A framework for grain commodity trading decision support in South Africa
- Authors: Ayankoya, Kayode Anthony
- Date: 2016
- Subjects: Grain trade -- South Africa Commodity exchanges -- South Africa Food industry and trade -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11437 , vital:26925
- Description: In several countries around the world, grain commodities are traded as assets on stock exchanges. This indicate that the market and effectively the prices of the grain commodities in such countries, are controlled by several local and international economic, political and social factors that are rapidly changing. As a result, the prices of some grain commodities are volatile and trading in such commodities are prone to price-related risks. There are different trading strategies for minimising price-related risks and maximising profits. But empirical research suggests that making the right decision for effective grain commodities trading has been a difficult task for stakeholders due to high volatility of grain commodities prices. Studies have shown that this is more challenging among grain commodities farmers because of their lack of skills and the time to sift through and make sense of the datasets on the plethora of factors that influence the grain commodities market. This thesis focused on providing an answer for the main research problem that grain farmers in South Africa do not take full advantage of all the available strategies for trading their grain commodities because of the complexities associated with monitoring the large datasets that influence the grain commodities market. The main objective set by this study is to design a framework that can be followed to collect, integrate and analyse datasets that influence trading decisions of grain farmers in South Africa about grain commodities. This study takes advantage of the developments in Big Data and Data Science to achieve the set objective using the Design Science Research (DSR) methodology. The prediction of future prices of grain commodities for the different trading strategies was identified as an important factor for making better decisions when trading grain commodities and the key factors that influence the prices were identified. This was followed by a critical review of the literature to determine how the concepts of Big Data and Data Science can be leveraged for an effective grain commodities trading decision support. This resulted in a proposed framework for grain commodities trading. The proposed framework suggested an investigation of the factors that influence the prices of grain commodities as the basis for acquiring the relevant datasets. The proposed framework suggested the adoption of the Big Data approach in acquiring, preparing and integrating relevant datasets from several sources. Furthermore, it was suggested that algorithmic models for predicting grain commodities prices can be developed on top of the data layer of the proposed framework to provide real-time decision support. The proposed framework suggests the need for a carefully designed visualisation of the result and the collected data that promotes user experience. Lastly, the proposed framework included a technology consideration component to support the Big Data and Data Science approach of the framework. To demonstrate that the proposed framework addressed the main problem of this research, datasets from several sources on trading white maize in South Africa and the factors that influence market were streamed, integrated and analysed. Backpropagation Neural Network algorithm was used for modelling the prices of white maize for spot and futures trading strategies were predicted. There are other modelling techniques such as the Box-Jenkins statistical time series analysis methodology. But, Neural Networks was identified as more suitable for time series data with complex patterns and relationships. A demonstration system was setup to provide effective decision support by using near real-time data to provide a dynamic predictive analytics for the spot and December futures contract prices of white maize in South Africa. Comparative analysis of predictions made using the model from the proposed framework to actual data indicated a significant degree of accuracy. A further evaluation was carried out by asking experienced traders to make predictions for the spot and December futures contract prices of white maize. The result of the exercise indicated that the predictions from the developed model were much closer to the actual prices. This indicated that the proposed framework is technically capable and generally useful. It also shows that the proposed framework can be used to provide decision support about trading grain commodities to stakeholders with lesser skills, experience and resources. The practical contribution of this thesis is that relevant datasets from several sources can be streamed into an integrated data source in real-time, which can be used as input for a real-time learning algorithmic model for predicting grain commodities prices. This will make it possible for a predictive analytics that responds to market volatility thereby providing an effective decision support for grain commodities trading. Another practical contribution of this thesis is a proposed framework that can be followed for developing a Decision Support System for trading in grain commodities. This thesis made theoretical contributions by building on the information processing theory and the decision making theory. The theoretical contribution of this thesis consists of the identification of Big Data approach, tools and techniques for eradicating uncertainty and equivocality in grain commodities trading decision making process.
- Full Text:
- Date Issued: 2016
- Authors: Ayankoya, Kayode Anthony
- Date: 2016
- Subjects: Grain trade -- South Africa Commodity exchanges -- South Africa Food industry and trade -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11437 , vital:26925
- Description: In several countries around the world, grain commodities are traded as assets on stock exchanges. This indicate that the market and effectively the prices of the grain commodities in such countries, are controlled by several local and international economic, political and social factors that are rapidly changing. As a result, the prices of some grain commodities are volatile and trading in such commodities are prone to price-related risks. There are different trading strategies for minimising price-related risks and maximising profits. But empirical research suggests that making the right decision for effective grain commodities trading has been a difficult task for stakeholders due to high volatility of grain commodities prices. Studies have shown that this is more challenging among grain commodities farmers because of their lack of skills and the time to sift through and make sense of the datasets on the plethora of factors that influence the grain commodities market. This thesis focused on providing an answer for the main research problem that grain farmers in South Africa do not take full advantage of all the available strategies for trading their grain commodities because of the complexities associated with monitoring the large datasets that influence the grain commodities market. The main objective set by this study is to design a framework that can be followed to collect, integrate and analyse datasets that influence trading decisions of grain farmers in South Africa about grain commodities. This study takes advantage of the developments in Big Data and Data Science to achieve the set objective using the Design Science Research (DSR) methodology. The prediction of future prices of grain commodities for the different trading strategies was identified as an important factor for making better decisions when trading grain commodities and the key factors that influence the prices were identified. This was followed by a critical review of the literature to determine how the concepts of Big Data and Data Science can be leveraged for an effective grain commodities trading decision support. This resulted in a proposed framework for grain commodities trading. The proposed framework suggested an investigation of the factors that influence the prices of grain commodities as the basis for acquiring the relevant datasets. The proposed framework suggested the adoption of the Big Data approach in acquiring, preparing and integrating relevant datasets from several sources. Furthermore, it was suggested that algorithmic models for predicting grain commodities prices can be developed on top of the data layer of the proposed framework to provide real-time decision support. The proposed framework suggests the need for a carefully designed visualisation of the result and the collected data that promotes user experience. Lastly, the proposed framework included a technology consideration component to support the Big Data and Data Science approach of the framework. To demonstrate that the proposed framework addressed the main problem of this research, datasets from several sources on trading white maize in South Africa and the factors that influence market were streamed, integrated and analysed. Backpropagation Neural Network algorithm was used for modelling the prices of white maize for spot and futures trading strategies were predicted. There are other modelling techniques such as the Box-Jenkins statistical time series analysis methodology. But, Neural Networks was identified as more suitable for time series data with complex patterns and relationships. A demonstration system was setup to provide effective decision support by using near real-time data to provide a dynamic predictive analytics for the spot and December futures contract prices of white maize in South Africa. Comparative analysis of predictions made using the model from the proposed framework to actual data indicated a significant degree of accuracy. A further evaluation was carried out by asking experienced traders to make predictions for the spot and December futures contract prices of white maize. The result of the exercise indicated that the predictions from the developed model were much closer to the actual prices. This indicated that the proposed framework is technically capable and generally useful. It also shows that the proposed framework can be used to provide decision support about trading grain commodities to stakeholders with lesser skills, experience and resources. The practical contribution of this thesis is that relevant datasets from several sources can be streamed into an integrated data source in real-time, which can be used as input for a real-time learning algorithmic model for predicting grain commodities prices. This will make it possible for a predictive analytics that responds to market volatility thereby providing an effective decision support for grain commodities trading. Another practical contribution of this thesis is a proposed framework that can be followed for developing a Decision Support System for trading in grain commodities. This thesis made theoretical contributions by building on the information processing theory and the decision making theory. The theoretical contribution of this thesis consists of the identification of Big Data approach, tools and techniques for eradicating uncertainty and equivocality in grain commodities trading decision making process.
