. The same is true for many other conditions, where delivery systems can determine the success or failure of treatment by controlling pharmacokinetic and dynamic properties. The mucosal linings of the oral cavities in addition offer adorable route of administration for systematic drug delivery, improving drug therapeutic performance and often preferred by clinicians and patients. Liposomes are tiny spherical sacs of phospholipid molecules enclosing water droplets, formed (artificially) to carry drugs or other substances into the tissues by crossing and targeting to specific organelles. This work therefore focused on preparation of liposomes and liposomal buccal films (BFs) for potential buccal delivery of efavirenz, an ARVD model endowed with poor solubility and several side effects. The liposomes were prepared by thin film hydration method using crude soybean lecithin (CL) and cholesterol. Efavirenz loaded liposomes were evaluated for particle size, Zeta potential (ZP), morphology, encapsulation efficiency (EE%) and release kinetics studies. The physiochemical properties of the liposomes were also evaluated using Differential Scanning Calorimetry (DSC), X-ray diffraction (XRD), energy dispersity spectroscopy (EDS), and Fourier transform infrared (FTIR), while the formulation with the best encapsulation efficiency was used as the solvent medium for the buccal film formation. The buccal films were prepared using solvent casting method, where the liposomal suspension was used as the dispersing medium. The films were optimized for physical properties (thickness, weight variation and folding endurance) using digital Vernier calliper and digital weighing balance. The physiochemical properties of the selected BFs films made of Carbopol (CP) and its combination with Pluronic F127 (PF127) were further characterized using XRD, DSC, FTIR, Transmission Electron Microscopy (TEM), EDS and Scanning Electron Microscopy (SEM). The permeation study of the selected BFs was investigated using Franz diffusion cell. The BFs composed of CP alone or its combination with PF127 demonstrated much better bio-adhesive properties than the films made of other polymers (like Hydroxyl propyl methyl cellulose, HPMC) alone or in combination with PF127. The developed liposome formulation showed high encapsulation 98.8 ± 0.01 % in CL to cholesterol mass ratio of 1:1 and total lipid to drug mass ratio of 2:1. The average particle size 104.82 ± 2.29 nm and Zeta potential -50.33 ± 0.95 mV of these liposomes were found to be attractive for targeted delivery to the HIV infected cells. The CP based BFs (without and with PF127) exhibited good film thickness 0.88 ± 0.10 and 0.76 ± 0.14 mm, with weight uniformity 68.22 ± 1.04 and 86.28 ± 2. 16 mg, satisfactory flexibility values 258 and 321, and slightly acidic pH 6.43 ± 0.76 and 6.32 ± 0.01. The swelling percentage was found to be 50 % for CP film alone and 78 % for CP film with PF127. The cumulative amount of drug that permeated through the buccal epithelium over 24 hours was about 66 % from CP film alone and 75 % from CP film with PF127. Since no evidence of the liposomal encapsulation of EFV have been reported to our knowledge, we find the insights from the present study valuable as a set of preliminary data to encourage further investigations of the encapsulation and delivery of EFV like antiretrovirals for enhanced solubility, site targeting and prolonged release using crude soybean lecithin and mucoadhesive polymers, which holds some added economical values as naturally occurring lipid and polymeric mixtures as a promising delivery systems for buccal delivery of ARVDs.
- Full Text:
- Date Issued: 2020
Generation of a virtual library of terpenes using graph theory, and its application in exploration of the mechanisms of terpene biosynthesis
- Authors: Dendera, Washington
- Date: 2020
- Subjects: Terpenes , Plants -- Metabolism , Computational biology , Bioinformatics , Organic compounds -- Synthesis , Monoterpenes , Molecular biology -- Computer simulation
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/123453 , vital:35439
- Description: Terpenes form a large group of organic compounds which have proven to be of use to many living organisms being used by plants for metabolism (Pichersky and Gershenzon, 1934; McGarvey and Croteau, 1995; Gershenzon and Dudareva, 2007), defence or as a means to attract pollinators and also used by humans in medical, pharmaceutical and food industry (Bicas, Dionísio and Pastore, 2009; Marmulla and Harder, 2014; Kandi et al., 2015). Following on literature methods to generate chemical libraries using graph theoretic techniques, complete libraries of all possible terpene isomers have been constructed with the goal of construction of derivative libraries of possible carbocation intermediates which are important in the elucidation of mechanisms in the biosynthesis of terpenes. Virtual library generation of monoterpenes was first achieved by generating graphs of order 7, 8, 9 and 10 using the Nauty and Traces suite. These were screened and processed with a set of collated Python scripts written to recognize the graphs in text format and translate them to molecules, minimizing through Tinker whilst discarding graphs that violate chemistry laws. As a result of the computational time required only order 7 and order 10 graphs were processed. Out of the 873 graphs generated from order seven, 353 were converted to molecules and from the 11,7 million produced from order 10 half were processed resulting in the production of 442928 compounds (repeats included). For screening, 55 366 compounds were docked in the active site of limonene synthase; of these 2355 ligands had a good Vina docking score with a binding energy of between -7.0 and -7.4 kcal.mol-1. When these best docked molecules were overlaid in the active site a map of possible ligand positions within the active site of limonene synthase was traced out.
- Full Text:
- Date Issued: 2020
- Authors: Dendera, Washington
- Date: 2020
- Subjects: Terpenes , Plants -- Metabolism , Computational biology , Bioinformatics , Organic compounds -- Synthesis , Monoterpenes , Molecular biology -- Computer simulation
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/123453 , vital:35439
- Description: Terpenes form a large group of organic compounds which have proven to be of use to many living organisms being used by plants for metabolism (Pichersky and Gershenzon, 1934; McGarvey and Croteau, 1995; Gershenzon and Dudareva, 2007), defence or as a means to attract pollinators and also used by humans in medical, pharmaceutical and food industry (Bicas, Dionísio and Pastore, 2009; Marmulla and Harder, 2014; Kandi et al., 2015). Following on literature methods to generate chemical libraries using graph theoretic techniques, complete libraries of all possible terpene isomers have been constructed with the goal of construction of derivative libraries of possible carbocation intermediates which are important in the elucidation of mechanisms in the biosynthesis of terpenes. Virtual library generation of monoterpenes was first achieved by generating graphs of order 7, 8, 9 and 10 using the Nauty and Traces suite. These were screened and processed with a set of collated Python scripts written to recognize the graphs in text format and translate them to molecules, minimizing through Tinker whilst discarding graphs that violate chemistry laws. As a result of the computational time required only order 7 and order 10 graphs were processed. Out of the 873 graphs generated from order seven, 353 were converted to molecules and from the 11,7 million produced from order 10 half were processed resulting in the production of 442928 compounds (repeats included). For screening, 55 366 compounds were docked in the active site of limonene synthase; of these 2355 ligands had a good Vina docking score with a binding energy of between -7.0 and -7.4 kcal.mol-1. When these best docked molecules were overlaid in the active site a map of possible ligand positions within the active site of limonene synthase was traced out.