- Full Text:
- Date Issued: 2016
Development of a small production platform for citronellal processing
- Mafu, Lubabalo Rowan, Zeelie, Ben
- Authors: Mafu, Lubabalo Rowan , Zeelie, Ben
- Date: 2016
- Subjects: Organic compounds -- Synthesis , Plasticizers
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8488 , vital:26370
- Description: The aim of the project was to develop a small production platform for citronellal processing. The objective of the study was to develop a single continuous flow reactor system for the synthesis of novel derivatives of citronellal and isopulegol. The first step was to develop a continuous flow reactor system for the isopulegol synthesis. The stainless steel tubular fixed-bed reactor equipped with a reaction column (I.D: 9.53 mm and length: 120 mm) was used for the study. The reactor column was packed with H-ZMS-5 zeolite extrusion catalyst. The solvent-free cyclisation reaction of citronellal was investigated and at optimum conditions, 100% of citronellal conversion and almost 100% selectivity towards isopulegol was achieved. A good catalytic performance was observed from the H-ZSM-5 catalyst and proved to be stable for a prolonged reaction time. The second reaction step was to develop a continuous flow reactor system for the synthesis of isopulegyl-ether derivatives. A UniQsis FlowSyn reactor system equipped with a stainless steel reactor column was used for the study. The reactor column was packed with amberlyst-15 dry catalyst. Wherein, n-propanol was employed as a model etherifying agent and as a reaction solvent. At optimum reaction condition, only 30% selectivity of isopulegyl propoxy-ether was achieved. The reaction was found to depend highly on temperature and residence time. The increase of these parameters was found to increase the side reactions and reduced the selectivity of the desired product. Other heterogeneous catalysts such as H-beta zeolite, aluminium pillared clay, Aluminium oxide and H-ZSM-5 were also evaluated in the reaction. Among these catalysts, a catalytic activity was observed with H-beta zeolite (19%) and aluminium pillared clay (5%). Based on these results, none of the evaluated catalysts provided the desired selectivity (greater than 70%) towards the isopulegyl propoxy-ether, therefore the process was not investigated further. In light of this, the isopulegol etherification synthetic route was terminated. Consequently, another analogue of citronellal was used as an alternative intermediate in place of isopulegol, namely para-menthane-3,8-diol (PMD). The initial studies for the synthesis of the novel PMD di-esters from isopulegol were performed in the batch-scale reactor. In a solvent-free reaction, acetic anhydride was initially used as a model acetylating agent. The reaction was performed using polymer-bound scandium triflate (PS-Sc(OTf)3) catalyst. The effect of reaction parameters such as temperature, molar ratio, and reaction time were studied towards the PMD conversion and di-esters selectivity. At optimum reaction conditions, PMD conversion of 70% and di-acetate selectivity of 67% were observed. The reaction was found to follow the zeroth-order kinetics with respect to PMD conversion and obeyed the Arrhenius equation. Other types of di-ester derivatives were synthesized from PMD by varying the carbon chain length of the acetylating agent. The prepared compounds were separated from the product mixtures by vacuum distillation, purified on a column chromatography and characterised by FT-IR, GC-MS, and 1H-NMR, 13C-NMR. The developed methodology was optimised in flow by using an ArrheniumOne microwave-assisted continuous-flow fixed-bed reactor system. A detailed experimental design was used to carry-out the reactions. The reaction parameters such as temperature and flow-rate were studied towards the PMD conversion and di-ester selectivity. From the experimental design analysis, the di-ester selectivity was found to depend highly on the residence time (flow-rate) and significantly on temperature. The PMD conversion and di-ester selectivity were found to increase with decrease in the flow-rate. The conversion and selectivity achieved in the continuous flow process were significantly higher than the achieved in the batch-scale process with respect to the residence time.
- Full Text:
- Date Issued: 2016
- Authors: Mafu, Lubabalo Rowan , Zeelie, Ben
- Date: 2016
- Subjects: Organic compounds -- Synthesis , Plasticizers
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8488 , vital:26370
- Description: The aim of the project was to develop a small production platform for citronellal processing. The objective of the study was to develop a single continuous flow reactor system for the synthesis of novel derivatives of citronellal and isopulegol. The first step was to develop a continuous flow reactor system for the isopulegol synthesis. The stainless steel tubular fixed-bed reactor equipped with a reaction column (I.D: 9.53 mm and length: 120 mm) was used for the study. The reactor column was packed with H-ZMS-5 zeolite extrusion catalyst. The solvent-free cyclisation reaction of citronellal was investigated and at optimum conditions, 100% of citronellal conversion and almost 100% selectivity towards isopulegol was achieved. A good catalytic performance was observed from the H-ZSM-5 catalyst and proved to be stable for a prolonged reaction time. The second reaction step was to develop a continuous flow reactor system for the synthesis of isopulegyl-ether derivatives. A UniQsis FlowSyn reactor system equipped with a stainless steel reactor column was used for the study. The reactor column was packed with amberlyst-15 dry catalyst. Wherein, n-propanol was employed as a model etherifying agent and as a reaction solvent. At optimum reaction condition, only 30% selectivity of isopulegyl propoxy-ether was achieved. The reaction was found to depend highly on temperature and residence time. The increase of these parameters was found to increase the side reactions and reduced the selectivity of the desired product. Other heterogeneous catalysts such as H-beta zeolite, aluminium pillared clay, Aluminium oxide and H-ZSM-5 were also evaluated in the reaction. Among these catalysts, a catalytic activity was observed with H-beta zeolite (19%) and aluminium pillared clay (5%). Based on these results, none of the evaluated catalysts provided the desired selectivity (greater than 70%) towards the isopulegyl propoxy-ether, therefore the process was not investigated further. In light of this, the isopulegol etherification synthetic route was terminated. Consequently, another analogue of citronellal was used as an alternative intermediate in place of isopulegol, namely para-menthane-3,8-diol (PMD). The initial studies for the synthesis of the novel PMD di-esters from isopulegol were performed in the batch-scale reactor. In a solvent-free reaction, acetic anhydride was initially used as a model acetylating agent. The reaction was performed using polymer-bound scandium triflate (PS-Sc(OTf)3) catalyst. The effect of reaction parameters such as temperature, molar ratio, and reaction time were studied towards the PMD conversion and di-esters selectivity. At optimum reaction conditions, PMD conversion of 70% and di-acetate selectivity of 67% were observed. The reaction was found to follow the zeroth-order kinetics with respect to PMD conversion and obeyed the Arrhenius equation. Other types of di-ester derivatives were synthesized from PMD by varying the carbon chain length of the acetylating agent. The prepared compounds were separated from the product mixtures by vacuum distillation, purified on a column chromatography and characterised by FT-IR, GC-MS, and 1H-NMR, 13C-NMR. The developed methodology was optimised in flow by using an ArrheniumOne microwave-assisted continuous-flow fixed-bed reactor system. A detailed experimental design was used to carry-out the reactions. The reaction parameters such as temperature and flow-rate were studied towards the PMD conversion and di-ester selectivity. From the experimental design analysis, the di-ester selectivity was found to depend highly on the residence time (flow-rate) and significantly on temperature. The PMD conversion and di-ester selectivity were found to increase with decrease in the flow-rate. The conversion and selectivity achieved in the continuous flow process were significantly higher than the achieved in the batch-scale process with respect to the residence time.