- Full Text:
- Date Issued: 2020
Get sleep or get stumped: sleep behaviour in elite South African cricket players during competition
- Authors: McEwan, Kayla
- Date: 2020
- Subjects: Sleep -- Physiological aspects , Cricket players -- Health and hygiene , Cricket players -- South Africa -- Health and hygiene , Cricket -- Health aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/147950 , vital:38696
- Description: Introduction: Good sleep behaviour is associated with achieving optimal athletic performance and reducing the risk of injury. Elite cricket players have unique physical and cognitive demands, and must accommodate for congested competition and travel schedules (all of which increase the risk of disruptive sleep). Further, the political pressures and socioeconomic barriers in South African cricket could affect the sleep of the country’s elite players. Previous research in cricket has focussed on the impact that nutrition, equipment specifications, movement physiology and psychology could elicit on performance (where many professional teams hire support staff to supervise these disciplines); however, there is limited empirical application of sleep research in elite cricket players. Therefore, this study aimed to characterise the sleep behaviours of elite South African cricket players during periods of competition and investigate the relationship between pre-match sleep and cricket performance. Methods: A longitudinal field-based investigation was implemented to monitor the sleep behaviour of 26 elite South African cricket players (age: 28.6 ± 4.0 years; height: 1.8 ± 0.1 m; weight: 85.7 ± 10.8 kg; elite experience: 3.7 ± 4.0 years) during home and away competitive tours. The Morningness-Eveningness Questionnaire and Athlete Sleep Behaviour Questionnaire were administered to identify chronotype and poor sleep behaviours. Players completed an altered version of the Core Consensus Sleep Diary every morning post-travel, pre-match and post-match. Linear mixed model regression was used to compare differences in sleep variables between time-periods, match venues, player roles, match formats, sleep medication and racial groups. Spearman’s correlation (rs) was used to assess the relationship of substance use (alcohol and caffeine), age, elite experience and match performance with selected sleep indices. Statistical significance for all measures was accepted at p < 0.05. Hedge’s (g) were used as the measure of effect size. Results: Light-emitting technology use, effects of travel, late evening alcohol consumption and muscle soreness were the main factors that impacted sleep. Post-match total sleep time (06:31 ± 01:09) was significantly (p < 0.05) shorter compared to post-travel (07:53 ± 01:07; g = 1.19 [0.81;1.57]) and pre-match (08:43 ± 01:03; g = 1.97 [1.55;2.39]) total sleep time. Post-travel sleep onset latency and sleep efficiency were significantly (p < 0.05) shorter (g = 0.74 [0.29;1.29]) and higher (g = 1.35 [0.76;1.94]) at home than away. Although not significant (p > 0.05), allrounders took longer to fall asleep (g = 0.90 [0.23;1.57]), obtained less total sleep (0.76 [0.29;1.42]) and had lower morning freshness scores (g = 1.10 [0.42;1.78]) the night before a match compared to batsmen. Wake after sleep onset and get up time were moderately longer (g = 0.61 [0.22;1.26]) and later (g = 0.62 [0.27;1.17]) before. Twenty20 matches compared to One-Day International matches respectively. Further, sleep duration significantly declined from pre-match to post-match during the multi-day Test format (p = 0.04, g= 0.75 [0.40;1.12]). Late alcohol consumption was significantly (p < 0.05) correlated with a decrease in total sleep time, regardless of match venue (home: rs (49) = -0.69; away: rs (27) = -0.57). During the away condition, an increase in age was significantly associated with longer wake after sleep onset durations (rs (13) = 0.52, p = 0.0003), while greater elite experience was significantly associated with longer total sleep time (rs (72) = 0.36, p = 0.02). The non-sleep medication group took significantly longer to fall asleep compared to the sleep medication group during the first week of the away condition (p = 0.02, g = 0.75 [0.25;1.26]) particularly on nights following transmeridian travel. Although not significant ( p > 0.05), Asian/Indian players had moderately longer sleep onset latencies (g = 1.07 [0.66;1.47]), wake after sleep onset durations (g = 0.86 [0.42;1.29]), and lower subjective sleep quality (g = 0.86 [0.46;1.26]) and morning freshness scores (g = 0.89 [0.47;1.27]) compared to Whites. Similarly, Black Africans had moderately lower subjective sleep quality scores compared to Whites (g = 0.71 [0.43;0.97]). Longer sleep onset latencies and shorter total sleep times were significantly (p < 0.05) associated with poorer One-Day International (rs (28) = -0.57) and Test (rs (12) = 0.59) batting performances respectively. Higher subjective sleep quality scores were significantly associated with better Twenty20 bowling economies (rs (8) = -0.52). Discussion: There was no evidence of poor pre-match sleep behaviour, irrespective of venue; however, the most apparent disruption to sleep occurred post-match (similar to that found in other team-sports). Most disparities in sleep between match venues existed post-travel, with better sleep behaviour observed during the home condition. The differences in sleep patterns found in all three match formats were expected given the variations in format scheduling and duration. Although sleep medication was shown to promote better sleep, its long-term effectiveness was limited. The results promote the implementation of practical strategies aimed to reduce bedtime light-emitting technology use, late evening alcohol consumption and muscle pain. Inter-individual sleep behaviour was found between player roles, age, experience level and race. Moderate associations existed between sleep and markers of batting performance, specifically for the longer, strategic formats of the game. Conclusion: The current study provided new insight of the sleep behaviour in elite South African cricket players during competition. Individualized sleep monitoring practices are encouraged, with specific supervision over older, less experienced players as well as the racial minorities and allrounders of the team. The poor post-match sleep behaviour, together with the sleep and performance correlations, provide ideal opportunities for future interventions to focus on match recovery and the use sleep monitoring as a competitive advantage.
- Full Text:
- Date Issued: 2020
- Authors: McEwan, Kayla
- Date: 2020
- Subjects: Sleep -- Physiological aspects , Cricket players -- Health and hygiene , Cricket players -- South Africa -- Health and hygiene , Cricket -- Health aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/147950 , vital:38696
- Description: Introduction: Good sleep behaviour is associated with achieving optimal athletic performance and reducing the risk of injury. Elite cricket players have unique physical and cognitive demands, and must accommodate for congested competition and travel schedules (all of which increase the risk of disruptive sleep). Further, the political pressures and socioeconomic barriers in South African cricket could affect the sleep of the country’s elite players. Previous research in cricket has focussed on the impact that nutrition, equipment specifications, movement physiology and psychology could elicit on performance (where many professional teams hire support staff to supervise these disciplines); however, there is limited empirical application of sleep research in elite cricket players. Therefore, this study aimed to characterise the sleep behaviours of elite South African cricket players during periods of competition and investigate the relationship between pre-match sleep and cricket performance. Methods: A longitudinal field-based investigation was implemented to monitor the sleep behaviour of 26 elite South African cricket players (age: 28.6 ± 4.0 years; height: 1.8 ± 0.1 m; weight: 85.7 ± 10.8 kg; elite experience: 3.7 ± 4.0 years) during home and away competitive tours. The Morningness-Eveningness Questionnaire and Athlete Sleep Behaviour Questionnaire were administered to identify chronotype and poor sleep behaviours. Players completed an altered version of the Core Consensus Sleep Diary every morning post-travel, pre-match and post-match. Linear mixed model regression was used to compare differences in sleep variables between time-periods, match venues, player roles, match formats, sleep medication and racial groups. Spearman’s correlation (rs) was used to assess the relationship of substance use (alcohol and caffeine), age, elite experience and match performance with selected sleep indices. Statistical significance for all measures was accepted at p < 0.05. Hedge’s (g) were used as the measure of effect size. Results: Light-emitting technology use, effects of travel, late evening alcohol consumption and muscle soreness were the main factors that impacted sleep. Post-match total sleep time (06:31 ± 01:09) was significantly (p < 0.05) shorter compared to post-travel (07:53 ± 01:07; g = 1.19 [0.81;1.57]) and pre-match (08:43 ± 01:03; g = 1.97 [1.55;2.39]) total sleep time. Post-travel sleep onset latency and sleep efficiency were significantly (p < 0.05) shorter (g = 0.74 [0.29;1.29]) and higher (g = 1.35 [0.76;1.94]) at home than away. Although not significant (p > 0.05), allrounders took longer to fall asleep (g = 0.90 [0.23;1.57]), obtained less total sleep (0.76 [0.29;1.42]) and had lower morning freshness scores (g = 1.10 [0.42;1.78]) the night before a match compared to batsmen. Wake after sleep onset and get up time were moderately longer (g = 0.61 [0.22;1.26]) and later (g = 0.62 [0.27;1.17]) before. Twenty20 matches compared to One-Day International matches respectively. Further, sleep duration significantly declined from pre-match to post-match during the multi-day Test format (p = 0.04, g= 0.75 [0.40;1.12]). Late alcohol consumption was significantly (p < 0.05) correlated with a decrease in total sleep time, regardless of match venue (home: rs (49) = -0.69; away: rs (27) = -0.57). During the away condition, an increase in age was significantly associated with longer wake after sleep onset durations (rs (13) = 0.52, p = 0.0003), while greater elite experience was significantly associated with longer total sleep time (rs (72) = 0.36, p = 0.02). The non-sleep medication group took significantly longer to fall asleep compared to the sleep medication group during the first week of the away condition (p = 0.02, g = 0.75 [0.25;1.26]) particularly on nights following transmeridian travel. Although not significant ( p > 0.05), Asian/Indian players had moderately longer sleep onset latencies (g = 1.07 [0.66;1.47]), wake after sleep onset durations (g = 0.86 [0.42;1.29]), and lower subjective sleep quality (g = 0.86 [0.46;1.26]) and morning freshness scores (g = 0.89 [0.47;1.27]) compared to Whites. Similarly, Black Africans had moderately lower subjective sleep quality scores compared to Whites (g = 0.71 [0.43;0.97]). Longer sleep onset latencies and shorter total sleep times were significantly (p < 0.05) associated with poorer One-Day International (rs (28) = -0.57) and Test (rs (12) = 0.59) batting performances respectively. Higher subjective sleep quality scores were significantly associated with better Twenty20 bowling economies (rs (8) = -0.52). Discussion: There was no evidence of poor pre-match sleep behaviour, irrespective of venue; however, the most apparent disruption to sleep occurred post-match (similar to that found in other team-sports). Most disparities in sleep between match venues existed post-travel, with better sleep behaviour observed during the home condition. The differences in sleep patterns found in all three match formats were expected given the variations in format scheduling and duration. Although sleep medication was shown to promote better sleep, its long-term effectiveness was limited. The results promote the implementation of practical strategies aimed to reduce bedtime light-emitting technology use, late evening alcohol consumption and muscle pain. Inter-individual sleep behaviour was found between player roles, age, experience level and race. Moderate associations existed between sleep and markers of batting performance, specifically for the longer, strategic formats of the game. Conclusion: The current study provided new insight of the sleep behaviour in elite South African cricket players during competition. Individualized sleep monitoring practices are encouraged, with specific supervision over older, less experienced players as well as the racial minorities and allrounders of the team. The poor post-match sleep behaviour, together with the sleep and performance correlations, provide ideal opportunities for future interventions to focus on match recovery and the use sleep monitoring as a competitive advantage.