- Full Text:
- Date Issued: 2016
An investigation of the morphological and electrochemical properties of spinel cathode oxide materials used in li-ion batteries
- Authors: Snyders, Charmelle
- Date: 2016
- Subjects: Lithium ion batteries Cathodes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12929 , vital:27135
- Description: Li-ion batteries have become the more dominant battery type used in portable electronic devices such as cell phones, computers and more recently their application in full electric vehicles (EV). Li-ion batteries have many advantages over the traditional rechargeable systems (Pb-acid and Ni-MH) such as their higher energy density, low self-discharge, long capacity cycle life and relatively maintenance free. Due to their commercial advantages, a lot of research is done in developing new novel Li-ion electrode materials, improving existing ones and to reduce manufacturing costs in order to make them more cost effective in their applications. This study looked at the cathode material chemistry that has a typical spinel manganese oxide (LiMn2O4) type structure. For comparison the study also considered the influence of doping the phase with various metals such as Al, Mg, Co and Ni that were made as precursors using various carboxylic acids (Citric, Ascorbic, Succinic and Poly-acrylic acid) from a sol-gel process. Traditional batch methods of synthesizing the electrode material is costly and do not necessarily provide optimized electrochemical performance. Alternative continuous less energy intensive methods would help reduce the costs of the preparation of the electrode materials. This study investigated the influence of two synthesis techniques on the materials physical and electrochemical characteristics. These synthesis methods included the use of a typical batch sol-gel method and the continuous spray-drying technique. The spinel materials were prepared and characterized by Powder X-Ray Diffraction (PXRD) to confirm the formation of various phases during the synthesis process. In addition, in-situ PXRD techniques were used to track the phase changes that occurred in the typical batch synthesis process from a sol-gel mixture to the final crystalline spinel oxide. The materials were also characterized by thermal gravimetric analysis (TGA), whereby the materials decomposition mechanisms were observed as the precursor was gradually heated to the final oxide. These synthesized materials prepared under various conditions were then used to build suitable Li-ion coin type of cells, whereby their electrochemical properties were tested by simple capacity tests and electrochemical impedance spectroscopy (EIS). EIS measurements were done on the built cells with the various materials at various charge voltages. TG analysis showed that the materials underwent multiple decomposition steps upon heating for the doped lithium manganese oxides, whereas the undoped oxide showed only a single decomposition step. The results showed that all the materials achieved their weight loss below 400 °C, and that the final spinel oxide had already formed. The in-situ PXRD analysis showed the progression of the phase transitions where certain of the materials changed from a crystalline precursor to an amorphous intermediate phase and then finally to the spinel cathode oxide (Li1.03Mg0.2Mn1.77O4, and LiCo1.09Mn0.91O4). For other materials, the precursor would start as an amorphous phase, and then upon heating, convert into an impure intermediate phase (Mn2O3) before forming the final spinel oxide (Li1.03Mn1.97O4 and LiNi0.5Mn1.5O4). The in-situ study also showed the increases in the materials respective lattice parameters of the crystalline unit cells upon heating and the significant increases in their crystallite sizes when heated above 600 °C. Hence the results implied that a type of sintering of the particles would occur at temperatures above 600 °C, thereby increasing the respective crystallite size. The study showed that the cathode active materials made by the sol-gel spray-drying method would give a material that had a significantly larger surface area and a smaller crystallite size when compared to the materials made by the batch process. The electrochemical analysis showed that there was only a slight increase in the discharge capacities of the cells made with the spray-drying technique when compared to the cells made with the materials from the batch sol-gel technique. Whereas, the EIS study showed that there were distinct differences in the charging behavior of the cells made with the various materials using different synthesis techniques. The EIS results showed that there was a general decrease in the cells charge transfer resistance (Rct) as the charge potential increased regardless of the synthesis method used for the various materials. The results also showed that the lithium-ion diffusion coefficient (DLi) obtained from EIS measurements were in most of the samples higher for the cathode materials that had a larger surface area. This implied that the Li-ion could diffuse at a faster rate through the bulk material. The study concluded that by optimizing the synthesis process in terms of the careful control of the thermal parameters, the Li-ion batteries‟ cathode active material of the manganese spinel type could be optimized and be manufactured by using a continuous flow micro spray process.
- Full Text:
- Date Issued: 2016
- Authors: Snyders, Charmelle
- Date: 2016
- Subjects: Lithium ion batteries Cathodes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12929 , vital:27135
- Description: Li-ion batteries have become the more dominant battery type used in portable electronic devices such as cell phones, computers and more recently their application in full electric vehicles (EV). Li-ion batteries have many advantages over the traditional rechargeable systems (Pb-acid and Ni-MH) such as their higher energy density, low self-discharge, long capacity cycle life and relatively maintenance free. Due to their commercial advantages, a lot of research is done in developing new novel Li-ion electrode materials, improving existing ones and to reduce manufacturing costs in order to make them more cost effective in their applications. This study looked at the cathode material chemistry that has a typical spinel manganese oxide (LiMn2O4) type structure. For comparison the study also considered the influence of doping the phase with various metals such as Al, Mg, Co and Ni that were made as precursors using various carboxylic acids (Citric, Ascorbic, Succinic and Poly-acrylic acid) from a sol-gel process. Traditional batch methods of synthesizing the electrode material is costly and do not necessarily provide optimized electrochemical performance. Alternative continuous less energy intensive methods would help reduce the costs of the preparation of the electrode materials. This study investigated the influence of two synthesis techniques on the materials physical and electrochemical characteristics. These synthesis methods included the use of a typical batch sol-gel method and the continuous spray-drying technique. The spinel materials were prepared and characterized by Powder X-Ray Diffraction (PXRD) to confirm the formation of various phases during the synthesis process. In addition, in-situ PXRD techniques were used to track the phase changes that occurred in the typical batch synthesis process from a sol-gel mixture to the final crystalline spinel oxide. The materials were also characterized by thermal gravimetric analysis (TGA), whereby the materials decomposition mechanisms were observed as the precursor was gradually heated to the final oxide. These synthesized materials prepared under various conditions were then used to build suitable Li-ion coin type of cells, whereby their electrochemical properties were tested by simple capacity tests and electrochemical impedance spectroscopy (EIS). EIS measurements were done on the built cells with the various materials at various charge voltages. TG analysis showed that the materials underwent multiple decomposition steps upon heating for the doped lithium manganese oxides, whereas the undoped oxide showed only a single decomposition step. The results showed that all the materials achieved their weight loss below 400 °C, and that the final spinel oxide had already formed. The in-situ PXRD analysis showed the progression of the phase transitions where certain of the materials changed from a crystalline precursor to an amorphous intermediate phase and then finally to the spinel cathode oxide (Li1.03Mg0.2Mn1.77O4, and LiCo1.09Mn0.91O4). For other materials, the precursor would start as an amorphous phase, and then upon heating, convert into an impure intermediate phase (Mn2O3) before forming the final spinel oxide (Li1.03Mn1.97O4 and LiNi0.5Mn1.5O4). The in-situ study also showed the increases in the materials respective lattice parameters of the crystalline unit cells upon heating and the significant increases in their crystallite sizes when heated above 600 °C. Hence the results implied that a type of sintering of the particles would occur at temperatures above 600 °C, thereby increasing the respective crystallite size. The study showed that the cathode active materials made by the sol-gel spray-drying method would give a material that had a significantly larger surface area and a smaller crystallite size when compared to the materials made by the batch process. The electrochemical analysis showed that there was only a slight increase in the discharge capacities of the cells made with the spray-drying technique when compared to the cells made with the materials from the batch sol-gel technique. Whereas, the EIS study showed that there were distinct differences in the charging behavior of the cells made with the various materials using different synthesis techniques. The EIS results showed that there was a general decrease in the cells charge transfer resistance (Rct) as the charge potential increased regardless of the synthesis method used for the various materials. The results also showed that the lithium-ion diffusion coefficient (DLi) obtained from EIS measurements were in most of the samples higher for the cathode materials that had a larger surface area. This implied that the Li-ion could diffuse at a faster rate through the bulk material. The study concluded that by optimizing the synthesis process in terms of the careful control of the thermal parameters, the Li-ion batteries‟ cathode active material of the manganese spinel type could be optimized and be manufactured by using a continuous flow micro spray process.
- Full Text:
- Date Issued: 2016
Modelling dispersal processes in impala-cheetah-lion ecosystems with infection in the lions
- Authors: Mbava, Willard
- Date: 2016
- Subjects: Predation (Biology) -- South Africa -- Kruger National Park Endangered species -- South Africa -- Kruger National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11782 , vital:26968
- Description: The study involved the predator-prey interaction of three species namely the predator (Cheetah Acinonyx jubatus), the super-predator (Lion Panthera leo), and their common prey (Impala Aepyceros melampus). The study area is the Kruger National Park. The predator being an endangered species, faces a survival problem. It is frequently killed by the super-predator to reduce competition for prey. The super-predator also scares away the predator o_ its kills. The prey forms the main diet of the predator. The plight of the predator motivated the author to formulate disease and reaction-diffusion models for the species interactions. The purpose of the models were to predict and explain the effect of large competition from the super-predator on the predator population. Important parameters related to additional predator mortality due to presence of super-predator, the disease incidence rate and induced death rate formed the focal points of the analysis. The dynamics of a predator-prey model with disease in super-predator were investigated. The super-predator species is infected with bovine Tuberculosis. In the study, the disease is considered as biological control to allow the predator population to regain from low numbers. The results highlight that in the absence of additional mortality on the predator by the super-predator, the predator population survives extinction. Furthermore, at current levels of disease incidence, the super-predator population is wiped out by the disease. However, the super-predator population survives extinction if the disease incidence rate is low. Persistence of all populations is possible in the case of low disease incidence rate and no additional mortality imparted on the predator. Furthermore, a two-species subsystem, prey and predator, is considered as a special case to determine the effect of super-predator removal from the system, on the survival of the predator. This is treated as a contrasting case from the smaller parks. The results show that the predator population thrives well in the total absence of its main competitor, with its population rising to at least twice the initial value. A reaction-diffusion three-species predator-prey model was formulated and analysed. Stability of the temporal and the spatio-temporal systems, existence and non-existence of stationary steady state solutions were studied. Conditions for the emergence of stationary patterns were deduced. The results show that by choosing the diffusion coeffcient d2 > _D 2 suffciently large, a non-constant positive solution is generated, that is, stationary patterns emerge, depicting dispersal of species. Predators were observed to occupy habitats surrounding prey. However, super-predators were observed to alternate their habitats, from staying away from prey to invading prey habitat. In the investigation, strategies to determine ways in which the predator species could be saved from extinction and its population improved were devised, and these included isolation of the predator from the super-predator.
- Full Text:
- Date Issued: 2016
- Authors: Mbava, Willard
- Date: 2016
- Subjects: Predation (Biology) -- South Africa -- Kruger National Park Endangered species -- South Africa -- Kruger National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11782 , vital:26968
- Description: The study involved the predator-prey interaction of three species namely the predator (Cheetah Acinonyx jubatus), the super-predator (Lion Panthera leo), and their common prey (Impala Aepyceros melampus). The study area is the Kruger National Park. The predator being an endangered species, faces a survival problem. It is frequently killed by the super-predator to reduce competition for prey. The super-predator also scares away the predator o_ its kills. The prey forms the main diet of the predator. The plight of the predator motivated the author to formulate disease and reaction-diffusion models for the species interactions. The purpose of the models were to predict and explain the effect of large competition from the super-predator on the predator population. Important parameters related to additional predator mortality due to presence of super-predator, the disease incidence rate and induced death rate formed the focal points of the analysis. The dynamics of a predator-prey model with disease in super-predator were investigated. The super-predator species is infected with bovine Tuberculosis. In the study, the disease is considered as biological control to allow the predator population to regain from low numbers. The results highlight that in the absence of additional mortality on the predator by the super-predator, the predator population survives extinction. Furthermore, at current levels of disease incidence, the super-predator population is wiped out by the disease. However, the super-predator population survives extinction if the disease incidence rate is low. Persistence of all populations is possible in the case of low disease incidence rate and no additional mortality imparted on the predator. Furthermore, a two-species subsystem, prey and predator, is considered as a special case to determine the effect of super-predator removal from the system, on the survival of the predator. This is treated as a contrasting case from the smaller parks. The results show that the predator population thrives well in the total absence of its main competitor, with its population rising to at least twice the initial value. A reaction-diffusion three-species predator-prey model was formulated and analysed. Stability of the temporal and the spatio-temporal systems, existence and non-existence of stationary steady state solutions were studied. Conditions for the emergence of stationary patterns were deduced. The results show that by choosing the diffusion coeffcient d2 > _D 2 suffciently large, a non-constant positive solution is generated, that is, stationary patterns emerge, depicting dispersal of species. Predators were observed to occupy habitats surrounding prey. However, super-predators were observed to alternate their habitats, from staying away from prey to invading prey habitat. In the investigation, strategies to determine ways in which the predator species could be saved from extinction and its population improved were devised, and these included isolation of the predator from the super-predator.