- Full Text:
- Date Issued: 2020
Growth and photosynthetic responses of Acacia (Vachellia) seedlings to atmospheric CO2 increased from glacial to current concentrations: underlying mechanisms and ecological implications
- Authors: Anderson, Bruce Maurice
- Date: 2020
- Subjects: Acacia vachellia , Acacia vachellia -- Growth , Acacia -- South Africa
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/138182 , vital:37604
- Description: The African Acacia species Vachellia karroo, V. robusta, V. nilotica, and V. tortilis are some of the most invasive species implicated in bush encroachment and woody thickening of historically open savannas in southern Africa. This is partially explained by historic increases in atmospheric CO2 concentrations, which are proposed to have promoted the growth and survivorship of C3 tree seedlings relative to C4 grasses. However, the uniformity of CO2 responsiveness and differences among Vachellia species remain largely undetermined. Here we investigate the growth and photosynthetic responses of four Vachellia species, all implicated in woody encroachment, but originating from distinct climatic niches. Exposing these species to a range of sub-ambient CO2 concentrations (12 – 40 Pa) showed that V. karroo, V. robusta, V. nilotica and V. tortilis all responded strongly and fairly consistently to increasing CO2 concentrations, acting as a ‘functional type’ despite being selected from different geographic regions and having different climatic niches. Combined average net CO2 assimilation rates increased by 130% despite significant, but low levels of down-regulation and decreased stomatal conductance. The increased photosynthetic rates stimulated growth and biomass production in all compartments, with no significant differences in interspecific above and below ground allocation. Growth rates and dry biomass increased by 50% and 186%, respectively, while leaf level water use efficiency (ratio of net CO2 assimilation rate to transpiration rate) increased by an average of 218%. When this was scaled to the whole plant level, this stimulation was decreased to 80%. The decrease was the result of the CO2 stimulated increase in canopy areas, which increased leaf area for water loss. The seedlings’ total number of spinescent physical defenses, as well as the average mass and spine mass fraction also increased with rising CO2. These thicker spines could act as better deterrents against vertebrate browsers. Spine density was unchanged, however, showing that the increased spine numbers were associated with larger seedlings at higher CO2 rather than an increase in the number of spines per stem length. The stimulatory effects of increasing CO2 concentrations since the last glacial maximum and resultant increases in seedling growth and biomass are likely to have had important consequences for the survival and establishment of Acacia seedlings. Tolerance of drought and disturbance has been related to seedling size, hence stimulating the growth rate could confer disturbance tolerance and this tolerance would develop more rapidly with increasing CO2 concentrations. Furthermore, increased nitrogen and water use efficiency have the potential to support seedling establishment in environments where these resources would otherwise be limited at lower atmospheric CO2 concentrations. Resulting in a larger proportion of CO2 fertilization responsive woody seedlings surviving the seedling size classes, and persisting within historically open savannas. Where interspecific differences occurred they are likely to have arisen from adaptation to specific climates where these species are native and selection would have been driven by factors such climate, resource availability, levels of disturbance and competitive interactions. V. karroo had the highest growth rates and strong CO2 driven increases in biomass accumulation, despite having the lowest inherent photosynthetic rates. V. karroo also had the lowest increase in water use efficiency and high transpiration rates could potentially increase access to soil nutrients through mass flow. This species had the highest mean spine mass and showed significant increases in spine mass fraction at elevated CO2 concentrations, which may be important for deterring herbivores. V. robusta’s distribution to the mesic east coast of Africa suggests that water is an important limitation to its distribution. Hence, the CO2 stimulated increase in water use efficiency at both leaf and whole canopy level allows speculation that this may be an important driver of this species’ range expansion, which might continue if increasing levels of CO2 continue to promote water use efficiency. V. nilotica occupies a broad range of habitats, inhabiting large areas of the subtropics both north and south of the equator, with the strongest climatic correlates being the precipitation of the wettest quarter followed by high temperature seasonality. In response to increasing CO2, V. nilotica showed overall strong increases in growth, water use efficiency, and physical defenses. These responses may explain why V. nilotica has been such a successful encroacher in a broad range of habitats where limitations are likely to include multiple climatic factors and disturbances. V. tortilis has the widest distribution of all the species studied, covering broad ranges of Africa and only being excluded from the wettest parts of the equator and driest parts of the deserts. In these experiments this species showed the lowest biomass responsiveness to CO2, but had especially large increases in water use efficiency at both the leaf and canopy level. This may have been an important driver for this species’ encroachment into the more arid parts of its distribution, however this link will need to be verified with further experimentation.
- Full Text:
- Date Issued: 2020
- Authors: Anderson, Bruce Maurice
- Date: 2020
- Subjects: Acacia vachellia , Acacia vachellia -- Growth , Acacia -- South Africa
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/138182 , vital:37604
- Description: The African Acacia species Vachellia karroo, V. robusta, V. nilotica, and V. tortilis are some of the most invasive species implicated in bush encroachment and woody thickening of historically open savannas in southern Africa. This is partially explained by historic increases in atmospheric CO2 concentrations, which are proposed to have promoted the growth and survivorship of C3 tree seedlings relative to C4 grasses. However, the uniformity of CO2 responsiveness and differences among Vachellia species remain largely undetermined. Here we investigate the growth and photosynthetic responses of four Vachellia species, all implicated in woody encroachment, but originating from distinct climatic niches. Exposing these species to a range of sub-ambient CO2 concentrations (12 – 40 Pa) showed that V. karroo, V. robusta, V. nilotica and V. tortilis all responded strongly and fairly consistently to increasing CO2 concentrations, acting as a ‘functional type’ despite being selected from different geographic regions and having different climatic niches. Combined average net CO2 assimilation rates increased by 130% despite significant, but low levels of down-regulation and decreased stomatal conductance. The increased photosynthetic rates stimulated growth and biomass production in all compartments, with no significant differences in interspecific above and below ground allocation. Growth rates and dry biomass increased by 50% and 186%, respectively, while leaf level water use efficiency (ratio of net CO2 assimilation rate to transpiration rate) increased by an average of 218%. When this was scaled to the whole plant level, this stimulation was decreased to 80%. The decrease was the result of the CO2 stimulated increase in canopy areas, which increased leaf area for water loss. The seedlings’ total number of spinescent physical defenses, as well as the average mass and spine mass fraction also increased with rising CO2. These thicker spines could act as better deterrents against vertebrate browsers. Spine density was unchanged, however, showing that the increased spine numbers were associated with larger seedlings at higher CO2 rather than an increase in the number of spines per stem length. The stimulatory effects of increasing CO2 concentrations since the last glacial maximum and resultant increases in seedling growth and biomass are likely to have had important consequences for the survival and establishment of Acacia seedlings. Tolerance of drought and disturbance has been related to seedling size, hence stimulating the growth rate could confer disturbance tolerance and this tolerance would develop more rapidly with increasing CO2 concentrations. Furthermore, increased nitrogen and water use efficiency have the potential to support seedling establishment in environments where these resources would otherwise be limited at lower atmospheric CO2 concentrations. Resulting in a larger proportion of CO2 fertilization responsive woody seedlings surviving the seedling size classes, and persisting within historically open savannas. Where interspecific differences occurred they are likely to have arisen from adaptation to specific climates where these species are native and selection would have been driven by factors such climate, resource availability, levels of disturbance and competitive interactions. V. karroo had the highest growth rates and strong CO2 driven increases in biomass accumulation, despite having the lowest inherent photosynthetic rates. V. karroo also had the lowest increase in water use efficiency and high transpiration rates could potentially increase access to soil nutrients through mass flow. This species had the highest mean spine mass and showed significant increases in spine mass fraction at elevated CO2 concentrations, which may be important for deterring herbivores. V. robusta’s distribution to the mesic east coast of Africa suggests that water is an important limitation to its distribution. Hence, the CO2 stimulated increase in water use efficiency at both leaf and whole canopy level allows speculation that this may be an important driver of this species’ range expansion, which might continue if increasing levels of CO2 continue to promote water use efficiency. V. nilotica occupies a broad range of habitats, inhabiting large areas of the subtropics both north and south of the equator, with the strongest climatic correlates being the precipitation of the wettest quarter followed by high temperature seasonality. In response to increasing CO2, V. nilotica showed overall strong increases in growth, water use efficiency, and physical defenses. These responses may explain why V. nilotica has been such a successful encroacher in a broad range of habitats where limitations are likely to include multiple climatic factors and disturbances. V. tortilis has the widest distribution of all the species studied, covering broad ranges of Africa and only being excluded from the wettest parts of the equator and driest parts of the deserts. In these experiments this species showed the lowest biomass responsiveness to CO2, but had especially large increases in water use efficiency at both the leaf and canopy level. This may have been an important driver for this species’ encroachment into the more arid parts of its distribution, however this link will need to be verified with further experimentation.
- Full Text:
- Date Issued: 2020
Identification of SANCDB compounds against G2019S and I2020T variants of leucine-rich repeat Kinase 2 (LRRK2) for the development of drugs against Parkinson’s Disease
- Authors: Baye, Bertha Cinthia
- Date: 2020
- Subjects: Antiparkinsonian agents , Parkinson's disease -- Treatment , Protein kinases , Parkinson's disease -- Chemotherapy , Molecules -- Models
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/138764 , vital:37671
- Description: Parkinson’s disease is a type of movement disorder that occurs when nerve cells in the brain stop producing dopamine. It is the second neurodegenerative disease affecting 1-2% of people above the ages of 65 years old. There is a worldwide prevalence of 7 to 10 million affected people of all cultures and race. Studies have shown that mutation that causes Parkinson’s disease result in increased kinase activity. The c.6055 G > A in exon 41 is the most prevalent LRRK2 variation which causes a substitution of glycine to serine in G2019S in the highly activated loop of its MAP kinase domain. The LRRK2 G2019S variant is the most common genetic determinant of Parkinson’s disease identified to date. This work focused on building accurate 3D models of the LRRK2 kinase domain, that were used for large-scale in silico docking against South African natural compounds from the South African Natural Compounds Database (SANCDB; https://sancdb.rubi.ru.ac.za/). Molecular docking was performed to identify compounds that formed interactions with the active site of the protein and had the lowest binding energy scores. Molecular dynamics simulations showed different movements of the protein-ligand complexes and behavioural difference of the wildtype and the variants, all three structures proved to be compact. Network analysis was done to study residue interactions, contact maps, dynamic cross correlations, average BC and average L were used to study the residue interactions and general residue contribution to the functioning of the protein..
- Full Text:
- Date Issued: 2020
- Authors: Baye, Bertha Cinthia
- Date: 2020
- Subjects: Antiparkinsonian agents , Parkinson's disease -- Treatment , Protein kinases , Parkinson's disease -- Chemotherapy , Molecules -- Models
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/138764 , vital:37671
- Description: Parkinson’s disease is a type of movement disorder that occurs when nerve cells in the brain stop producing dopamine. It is the second neurodegenerative disease affecting 1-2% of people above the ages of 65 years old. There is a worldwide prevalence of 7 to 10 million affected people of all cultures and race. Studies have shown that mutation that causes Parkinson’s disease result in increased kinase activity. The c.6055 G > A in exon 41 is the most prevalent LRRK2 variation which causes a substitution of glycine to serine in G2019S in the highly activated loop of its MAP kinase domain. The LRRK2 G2019S variant is the most common genetic determinant of Parkinson’s disease identified to date. This work focused on building accurate 3D models of the LRRK2 kinase domain, that were used for large-scale in silico docking against South African natural compounds from the South African Natural Compounds Database (SANCDB; https://sancdb.rubi.ru.ac.za/). Molecular docking was performed to identify compounds that formed interactions with the active site of the protein and had the lowest binding energy scores. Molecular dynamics simulations showed different movements of the protein-ligand complexes and behavioural difference of the wildtype and the variants, all three structures proved to be compact. Network analysis was done to study residue interactions, contact maps, dynamic cross correlations, average BC and average L were used to study the residue interactions and general residue contribution to the functioning of the protein..