- Full Text:
- Date Issued: 2016
Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups
- Authors: Mukiza, Janvier
- Date: 2016
- Subjects: Rhenium Thiols Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12308 , vital:27053
- Description: The chemistry of rhenium has received considerable interest due to its versatility in various catalytic applications, fixation and especially the potential use of 186Re and 188Re radionuclides in nuclear medicine. This study investigates the synthesis and characterisation of rhenium complexes with potentially multidentate ligands containing the amino, imino, hydroxyl and thiol groups. It reports new rhenium complexes in the +1, +3, +4 and +5 oxidation states, which display structural diversity, from monomers to ligand-bridged dimers as well as metal-metal multiply bonded dimers. The reaction of orotic acid (H2oa) and 2-mercapto-orotic acid (H2moa) with trans- [ReOX3(PPh3)2] (X = Cl, Br) were studied and led to the formation of ligand-bridged dimers with metal-metal multiple bonds i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-X)(μ-O)(μ-oa)[Re2 IVX2(OiPr)(PPh3)2] and (μ-Cl)(μ-O)(μ-moa)2[Re(PPh3)]2. The reaction of H2oa with [ReO2(py)4]Cl, [Re(dab)Br3(PPh3)2] (H2dab = 1,2- diaminobenzene) and [Re(CO)5Cl] were also studied and monomeric complexes [ReO(py)2(OEt)(oa)], [Re(dab)Br(oa)(PPh3)2] and (Ph4P)[Re(CO)3(H2O)(oa)] were isolated. The treatment of 5-amino-orotic acid (H2aoa) with [ReOBr3(PPh3)2] led to dimers with metal-metal triple bonds ReIV≡ReIV i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-Br)(μ-O)(μ-oa)[Re2 IVBr2(OiPr)(PPh3)2], as well as the monomer [ReV(apd)Br(aoa)(PPh3)2] (apd2− = 5-imidopyrimidine-2,4-dione). The chelating ligand 5-aminopyrimidine-2,4-dione (H2apd) was formed by oxorhenium(V)-catalysed decarboxylation of 5-amino-orotic acid (H2aoa) (see Scheme 1). The reaction of the Schiff base derivative of 5-amino-ortic acid, salicylimine-orotic acid (H2soa), with trans-[ReOI2(OEt)(PPh3)2] in ethanol was also investigated and led to the formation of the rhenium(III) complex salt [Re(coa)I(PPh3)2]I [Hcoa = 5-(2- hydroxybenzylideneamino)pyrimidine-2,4(1H,3H)-dione]. The chelating Hcoa is also formed from the oxorhenium(V)-catalysed decarboxylation of H2soa and coordinates to the rhenium(III) ion as a monoanionic tridentate N,O,O-donor chelate via the phenolate and ketonic oxygens, and the imino nitrogen atom. However, decarboxylation of H2soa was not observed in its reaction with [ReOCl3(PPh3)2], which led to the isolation of [ReOCl(soa)(PPh3)]. The reaction of the carboxamide derivative of 5-aminoorotic acid, 5-(5-aminopyrimidine-2,4(1H,3H)- dioxamido)-1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-carboxylic acid (H2ampa) with [Re(CO)5Cl] in ethanol led to the formation of a zwitterionic rhenium(I) complex [Re(CO)3(H2O)(amef)] [amef = {5-(5-ammoniumpyrimidine-2,4(1H,3H)-dioxamido)- 1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-ethylformate}]. The chelating ion amef was formed from the combined tricarbonylrhenium(I)-catalysed esterification and aminoprotonation of H2ampa (see Scheme 1) and coordinates to the fac-[Re(CO)3]+ core as a dianionic bidentate N,N-donor chelate via the amido nitrgens.
- Full Text:
- Date Issued: 2016
- Authors: Mukiza, Janvier
- Date: 2016
- Subjects: Rhenium Thiols Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12308 , vital:27053
- Description: The chemistry of rhenium has received considerable interest due to its versatility in various catalytic applications, fixation and especially the potential use of 186Re and 188Re radionuclides in nuclear medicine. This study investigates the synthesis and characterisation of rhenium complexes with potentially multidentate ligands containing the amino, imino, hydroxyl and thiol groups. It reports new rhenium complexes in the +1, +3, +4 and +5 oxidation states, which display structural diversity, from monomers to ligand-bridged dimers as well as metal-metal multiply bonded dimers. The reaction of orotic acid (H2oa) and 2-mercapto-orotic acid (H2moa) with trans- [ReOX3(PPh3)2] (X = Cl, Br) were studied and led to the formation of ligand-bridged dimers with metal-metal multiple bonds i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-X)(μ-O)(μ-oa)[Re2 IVX2(OiPr)(PPh3)2] and (μ-Cl)(μ-O)(μ-moa)2[Re(PPh3)]2. The reaction of H2oa with [ReO2(py)4]Cl, [Re(dab)Br3(PPh3)2] (H2dab = 1,2- diaminobenzene) and [Re(CO)5Cl] were also studied and monomeric complexes [ReO(py)2(OEt)(oa)], [Re(dab)Br(oa)(PPh3)2] and (Ph4P)[Re(CO)3(H2O)(oa)] were isolated. The treatment of 5-amino-orotic acid (H2aoa) with [ReOBr3(PPh3)2] led to dimers with metal-metal triple bonds ReIV≡ReIV i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-Br)(μ-O)(μ-oa)[Re2 IVBr2(OiPr)(PPh3)2], as well as the monomer [ReV(apd)Br(aoa)(PPh3)2] (apd2− = 5-imidopyrimidine-2,4-dione). The chelating ligand 5-aminopyrimidine-2,4-dione (H2apd) was formed by oxorhenium(V)-catalysed decarboxylation of 5-amino-orotic acid (H2aoa) (see Scheme 1). The reaction of the Schiff base derivative of 5-amino-ortic acid, salicylimine-orotic acid (H2soa), with trans-[ReOI2(OEt)(PPh3)2] in ethanol was also investigated and led to the formation of the rhenium(III) complex salt [Re(coa)I(PPh3)2]I [Hcoa = 5-(2- hydroxybenzylideneamino)pyrimidine-2,4(1H,3H)-dione]. The chelating Hcoa is also formed from the oxorhenium(V)-catalysed decarboxylation of H2soa and coordinates to the rhenium(III) ion as a monoanionic tridentate N,O,O-donor chelate via the phenolate and ketonic oxygens, and the imino nitrogen atom. However, decarboxylation of H2soa was not observed in its reaction with [ReOCl3(PPh3)2], which led to the isolation of [ReOCl(soa)(PPh3)]. The reaction of the carboxamide derivative of 5-aminoorotic acid, 5-(5-aminopyrimidine-2,4(1H,3H)- dioxamido)-1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-carboxylic acid (H2ampa) with [Re(CO)5Cl] in ethanol led to the formation of a zwitterionic rhenium(I) complex [Re(CO)3(H2O)(amef)] [amef = {5-(5-ammoniumpyrimidine-2,4(1H,3H)-dioxamido)- 1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-ethylformate}]. The chelating ion amef was formed from the combined tricarbonylrhenium(I)-catalysed esterification and aminoprotonation of H2ampa (see Scheme 1) and coordinates to the fac-[Re(CO)3]+ core as a dianionic bidentate N,N-donor chelate via the amido nitrgens.
- Full Text:
- Date Issued: 2016
Scalable chemistry involving diazonium salts
- Authors: Akwi, Faith Mary
- Date: 2016
- Subjects: Azo compounds -- Synthesis , Chemical processes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6909 , vital:21162
- Description: Herein an alternative approach aimed at reducing the cost of numbering up technique as a scale up strategy for chemical processes from the laboratory bench top to the industry is explored. The effect of increasing channel size on the reaction conversion of the synthesis of azo compounds is investigated. This was achieved via a systematic investigative understanding of the synthesis in microreactors where a proof of concept study was performed to determine the optimum reaction parameters in azo coupling reactions involving couplers with aminated or hydroxylated groups in Little Things Factory-MS microreactors (Channel diameter: 1.0 mm) It was found that at slightly alkaline conditions (pH 8.55) and at a temperature of 25 °C, excellent conversions were attained in the azo coupling reaction of the diazonium salt solution of 2,4-dimethylaniline to 2-naphthol. On the other hand, the azo coupling reaction of the diazonium salt solution of p-nitroaniline to diphenylamine was found to thrive at a pH of 5.71 and at a temperature of 25 °C. Using, these optimized reaction parameters, the in-situ and reactive quench of diazonium salts in LTF-MS microreactors was investigated where it was found that at a flow rate of 0.2 ml/min, 0.03 ml/min and 0.07 ml/min of diazotizable amine & HCl, sodium nitrite and coupler solutions respectively, a conversion of 98% is achieved in approximately 2.4 minutes. A library of azo compounds was thus generated under these reaction conditions from couplers with aminated or hydroxylated aromatic aromatic systems. The scaled up synthesis of these compounds in a homemade PTFE tubing (ID 1.5 mm) reactor system was thereafter investigated and comparable conversions were observed. Capitalizing on the benefits of a large surface area and the short molecular diffusion distances observed in microreactors, in-situ phase transfer catalyzed azo coupling reaction of diphenylamine to p-nitroaniline was also explored. In this investigation a rapid and easy optimization protocol that yielded a 99%, 22% and 33% conversion of diphenylamine, carbazole and triphenylamine respectively in approximately 2.4 minutes using Chemtrix microreactors was established. On increasing the microreactor channel internal diameter in the scaled up synthesis approach, it was found that a 0.5 mm increase in channel internal diameter does result in lower reaction conversions.