- Full Text:
- Date Issued: 2020
In vitro susceptibility of Staphylococcus aureus to porphyrin-silver mediated photodynamic antimicrobial chemotherapy
- Authors: Shabangu, Samuel Malewa
- Date: 2020
- Subjects: Porphyrins , Nanoparticles , Photochemotherapy , Drug resistance in microorganisms , Staphylococcus aureus
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167476 , vital:41484
- Description: This work reports on the syntheses and characterization of symmetrical and unsymmetrical porphyrin complexes namely, 5,10,15,20-tetra(4-pyridyl)-porphyrinato zinc(II) (1), 5,10,15,20-tetrathienyl porphyrinato zinc(II) (2), 5-(4-hydroxyphenyl)-10, 15, 20-tris(2-thienyl) porphyrinato zinc(II) (3), 5-(4-carboxyphenyl)-10,15,20-tris(pentafluorophenyl)- porphyrinato zinc(II) (4), 5-(4-carboxyphenyl)-10,15,20-triphenyl-porphyrinato zinc(II) (5) and 5-(4-carboxyphenyl)-10, 15, 20-tris(2-thienyl)-porphyrinato zinc(II) (6). The synthesis of silver nanoparticles (AgNPs) was also undertaken in this research work. Complexes 1, 2, 3 and 6 were linked to oleic acid/oleylamine functionalized nanoparticles via self-assembly and 4-6 were linked via covalent interaction through an amide bond to glutathione capped AgNPs. The effect of nature of bond along with symmetry were investigated, of interest were the five membered thienyl substituents. The photophysical and photochemical behaviour of the complexes and their conjugates with AgNPs were investigated in dimethylformamide. The porphyrin and AgNPs conjugates afforded an increase in singlet oxygen quantum yield. Complexes 1-6 and their conjugates were used for photodynamic antimicrobial chemotherapy of Staphylococcus aureus. The antimicrobial studies were done in two different concentrations of 0.36 and 2.0 μg/mL. The thienyl substituted porphyrin complexes and their conjugates gave better photodynamic activity as compared to phenyl analogues
- Full Text:
- Date Issued: 2020
- Authors: Shabangu, Samuel Malewa
- Date: 2020
- Subjects: Porphyrins , Nanoparticles , Photochemotherapy , Drug resistance in microorganisms , Staphylococcus aureus
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167476 , vital:41484
- Description: This work reports on the syntheses and characterization of symmetrical and unsymmetrical porphyrin complexes namely, 5,10,15,20-tetra(4-pyridyl)-porphyrinato zinc(II) (1), 5,10,15,20-tetrathienyl porphyrinato zinc(II) (2), 5-(4-hydroxyphenyl)-10, 15, 20-tris(2-thienyl) porphyrinato zinc(II) (3), 5-(4-carboxyphenyl)-10,15,20-tris(pentafluorophenyl)- porphyrinato zinc(II) (4), 5-(4-carboxyphenyl)-10,15,20-triphenyl-porphyrinato zinc(II) (5) and 5-(4-carboxyphenyl)-10, 15, 20-tris(2-thienyl)-porphyrinato zinc(II) (6). The synthesis of silver nanoparticles (AgNPs) was also undertaken in this research work. Complexes 1, 2, 3 and 6 were linked to oleic acid/oleylamine functionalized nanoparticles via self-assembly and 4-6 were linked via covalent interaction through an amide bond to glutathione capped AgNPs. The effect of nature of bond along with symmetry were investigated, of interest were the five membered thienyl substituents. The photophysical and photochemical behaviour of the complexes and their conjugates with AgNPs were investigated in dimethylformamide. The porphyrin and AgNPs conjugates afforded an increase in singlet oxygen quantum yield. Complexes 1-6 and their conjugates were used for photodynamic antimicrobial chemotherapy of Staphylococcus aureus. The antimicrobial studies were done in two different concentrations of 0.36 and 2.0 μg/mL. The thienyl substituted porphyrin complexes and their conjugates gave better photodynamic activity as compared to phenyl analogues
- Full Text:
- Date Issued: 2020
Initiating biological control for Nymphaea mexicana zuccarini (Nymphaeaceae) in South Africa
- Authors: Reid, Megan
- Date: 2020
- Subjects: Nymphaea mexicana zuccarini -- Biological control -- South Africa , Nymphaeaceae -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/144510 , vital:38352
- Description: Nymphaea mexicana Zuccarini (Nymphaeaceae) is an aquatic plant originating from south-eastern USA that is becoming increasingly invasive in South Africa as other invasive aquatic plants are being managed successfully through biological control. Mechanical and chemical control of aquatic weeds is expensive, damaging to the environment, and only effective in the short term, so biological control is more desirable as a management strategy for N. mexicana. The biological control of invasive alien plants requires that agents are host specific so that non-target risks are mitigated. For success to be achieved, it is important to ensure that the genetic structure of invasive populations is clarified so that agents can be collected from populations in the native range that match genetically to populations in the invasive range. This is especially important in cases where the morphology of invasive alien plants does not reflect genetic differences between populations. A previous study of the genetic structure of the invasive populations of N. mexicana in South Africa suggests the presence of hybrid forms of the plant in South Africa, with only one of these populations matching with samples from the native range. However, the study only used samples from two sites in the native range using amplified fragment length polymorphisms (AFLPs), so it was necessary to conduct further genetic analyses using samples from more sites in the native range. Hence, the first aim of this study was to develop a better understanding of the genetic structure of N. mexicana populations in the native and invaded range. Genetic samples were collected from sites in the native range during field surveys for potential biological control agents, and inter-simple sequence repeats (ISSRs) were used to compare the genetic structure of invasive and native populations of N. mexicana in South Africa. The results from these analyses suggest that seven of the 14 investigated invasive populations of N. mexicana in South Africa are genetically similar to populations in the native range, while the remaining seven populations are likely to be hybrid forms of the plant. This knowledge will be useful to target populations for biological control and highlights the need for further genetic analyses to determine the parentage of these hybrids so that biological control efforts are more likely to be successful. The initiation of a biological control programme requires that a series of steps are taken in order to maximise the likelihood that this form of intervention will be successful. The first few steps include: identification of the target weed and its genetic structure; exploration in the native range for potential biological control agents; and prioritisation of these agents based on factors such as climatic and genetic compatibility, feeding damage, abundance, and likely host range. Hence, the second aim of this study was to conduct surveys for potential biological control agents in the native range of N. mexicana, and to prioritise these agents. Field surveys were conducted between August and October in 2018 at 17 sites in Florida, Louisiana, and Texas, USA. Sites were selected based on climatic similarity of native sites compared to invasive sites by use of MaxEnt modelling. Native N. mexicana plants were searched for natural enemies, and these were prioritised based on feeding damage, abundance, incidence, and observations of field host range. Two species were prioritised: Bagous americanus LeConte (Coleoptera: Curculionidae) and Megamelus toddi Beamer (Hemiptera: Delphacidae). These species will be imported into quarantine facilities at Rhodes University for host specificity tests to be conducted. Understanding the factors that contribute to the successful establishment of biological control agents is important to improve the efficiency and reduce the costs incurred during the initiation of biological control programmes. Acquiring knowledge of the factors that predict the efficacy of biological control agents is similarly important, and these factors are discussed in the last chapter of this study. The challenges of the biological control of hybrids are also considered, and recommendations are made for the control of N. mexicana and other plants in South Africa.
- Full Text:
- Date Issued: 2020
- Authors: Reid, Megan
- Date: 2020
- Subjects: Nymphaea mexicana zuccarini -- Biological control -- South Africa , Nymphaeaceae -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/144510 , vital:38352
- Description: Nymphaea mexicana Zuccarini (Nymphaeaceae) is an aquatic plant originating from south-eastern USA that is becoming increasingly invasive in South Africa as other invasive aquatic plants are being managed successfully through biological control. Mechanical and chemical control of aquatic weeds is expensive, damaging to the environment, and only effective in the short term, so biological control is more desirable as a management strategy for N. mexicana. The biological control of invasive alien plants requires that agents are host specific so that non-target risks are mitigated. For success to be achieved, it is important to ensure that the genetic structure of invasive populations is clarified so that agents can be collected from populations in the native range that match genetically to populations in the invasive range. This is especially important in cases where the morphology of invasive alien plants does not reflect genetic differences between populations. A previous study of the genetic structure of the invasive populations of N. mexicana in South Africa suggests the presence of hybrid forms of the plant in South Africa, with only one of these populations matching with samples from the native range. However, the study only used samples from two sites in the native range using amplified fragment length polymorphisms (AFLPs), so it was necessary to conduct further genetic analyses using samples from more sites in the native range. Hence, the first aim of this study was to develop a better understanding of the genetic structure of N. mexicana populations in the native and invaded range. Genetic samples were collected from sites in the native range during field surveys for potential biological control agents, and inter-simple sequence repeats (ISSRs) were used to compare the genetic structure of invasive and native populations of N. mexicana in South Africa. The results from these analyses suggest that seven of the 14 investigated invasive populations of N. mexicana in South Africa are genetically similar to populations in the native range, while the remaining seven populations are likely to be hybrid forms of the plant. This knowledge will be useful to target populations for biological control and highlights the need for further genetic analyses to determine the parentage of these hybrids so that biological control efforts are more likely to be successful. The initiation of a biological control programme requires that a series of steps are taken in order to maximise the likelihood that this form of intervention will be successful. The first few steps include: identification of the target weed and its genetic structure; exploration in the native range for potential biological control agents; and prioritisation of these agents based on factors such as climatic and genetic compatibility, feeding damage, abundance, and likely host range. Hence, the second aim of this study was to conduct surveys for potential biological control agents in the native range of N. mexicana, and to prioritise these agents. Field surveys were conducted between August and October in 2018 at 17 sites in Florida, Louisiana, and Texas, USA. Sites were selected based on climatic similarity of native sites compared to invasive sites by use of MaxEnt modelling. Native N. mexicana plants were searched for natural enemies, and these were prioritised based on feeding damage, abundance, incidence, and observations of field host range. Two species were prioritised: Bagous americanus LeConte (Coleoptera: Curculionidae) and Megamelus toddi Beamer (Hemiptera: Delphacidae). These species will be imported into quarantine facilities at Rhodes University for host specificity tests to be conducted. Understanding the factors that contribute to the successful establishment of biological control agents is important to improve the efficiency and reduce the costs incurred during the initiation of biological control programmes. Acquiring knowledge of the factors that predict the efficacy of biological control agents is similarly important, and these factors are discussed in the last chapter of this study. The challenges of the biological control of hybrids are also considered, and recommendations are made for the control of N. mexicana and other plants in South Africa.