- Full Text:
- Date Issued: 2016
- Authors: Akwi, Faith Mary
- Date: 2016
- Subjects: Azo compounds -- Synthesis , Chemical processes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6909 , vital:21162
- Description: Herein an alternative approach aimed at reducing the cost of numbering up technique as a scale up strategy for chemical processes from the laboratory bench top to the industry is explored. The effect of increasing channel size on the reaction conversion of the synthesis of azo compounds is investigated. This was achieved via a systematic investigative understanding of the synthesis in microreactors where a proof of concept study was performed to determine the optimum reaction parameters in azo coupling reactions involving couplers with aminated or hydroxylated groups in Little Things Factory-MS microreactors (Channel diameter: 1.0 mm) It was found that at slightly alkaline conditions (pH 8.55) and at a temperature of 25 °C, excellent conversions were attained in the azo coupling reaction of the diazonium salt solution of 2,4-dimethylaniline to 2-naphthol. On the other hand, the azo coupling reaction of the diazonium salt solution of p-nitroaniline to diphenylamine was found to thrive at a pH of 5.71 and at a temperature of 25 °C. Using, these optimized reaction parameters, the in-situ and reactive quench of diazonium salts in LTF-MS microreactors was investigated where it was found that at a flow rate of 0.2 ml/min, 0.03 ml/min and 0.07 ml/min of diazotizable amine & HCl, sodium nitrite and coupler solutions respectively, a conversion of 98% is achieved in approximately 2.4 minutes. A library of azo compounds was thus generated under these reaction conditions from couplers with aminated or hydroxylated aromatic aromatic systems. The scaled up synthesis of these compounds in a homemade PTFE tubing (ID 1.5 mm) reactor system was thereafter investigated and comparable conversions were observed. Capitalizing on the benefits of a large surface area and the short molecular diffusion distances observed in microreactors, in-situ phase transfer catalyzed azo coupling reaction of diphenylamine to p-nitroaniline was also explored. In this investigation a rapid and easy optimization protocol that yielded a 99%, 22% and 33% conversion of diphenylamine, carbazole and triphenylamine respectively in approximately 2.4 minutes using Chemtrix microreactors was established. On increasing the microreactor channel internal diameter in the scaled up synthesis approach, it was found that a 0.5 mm increase in channel internal diameter does result in lower reaction conversions.
- Full Text:
- Date Issued: 2016
Leonotis leonurus: understanding the mechanism of anti-diabetic action and investigating a nano drug delivery system
- Odei-Addo, Frank, Levendal, Ruby-Ann
- Authors: Odei-Addo, Frank , Levendal, Ruby-Ann
- Date: 2016
- Subjects: Diabetes Plant extracts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/13116 , vital:27153
- Description: Diabetes mellitus is a metabolic disease characterised by hyperglycaemia resulting from defects in insulin secretion, insulin action, or both. The leaf extract of Leonotis leonurus and its active compound marrubiin, have been shown to possess anti-diabetic, antiplatelet, anti-inflammatory and anti-coagulation activity. In the present study, the mechanism by which L. leonurus and marrubiin exert their anti-diabetic properties, the cross-talk between the peripheral tissues and a nano drug delivery system were investigated. Marrubiin in the plant extract was effectively quantified by an optimised reversed phase highperformance liquid chromatography (HPLC) protocol using a pentafluorophenyl (PFP) column with water and acetonitrile (50:50) as mobile phase, and a flow rate of 1ml/min. The chemical structure was determined using liquid chromatography-tandem mass spectroscopy LC-MS/MS. Real-time quantitative polymerase chain reaction (RT-qPCR) gene expression of selected adipokines and proteins implicated in Type-2 diabetes (T2D) were investigated in specific peripheral tissues isolated from an in vivo obese rat model. An in vitro cell culture model was used to determine the crosstalk between the peripheral tissues and pancreatic (INS-1E) β-cells. Various nanoformulations of L. leonurus extract were prepared and their effect on cytotoxicity (in Chang liver and INS-1 cells), insulin-mediated glucose uptake (Change liver cells) and insulin secretion (INS-1) were investigated. The average yield of marrubiin from the plant extract was 10% (n=3), with a molecular mass of 333.20Da and a molecular formula of C20H29O4 +. Results from the in vivo study showed that the L. leonurus extract significantly (p<0.05) enhanced the gene expression of adiponectin, peroxisome proliferator-activated receptor gamma (PPAR-γ), glucokinase (GK), uncoupling protein-2 (UCP-2) and reduced leptin in adipose tissue, but resistin, glucose transporters (GLUT), fatty acid synthase (FAS), insulin receptor substrate -1 (IRS-1) and phosphoenolpyruvate carboxykinase (PEPCK) gene expression were not affected. Marrubiin decreased gene expression of leptin and resistin, and increased IRS-1 and glucokinase in adipose tissue. In liver and muscle tissues, marrubiin and the L. leonurus extract reduced gene expression of PPAR-γ, IRS-1, glucokinase and PEPCK. In the in vitro crosstalk study (under normoglycaemic and hyperglycaemic conditions), conditioned medium from 3T3-L1 cells significantly (p<0.01) enhanced insulin secretion. This was not observed in INS-1E cells exposed to muscle- and liver-conditioned medium, respectively. The in vitro studies using a nanostructured lipid formulation (NLC) of the plant extract was not cytotoxic to either INS-1 and Chang liver cells. The NLC formulation significantly (p<0.05) enhanced glucose uptake in Chang liver cells and improved chronic insulin release in INS-1 cells (p<0.05). Based on the above findings from the in vivo and in vitro studies, both L. leonurus and marrubiin exerted an insulinotropic effect via adipose tissue on pancreatic β-cells. The findings in the in vivo study showed that marrubiin and the L. leonurus extract were employing their major anti-diabetic action via the adipose tissue.
- Full Text:
- Date Issued: 2016
- Authors: Odei-Addo, Frank , Levendal, Ruby-Ann
- Date: 2016
- Subjects: Diabetes Plant extracts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/13116 , vital:27153
- Description: Diabetes mellitus is a metabolic disease characterised by hyperglycaemia resulting from defects in insulin secretion, insulin action, or both. The leaf extract of Leonotis leonurus and its active compound marrubiin, have been shown to possess anti-diabetic, antiplatelet, anti-inflammatory and anti-coagulation activity. In the present study, the mechanism by which L. leonurus and marrubiin exert their anti-diabetic properties, the cross-talk between the peripheral tissues and a nano drug delivery system were investigated. Marrubiin in the plant extract was effectively quantified by an optimised reversed phase highperformance liquid chromatography (HPLC) protocol using a pentafluorophenyl (PFP) column with water and acetonitrile (50:50) as mobile phase, and a flow rate of 1ml/min. The chemical structure was determined using liquid chromatography-tandem mass spectroscopy LC-MS/MS. Real-time quantitative polymerase chain reaction (RT-qPCR) gene expression of selected adipokines and proteins implicated in Type-2 diabetes (T2D) were investigated in specific peripheral tissues isolated from an in vivo obese rat model. An in vitro cell culture model was used to determine the crosstalk between the peripheral tissues and pancreatic (INS-1E) β-cells. Various nanoformulations of L. leonurus extract were prepared and their effect on cytotoxicity (in Chang liver and INS-1 cells), insulin-mediated glucose uptake (Change liver cells) and insulin secretion (INS-1) were investigated. The average yield of marrubiin from the plant extract was 10% (n=3), with a molecular mass of 333.20Da and a molecular formula of C20H29O4 +. Results from the in vivo study showed that the L. leonurus extract significantly (p<0.05) enhanced the gene expression of adiponectin, peroxisome proliferator-activated receptor gamma (PPAR-γ), glucokinase (GK), uncoupling protein-2 (UCP-2) and reduced leptin in adipose tissue, but resistin, glucose transporters (GLUT), fatty acid synthase (FAS), insulin receptor substrate -1 (IRS-1) and phosphoenolpyruvate carboxykinase (PEPCK) gene expression were not affected. Marrubiin decreased gene expression of leptin and resistin, and increased IRS-1 and glucokinase in adipose tissue. In liver and muscle tissues, marrubiin and the L. leonurus extract reduced gene expression of PPAR-γ, IRS-1, glucokinase and PEPCK. In the in vitro crosstalk study (under normoglycaemic and hyperglycaemic conditions), conditioned medium from 3T3-L1 cells significantly (p<0.01) enhanced insulin secretion. This was not observed in INS-1E cells exposed to muscle- and liver-conditioned medium, respectively. The in vitro studies using a nanostructured lipid formulation (NLC) of the plant extract was not cytotoxic to either INS-1 and Chang liver cells. The NLC formulation significantly (p<0.05) enhanced glucose uptake in Chang liver cells and improved chronic insulin release in INS-1 cells (p<0.05). Based on the above findings from the in vivo and in vitro studies, both L. leonurus and marrubiin exerted an insulinotropic effect via adipose tissue on pancreatic β-cells. The findings in the in vivo study showed that marrubiin and the L. leonurus extract were employing their major anti-diabetic action via the adipose tissue.
- Full Text:
- Date Issued: 2016
Factors influencing wetland distribution and structure, including ecosystem function of ephemeral wetlands, in Nelson Mandela Bay Municipality (NMBM), South Africa
- Melly, Brigitte Leigh, Gama, Phumelele T
- Authors: Melly, Brigitte Leigh , Gama, Phumelele T
- Date: 2016
- Subjects: Wetland management -- South Africa Wetland ecology -- South Africa -- Nelson Mandela Bay Municipality
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11721 , vital:26960
- Description: The Nelson Mandela Bay Municipality (NMBM) is a semi-arid area along the southern coastline of South Africa (SA). Until recently, there was no systematic approach to research on wetland systems in the NMBM. The systematic identification of wetlands was made more difficult by the relatively large number of small, ephemeral systems that can be difficult to delineate. This has meant that fundamental knowledge on wetland distribution, structure and function has been limited and, consequently, management and conservation strategies have been based on knowledge on systems from other regions of the country. Environmental processes occur at different spatial and temporal scales. These processes have an effect on the abiotic factors and biotic structure of wetlands, resulting in inherently complex systems. The location of the NMBM provides a good study area to research some of these environmental and biological attributes at different spatial scales, due to the variability in the underlying geology, geomorphology, vegetation types and the spatial and temporal variability in rainfall, within a relatively small area of 1951 km2. Thus, the aim of this study was to determine the factors influencing wetland distribution, structure and ecosystem functioning within the NMBM. The first Research Objective of work presented here was to identify wetlands using visual interpretation of aerial photographs. A total of 1712 wetlands were identified within the NMBM using aerial photographs, covering an area of 17.88 km2 (Chapter 5). The majority of these wetlands were depressions, seeps and wetland flats. Valley bottom wetlands (channelled and unchannelled) and floodplain wetlands were also identified. A range of wetland sizes was recorded, with 86% of the wetlands being less than 1 ha in size and the largest natural wetland being a floodplain wetland of 57 ha, located south of the Swartkops River. The identified wetlands were used to create a wetland occurrence model using logistic regression (LR) techniques (Chapter 5), in accordance with Objective 2 of the study. An accuracy of 66% was obtained, which was considered acceptable for a semi-arid climate with a relatively high degree of spatial and temporal rainfall variability. The model also highlighted several key environmental variables that are associated with wetland occurrence and distribution at various spatial scales. Some of the important variables included precipitation, evapotranspiration, temperature, flow accumulation and groundwater occurrence. Wetland distribution patterns were described in Chapter 6. Spatial statistics were used to identify whether wetlands are clustered and, therefore, form mosaics within the surrounding landscape (Objective 3). Systems were found to be highly clustered, with 43% of wetlands located within 200 m of another system. Clustering and wetland presence was especially prominent in the southern portion of the Municipality, which is also associated with a higher mean annual precipitation. Smaller wetlands were also significantly more clustered than larger systems (Average Nearest Neighbour statistic, p-value < 0.0001). Average distances also significantly varied according to HGM type, with depressions being the most geographically isolated wetland type compared to the other HGM types. Overall, distances between wetlands indicated good proximal connectivity. Potentially vulnerable areas associated with wetland systems were identified successfully using landscape variables, in accordance with Objective 4. These variables were: land cover, slope gradient, flow accumulation, APAN evaporation, mean annual precipitation (MAP) and annual heat units. The existing Critical Biodiversity Network was also used in connection with these variables to further identify potentially vulnerable areas. The abiotic and biotic characteristics were decribed for three hydrogeomorphic (HGM) types at a total of 46 wetland sites (Chapter 7), as per Objective 5. Depressions, seeps and wetland flats were sampled across the different geological, vegetation and rainfall zones within the NMBM. The wetland sites were delineated up to Level 6 of the Classification System used in SA, and the various abiotic and biotic characteristics of these systems were defined. A total of 307 plant, 144 aquatic macroinvertebrate and 10 tadpole species were identified. Of these species, over 90 species were Eastern Cape and SA endemic species, as well as three threatened species on the IUCN Red List. Multivariate analyses (including Bray-Curtis similarity resemblance analyses, distance-based redundancy analyses, SIMPER analyses and BIOENV analysis in Primer), together with environmental data, were used to define community structure at an HGM level, in accordance with Objective 5. The importance of the spatial scale of the environmental data used to define plant and macroinvertebrate community structure was described in Chapter 7, to address Objective 6. The results showed that both broad-scale and site-level characteristics were important in distinguishing community structure within the HGM types that superseded general location, the sample timing or the stage of inundation. These results also indicated that a combination of both landscape and site-level data are important in defining the community structure in the various HGM types. Some of the important environmental variables that explained some of species assemblages were similar to those in the wetland occurrence model (Chapter 5), with some additional hydrological and soil physico-chemical parameters (e.g. soil electrical conductivity, soil pH, and surface and subsurface water nutrients). These significant variables indicate the complex, multi-scalar role of environmental attributes on wetland distribution, structure and function.