- Full Text:
- Date Issued: 2020
Investigation into the influence of an alien plant species on the soil microbiota of the sub-Antarctic, Marion Island
- Authors: Pienaar, Robert Daniel
- Date: 2020
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/124039 , vital:35531
- Description: Embargo applied. Embargo period to expire in April of 2021.
- Full Text:
- Date Issued: 2020
- Authors: Pienaar, Robert Daniel
- Date: 2020
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/124039 , vital:35531
- Description: Embargo applied. Embargo period to expire in April of 2021.
- Full Text:
- Date Issued: 2020
Managing the invasive aquatic plant Sagittaria platyphylla (Engelm.) J.G. Sm(Alismataceae): problems and prospects
- Ndlovu, Mpilonhle Sinothando
- Authors: Ndlovu, Mpilonhle Sinothando
- Date: 2020
- Subjects: Aquatic weeds -- Biological control -- South Africa , Sagittaria latifolia -- Biological control -- South Africa , Noxious weeds -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa , Listronotus , Insects as biological pest control agents
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167121 , vital:41439
- Description: Sagittaria platyphylla (Engelm.) J.G.Sm. (Alismataceae), commonly known as Delta arrowhead, is an invasive aquatic macrophyte native to southern United States of America (USA) that has become a serious weed in freshwater systems in South Africa, New Zealand, Australia, and recently China. In South Africa, the plant was first detected in Krantzkloof Nature Reserve, KwaZulu-Natal Province in 2008, and due to its known impact in other countries, it was listed as a Category 1a invader species under the National Environmental Management: Biodiversity Act 2004 (NEM: BA). This listing required mechanical and chemical control methods to be implemented by the South African National Biodiversity Institute’s (SANBI), Invasive Species Programme (ISP), with the aim of eradicating the weed. Despite the eradication efforts, by 2016, the weed was recognized as one of the country’s top 10 worst and fastest spreading invasive alien plants. Since its introduction in 2008, the plant has spread both within and between sites in South Africa, increasing from one site in 2008 to 72 sites by 2019. Once introduced into lotic systems, the plant spread rapidly downstream, in some cases up to 120km within six years, with an average of 10 km per year. Extirpation over the last ten years was only possible at a limited number of sites. Under the current management approach, the invasion is foreseen to spread to new sites within a 5 km radius of the current populations. Due to the failure of conventional control mechanisms, biological control is currently being considered as a potential control option. Four potential biological control agents are under investigation, but none have been released. Amongst them is the fruit and flower feeding weevil Listronotus appendiculatus Bohm. (Coleoptera: Curculionidae) which showed most potential as a suitable biological control agent. This study demonstrated that L. appendiculatus herbivory negatively influenced the overall fitness of S. platyphylla by reducing the plant’s growth rate and above ground biomass. Listronotus appendiculatus herbivory also reduced the plant’s size and the potential to kill adult plants. Most importantly, L. appendiculatus larval feeding damage significantly reduce viable-germinating seeds, the weed’s primary dispersal mechanism. Therefore, a biological control programme is advised to be integrated within the current management plan.
- Full Text:
- Date Issued: 2020
- Authors: Ndlovu, Mpilonhle Sinothando
- Date: 2020
- Subjects: Aquatic weeds -- Biological control -- South Africa , Sagittaria latifolia -- Biological control -- South Africa , Noxious weeds -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa , Listronotus , Insects as biological pest control agents
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167121 , vital:41439
- Description: Sagittaria platyphylla (Engelm.) J.G.Sm. (Alismataceae), commonly known as Delta arrowhead, is an invasive aquatic macrophyte native to southern United States of America (USA) that has become a serious weed in freshwater systems in South Africa, New Zealand, Australia, and recently China. In South Africa, the plant was first detected in Krantzkloof Nature Reserve, KwaZulu-Natal Province in 2008, and due to its known impact in other countries, it was listed as a Category 1a invader species under the National Environmental Management: Biodiversity Act 2004 (NEM: BA). This listing required mechanical and chemical control methods to be implemented by the South African National Biodiversity Institute’s (SANBI), Invasive Species Programme (ISP), with the aim of eradicating the weed. Despite the eradication efforts, by 2016, the weed was recognized as one of the country’s top 10 worst and fastest spreading invasive alien plants. Since its introduction in 2008, the plant has spread both within and between sites in South Africa, increasing from one site in 2008 to 72 sites by 2019. Once introduced into lotic systems, the plant spread rapidly downstream, in some cases up to 120km within six years, with an average of 10 km per year. Extirpation over the last ten years was only possible at a limited number of sites. Under the current management approach, the invasion is foreseen to spread to new sites within a 5 km radius of the current populations. Due to the failure of conventional control mechanisms, biological control is currently being considered as a potential control option. Four potential biological control agents are under investigation, but none have been released. Amongst them is the fruit and flower feeding weevil Listronotus appendiculatus Bohm. (Coleoptera: Curculionidae) which showed most potential as a suitable biological control agent. This study demonstrated that L. appendiculatus herbivory negatively influenced the overall fitness of S. platyphylla by reducing the plant’s growth rate and above ground biomass. Listronotus appendiculatus herbivory also reduced the plant’s size and the potential to kill adult plants. Most importantly, L. appendiculatus larval feeding damage significantly reduce viable-germinating seeds, the weed’s primary dispersal mechanism. Therefore, a biological control programme is advised to be integrated within the current management plan.
- Full Text:
- Date Issued: 2020
Metallophthalocyanines linked to metal nanoparticles and folic acid for use in photodynamic therapy of cancer and photoinactivation of bacterial microorganisms.
- Authors: Matlou, Gauta Gold
- Date: 2020
- Subjects: Cancer -- Photochemotherapy , Nanoparticles , Phthalocyanines , Anti-infective agents -- Therapeutic use , Photochemotherapy , Photochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/166540 , vital:41377
- Description: This thesis presents on the synthesis and characterization of novel asymmetric and symmetrical metallophthalocyanines (MPcs) substituted with carboxylic acid functional groups and centrally metallated with zinc and indium. The MPcs are further covalently linked to cysteine capped silver nanoparticles (cys-AgNPs), amino functionalized magnetic nanoparticles (AMNPs) and folic acid (FA) through an amide bond between the carboxylic group of MPcs and the amino group of FA, cys-AgNPs or AMNPs. The covalent linkage of MPcs to FA improved the water solubility of MPcs and allowed for singlet oxygen quantum yield determination in water. Asymmetric MPcs and their conjugates were found to have improved photochemical and photophysical properties compared to symmetrical MPcs and their conjugates. The heavy atom effect of AMNPs and AgNPs improved the triplet and singlet oxygen quantum yields of MPcs. MPcs and their conjugates (MPc-FA, MPc-AMNPs, MPc-AgNPs) were found to have lower in vitro dark cytotoxicity and higher photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. The water soluble MPc-FA had better PDT activity when compared to MPc-AMNPs due to the active targeting of folic acid-folate binding on cancer cell surface. MPcs and MPc-AgNPs conjugates also showed excellent in vitro cytotoxicity on S. aureus under light irradiation compared to dark cytotoxicity. The photosensitizing properties of MPcs and their conjugates are demonstrated for the first time in this thesis, both on breast cancer cells (MCF-7) through photodynamic therapy and on microorganisms (S. aureus) through photodynamic antimicrobial chemotherapy.
- Full Text:
- Date Issued: 2020
- Authors: Matlou, Gauta Gold
- Date: 2020
- Subjects: Cancer -- Photochemotherapy , Nanoparticles , Phthalocyanines , Anti-infective agents -- Therapeutic use , Photochemotherapy , Photochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/166540 , vital:41377
- Description: This thesis presents on the synthesis and characterization of novel asymmetric and symmetrical metallophthalocyanines (MPcs) substituted with carboxylic acid functional groups and centrally metallated with zinc and indium. The MPcs are further covalently linked to cysteine capped silver nanoparticles (cys-AgNPs), amino functionalized magnetic nanoparticles (AMNPs) and folic acid (FA) through an amide bond between the carboxylic group of MPcs and the amino group of FA, cys-AgNPs or AMNPs. The covalent linkage of MPcs to FA improved the water solubility of MPcs and allowed for singlet oxygen quantum yield determination in water. Asymmetric MPcs and their conjugates were found to have improved photochemical and photophysical properties compared to symmetrical MPcs and their conjugates. The heavy atom effect of AMNPs and AgNPs improved the triplet and singlet oxygen quantum yields of MPcs. MPcs and their conjugates (MPc-FA, MPc-AMNPs, MPc-AgNPs) were found to have lower in vitro dark cytotoxicity and higher photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. The water soluble MPc-FA had better PDT activity when compared to MPc-AMNPs due to the active targeting of folic acid-folate binding on cancer cell surface. MPcs and MPc-AgNPs conjugates also showed excellent in vitro cytotoxicity on S. aureus under light irradiation compared to dark cytotoxicity. The photosensitizing properties of MPcs and their conjugates are demonstrated for the first time in this thesis, both on breast cancer cells (MCF-7) through photodynamic therapy and on microorganisms (S. aureus) through photodynamic antimicrobial chemotherapy.
- Full Text:
- Date Issued: 2020
Mineralogy, geochemistry and origin of the Neoproterozoic Xaudum iron-formation in Botswana
- Authors: Ntantiso, Mawande
- Date: 2020
- Subjects: Xaudum iron-formation , Iron ores -- Botswana , Formations (Geology) -- Botswana , Mineralogy -- Botswana , Paleoclimatology -- Proterozoic
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167211 , vital:41447
- Description: Banded iron-formations (BIF) formed in three different geological periods in the Earth’s history, namely the Archean, Paleoproterozoic and Neoproterozoic. Each of these periods has a corresponding index BIF type attributed to them. The oldest is the Archean Algoma-type BIF which is typically dominated by smaller-volume BIF deposits associated with volcanic rocks and greenstone belts. The next is the volumetrically far more abundant Superior-type BIF of the Paleoproterozoic lacking any obvious volcanic relation. The youngest BIFs were deposited after a hiatus of a billion years in the Neoproterozoic and are believed to be genetically linked to Marinoan ice-age. The global re-introduction and distribution of BIF in the Neoproterozoic highlights a shift in the Earth’s tectonics, climate, biosphere and ocean chemistry from the older Archean and Paleoproterozoic counterparts. Various models have been postulated by researchers in attempts to explain how Neoproterozoic iron-formations formed. In all the available models, the Snowball Earth Hypothesis initially proposed by Kirshvink (1992) is an overarching concept. In this study, four cores from the Neoproterozoic Xaudum iron-formation (XIF) in Ngamiland, northwest of Botswana, were sampled and analysed following a partnership between Postgraduate Research in Iron and Manganese Ore Resources (PRIMOR) and Tsodilo Resources Ltd. The study sets out to explore the mineralogy and chemistry of XIF in order to determine its origin, constrain the redox conditions in the paleo-basin, assess it in the context of other Neoproterozoic iron-formations and older Archean and Paleoproterozoic iron-formations, and inform metallurgical processing. The mineralogy of XIF consists of magnetite, quartz, amphibole, garnet, biotite and chlorite in decreasing abundance. This mineral assemblage is characteristic of medium grade metamorphosed iron-formations. Algoma and Superior-type BIFs which experienced late-diagenetic and very low-grade metamorphism have a complex mineral assemblage consisting of hematite, magnetite, quartz, and several carbonate (dolomite-ankerite series and siderite) and silicate phases (greenalite, riebeckite and stilpnomelane). The geochemical results show that XIF has higher Mn3O4 and Al2O3 average contents when compared to Algoma and Superior type BIF. The detrital components in XIF correlate with High Field Strength Elements (HFSE) suggesting increased delivery of siliciclastic material during deposition. This trend is comparable to other NIF deposits suggesting a global high input of siliciclastic material into Neoproterozoic paleodepositional environments. This trend is different from Archean and Paleoproterozoic BIF deposits which are close to pure chemical sediments lacking measurable detrital contributions. In the XIF, bulk-rock Mn3O4 and Al2O3 in drillcore SW have higher averages of 2.4 and 2.6 wt. % respectively, compared to the other three cores. The Mn3O4 shows a positive statistical relationship with Co, suggesting that Neoproterozoic oceans and atmosphere were possibly more oxic than in the Archean and Paleoproterozoic. The Mn3O4 shows an antithetic relationship with Fe2O3 suggesting that the paleobasin was chemically heterogeneous in terms of redox conditions, with Fe2O3 depositing presumably in deeper parts removed from a detrital source, and Mn3O4 depositing possibly more proximal to a paleo-shoreline in a shallower setting where there was higher delivery of siliciclastic material from the continent due to correspondingly higher Al2O3 and TiO2 contents. The REE patterns of XIF show positive-sloping trends of depletion in LREE and enrichment in HREE which resemble those of seawater. However, the REE slope becomes a lot flatter and resembles closer the signature of PAAS and adjacent diamictite facies, which agrees with the idea of high siliciclastic input in the paleobasin comparable to other NIF. XIF also appears to lack clear Ce or Eu anomalies. The lack of the former points to the oceans possibly not being oxic enough to drive the fractionation of Ce into Mn oxides like in the modern oceans, or that the Ce behaviour is obscured by the high siliciclastic input in XIF. Similarly, the lack of positive Eu anomaly shows a weak to absent hydrothermal signal into to modern shallow seawater where Fe and Si were sourced, or detritally derived REE contamination. Extensive weathering under hot and humid climate during glacial retreat is shown by the low K2O/Al2O3 ratios and high CIA values ranging from 80-99. Re-glaciation signifies the return of cold and arid and it is represented by high K2O/Al2O3 ratios and low CIA values ranging from 64-78. The previous genetic models of NIF by Klein (1993), Baldwin et al. (2012) and Lechte and Wallace (2015) provide an essential foundation for the development of a XIF genetic model. The genetic model of XIF proposes deposition on an open continental shelf characterized by a steady influx of detrital material. The seawater has been anoxic since the Paleoproterozoic and further induced by basin stagnation due to the ice covering the basin. Two overlapping oxidative stages are assumed for the precipitation of Fe and Mn across lateral redox gradients in the paleobasin. The exact oxidative pathways and mechanisms for the above processes remains unconstrained.
- Full Text:
- Date Issued: 2020
- Authors: Ntantiso, Mawande
- Date: 2020
- Subjects: Xaudum iron-formation , Iron ores -- Botswana , Formations (Geology) -- Botswana , Mineralogy -- Botswana , Paleoclimatology -- Proterozoic
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167211 , vital:41447
- Description: Banded iron-formations (BIF) formed in three different geological periods in the Earth’s history, namely the Archean, Paleoproterozoic and Neoproterozoic. Each of these periods has a corresponding index BIF type attributed to them. The oldest is the Archean Algoma-type BIF which is typically dominated by smaller-volume BIF deposits associated with volcanic rocks and greenstone belts. The next is the volumetrically far more abundant Superior-type BIF of the Paleoproterozoic lacking any obvious volcanic relation. The youngest BIFs were deposited after a hiatus of a billion years in the Neoproterozoic and are believed to be genetically linked to Marinoan ice-age. The global re-introduction and distribution of BIF in the Neoproterozoic highlights a shift in the Earth’s tectonics, climate, biosphere and ocean chemistry from the older Archean and Paleoproterozoic counterparts. Various models have been postulated by researchers in attempts to explain how Neoproterozoic iron-formations formed. In all the available models, the Snowball Earth Hypothesis initially proposed by Kirshvink (1992) is an overarching concept. In this study, four cores from the Neoproterozoic Xaudum iron-formation (XIF) in Ngamiland, northwest of Botswana, were sampled and analysed following a partnership between Postgraduate Research in Iron and Manganese Ore Resources (PRIMOR) and Tsodilo Resources Ltd. The study sets out to explore the mineralogy and chemistry of XIF in order to determine its origin, constrain the redox conditions in the paleo-basin, assess it in the context of other Neoproterozoic iron-formations and older Archean and Paleoproterozoic iron-formations, and inform metallurgical processing. The mineralogy of XIF consists of magnetite, quartz, amphibole, garnet, biotite and chlorite in decreasing abundance. This mineral assemblage is characteristic of medium grade metamorphosed iron-formations. Algoma and Superior-type BIFs which experienced late-diagenetic and very low-grade metamorphism have a complex mineral assemblage consisting of hematite, magnetite, quartz, and several carbonate (dolomite-ankerite series and siderite) and silicate phases (greenalite, riebeckite and stilpnomelane). The geochemical results show that XIF has higher Mn3O4 and Al2O3 average contents when compared to Algoma and Superior type BIF. The detrital components in XIF correlate with High Field Strength Elements (HFSE) suggesting increased delivery of siliciclastic material during deposition. This trend is comparable to other NIF deposits suggesting a global high input of siliciclastic material into Neoproterozoic paleodepositional environments. This trend is different from Archean and Paleoproterozoic BIF deposits which are close to pure chemical sediments lacking measurable detrital contributions. In the XIF, bulk-rock Mn3O4 and Al2O3 in drillcore SW have higher averages of 2.4 and 2.6 wt. % respectively, compared to the other three cores. The Mn3O4 shows a positive statistical relationship with Co, suggesting that Neoproterozoic oceans and atmosphere were possibly more oxic than in the Archean and Paleoproterozoic. The Mn3O4 shows an antithetic relationship with Fe2O3 suggesting that the paleobasin was chemically heterogeneous in terms of redox conditions, with Fe2O3 depositing presumably in deeper parts removed from a detrital source, and Mn3O4 depositing possibly more proximal to a paleo-shoreline in a shallower setting where there was higher delivery of siliciclastic material from the continent due to correspondingly higher Al2O3 and TiO2 contents. The REE patterns of XIF show positive-sloping trends of depletion in LREE and enrichment in HREE which resemble those of seawater. However, the REE slope becomes a lot flatter and resembles closer the signature of PAAS and adjacent diamictite facies, which agrees with the idea of high siliciclastic input in the paleobasin comparable to other NIF. XIF also appears to lack clear Ce or Eu anomalies. The lack of the former points to the oceans possibly not being oxic enough to drive the fractionation of Ce into Mn oxides like in the modern oceans, or that the Ce behaviour is obscured by the high siliciclastic input in XIF. Similarly, the lack of positive Eu anomaly shows a weak to absent hydrothermal signal into to modern shallow seawater where Fe and Si were sourced, or detritally derived REE contamination. Extensive weathering under hot and humid climate during glacial retreat is shown by the low K2O/Al2O3 ratios and high CIA values ranging from 80-99. Re-glaciation signifies the return of cold and arid and it is represented by high K2O/Al2O3 ratios and low CIA values ranging from 64-78. The previous genetic models of NIF by Klein (1993), Baldwin et al. (2012) and Lechte and Wallace (2015) provide an essential foundation for the development of a XIF genetic model. The genetic model of XIF proposes deposition on an open continental shelf characterized by a steady influx of detrital material. The seawater has been anoxic since the Paleoproterozoic and further induced by basin stagnation due to the ice covering the basin. Two overlapping oxidative stages are assumed for the precipitation of Fe and Mn across lateral redox gradients in the paleobasin. The exact oxidative pathways and mechanisms for the above processes remains unconstrained.
- Full Text:
- Date Issued: 2020
Molecular simulations of potential agents and targets of Alzheimer’s disease
- Authors: Carlisle, Tanya
- Date: 2020
- Subjects: Alzheimer's disease -- Treatment , Alzheimer's disease -- Molecular aspects , Amyloid beta-protein precurs , Amyloid beta-protein
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/140025 , vital:37825
- Description: The World Alzheimer Report statedin 2016 that approximately 46.8 million people were living with dementia and this figure is expected to triple by 2050. Alzheimer’s Disease was discovered to be a precursor to dementia in 1976 and since then efforts to understand Alzheimer’s have been prioritized. To date, there are very few effective forms of treatment for Alzheimer’s, many are known to offer only mild calming of the symptoms and have side effects such as diarrhea, nausea, loss of appetite and sleep disturbances. This has been due to lack of understanding on how Alzheimer’s is caused. With the two main hallmarks of the disease now being more understood it has opened the doorway into the discovery of new treatments for this disease. This study focuses on the hallmark involving the aggregation of the β-amyloid protein to form plaques surrounding the neurons of the brain. Copper, Zinc and Iron have also been found in high concentrations in and surrounding these plaques. This study focused on the screening of the South African Natural Compound database (SANCDB) to discover hits that have potential destabilizing action against the Beta-amyloid aggregate. If one of these compounds could prove to have destabilizing action on the aggregate it could open the doorway to new potential forms of treatment. Over 700 SANCDB compounds were docked, and the top hits were taken to molecular dynamics to further study the interactions of the compounds and the aggregate. However, the hits identified had strong binding to the aggregate causing it to become stable instead of the desired effect of destabilizing the structure. This information, however, does not rule out the possibility of these compounds preventing the formation of the aggregates. Further, interactions of copper with β-amyloid and copper were determined by solubilizing the aggregate and introducing copper ions in a dynamics simulation. Possible interactions between copper and the methionine residues were visualised.
- Full Text:
- Date Issued: 2020
- Authors: Carlisle, Tanya
- Date: 2020
- Subjects: Alzheimer's disease -- Treatment , Alzheimer's disease -- Molecular aspects , Amyloid beta-protein precurs , Amyloid beta-protein
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/140025 , vital:37825
- Description: The World Alzheimer Report statedin 2016 that approximately 46.8 million people were living with dementia and this figure is expected to triple by 2050. Alzheimer’s Disease was discovered to be a precursor to dementia in 1976 and since then efforts to understand Alzheimer’s have been prioritized. To date, there are very few effective forms of treatment for Alzheimer’s, many are known to offer only mild calming of the symptoms and have side effects such as diarrhea, nausea, loss of appetite and sleep disturbances. This has been due to lack of understanding on how Alzheimer’s is caused. With the two main hallmarks of the disease now being more understood it has opened the doorway into the discovery of new treatments for this disease. This study focuses on the hallmark involving the aggregation of the β-amyloid protein to form plaques surrounding the neurons of the brain. Copper, Zinc and Iron have also been found in high concentrations in and surrounding these plaques. This study focused on the screening of the South African Natural Compound database (SANCDB) to discover hits that have potential destabilizing action against the Beta-amyloid aggregate. If one of these compounds could prove to have destabilizing action on the aggregate it could open the doorway to new potential forms of treatment. Over 700 SANCDB compounds were docked, and the top hits were taken to molecular dynamics to further study the interactions of the compounds and the aggregate. However, the hits identified had strong binding to the aggregate causing it to become stable instead of the desired effect of destabilizing the structure. This information, however, does not rule out the possibility of these compounds preventing the formation of the aggregates. Further, interactions of copper with β-amyloid and copper were determined by solubilizing the aggregate and introducing copper ions in a dynamics simulation. Possible interactions between copper and the methionine residues were visualised.
- Full Text:
- Date Issued: 2020
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
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
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