- Full Text:
- Date Issued: 2016
- Authors: Melly, Brigitte Leigh , Gama, Phumelele T
- Date: 2016
- Subjects: Wetland management -- South Africa Wetland ecology -- South Africa -- Nelson Mandela Bay Municipality
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11721 , vital:26960
- Description: The Nelson Mandela Bay Municipality (NMBM) is a semi-arid area along the southern coastline of South Africa (SA). Until recently, there was no systematic approach to research on wetland systems in the NMBM. The systematic identification of wetlands was made more difficult by the relatively large number of small, ephemeral systems that can be difficult to delineate. This has meant that fundamental knowledge on wetland distribution, structure and function has been limited and, consequently, management and conservation strategies have been based on knowledge on systems from other regions of the country. Environmental processes occur at different spatial and temporal scales. These processes have an effect on the abiotic factors and biotic structure of wetlands, resulting in inherently complex systems. The location of the NMBM provides a good study area to research some of these environmental and biological attributes at different spatial scales, due to the variability in the underlying geology, geomorphology, vegetation types and the spatial and temporal variability in rainfall, within a relatively small area of 1951 km2. Thus, the aim of this study was to determine the factors influencing wetland distribution, structure and ecosystem functioning within the NMBM. The first Research Objective of work presented here was to identify wetlands using visual interpretation of aerial photographs. A total of 1712 wetlands were identified within the NMBM using aerial photographs, covering an area of 17.88 km2 (Chapter 5). The majority of these wetlands were depressions, seeps and wetland flats. Valley bottom wetlands (channelled and unchannelled) and floodplain wetlands were also identified. A range of wetland sizes was recorded, with 86% of the wetlands being less than 1 ha in size and the largest natural wetland being a floodplain wetland of 57 ha, located south of the Swartkops River. The identified wetlands were used to create a wetland occurrence model using logistic regression (LR) techniques (Chapter 5), in accordance with Objective 2 of the study. An accuracy of 66% was obtained, which was considered acceptable for a semi-arid climate with a relatively high degree of spatial and temporal rainfall variability. The model also highlighted several key environmental variables that are associated with wetland occurrence and distribution at various spatial scales. Some of the important variables included precipitation, evapotranspiration, temperature, flow accumulation and groundwater occurrence. Wetland distribution patterns were described in Chapter 6. Spatial statistics were used to identify whether wetlands are clustered and, therefore, form mosaics within the surrounding landscape (Objective 3). Systems were found to be highly clustered, with 43% of wetlands located within 200 m of another system. Clustering and wetland presence was especially prominent in the southern portion of the Municipality, which is also associated with a higher mean annual precipitation. Smaller wetlands were also significantly more clustered than larger systems (Average Nearest Neighbour statistic, p-value < 0.0001). Average distances also significantly varied according to HGM type, with depressions being the most geographically isolated wetland type compared to the other HGM types. Overall, distances between wetlands indicated good proximal connectivity. Potentially vulnerable areas associated with wetland systems were identified successfully using landscape variables, in accordance with Objective 4. These variables were: land cover, slope gradient, flow accumulation, APAN evaporation, mean annual precipitation (MAP) and annual heat units. The existing Critical Biodiversity Network was also used in connection with these variables to further identify potentially vulnerable areas. The abiotic and biotic characteristics were decribed for three hydrogeomorphic (HGM) types at a total of 46 wetland sites (Chapter 7), as per Objective 5. Depressions, seeps and wetland flats were sampled across the different geological, vegetation and rainfall zones within the NMBM. The wetland sites were delineated up to Level 6 of the Classification System used in SA, and the various abiotic and biotic characteristics of these systems were defined. A total of 307 plant, 144 aquatic macroinvertebrate and 10 tadpole species were identified. Of these species, over 90 species were Eastern Cape and SA endemic species, as well as three threatened species on the IUCN Red List. Multivariate analyses (including Bray-Curtis similarity resemblance analyses, distance-based redundancy analyses, SIMPER analyses and BIOENV analysis in Primer), together with environmental data, were used to define community structure at an HGM level, in accordance with Objective 5. The importance of the spatial scale of the environmental data used to define plant and macroinvertebrate community structure was described in Chapter 7, to address Objective 6. The results showed that both broad-scale and site-level characteristics were important in distinguishing community structure within the HGM types that superseded general location, the sample timing or the stage of inundation. These results also indicated that a combination of both landscape and site-level data are important in defining the community structure in the various HGM types. Some of the important environmental variables that explained some of species assemblages were similar to those in the wetland occurrence model (Chapter 5), with some additional hydrological and soil physico-chemical parameters (e.g. soil electrical conductivity, soil pH, and surface and subsurface water nutrients). These significant variables indicate the complex, multi-scalar role of environmental attributes on wetland distribution, structure and function.
- Full Text:
- Date Issued: 2016
Diversity and ecological role of true crabs (crustacea, brachyura) in the St Lucia Estuary, iSimangaliso Wetland Park, in response to global change
- Authors: Peer, Nasreen
- Date: 2016
- Subjects: Crustacea -- South Africa -- KwaZulu-Natal Crustacea -- South Africa -- Saint Lucia, Lake , Global environmental change
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/45558 , vital:38669
- Description: This work has explored novel concepts of crab vulnerability, recovery and resilience under unprecedented climatic changes in South Africa’s first UNESCO World Heritage Site. By showing how large salinity shifts and prolonged interruption of the marine connection can drastically affect brachyuran diversity and community structure in St. Lucia Lake, the potential cascading effects on ecosystem functioning were estimated. Only 15 crab species were recorded within the system during this study, compared to the 26 species that were known to occur prior to the recent environmental shift (i.e. 58% decline). The impact of this biodiversity collapse has negatively affected the associated mangrove ecosystem in particular, with the entire community of fiddler crabs persisting only in a small area near the estuary mouth. Gut fluorescence measurements have shown that, due to a lack of tidal Influence, their grazing impact on microphytobenthic biomass may become unsustainable. However, although adults are able to survive in this environment, the larvae require a marine connection; and they are thus unable to tolerate the wide fluctuations in salinity currently prevailing in the system. The study concludes that brachyurans are key factors to consider during conservation planning, as they are crucial to maintaining ecosystem function in the face of environmental change. This research is of global relevance, as many similar estuarine and coastal lakes around the world are currently experiencing similar state shifts. All six chapters included in the thesis have already been published in the peer-reviewed literature; and the project results have also earned Nasreen the NRF award of Next-Generation Researcher of the Year for 2015.
- Full Text:
- Date Issued: 2016
- Authors: Peer, Nasreen
- Date: 2016
- Subjects: Crustacea -- South Africa -- KwaZulu-Natal Crustacea -- South Africa -- Saint Lucia, Lake , Global environmental change
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/45558 , vital:38669
- Description: This work has explored novel concepts of crab vulnerability, recovery and resilience under unprecedented climatic changes in South Africa’s first UNESCO World Heritage Site. By showing how large salinity shifts and prolonged interruption of the marine connection can drastically affect brachyuran diversity and community structure in St. Lucia Lake, the potential cascading effects on ecosystem functioning were estimated. Only 15 crab species were recorded within the system during this study, compared to the 26 species that were known to occur prior to the recent environmental shift (i.e. 58% decline). The impact of this biodiversity collapse has negatively affected the associated mangrove ecosystem in particular, with the entire community of fiddler crabs persisting only in a small area near the estuary mouth. Gut fluorescence measurements have shown that, due to a lack of tidal Influence, their grazing impact on microphytobenthic biomass may become unsustainable. However, although adults are able to survive in this environment, the larvae require a marine connection; and they are thus unable to tolerate the wide fluctuations in salinity currently prevailing in the system. The study concludes that brachyurans are key factors to consider during conservation planning, as they are crucial to maintaining ecosystem function in the face of environmental change. This research is of global relevance, as many similar estuarine and coastal lakes around the world are currently experiencing similar state shifts. All six chapters included in the thesis have already been published in the peer-reviewed literature; and the project results have also earned Nasreen the NRF award of Next-Generation Researcher of the Year for 2015.
- Full Text:
- Date Issued: 2016
Biocomposites from polyfurfuryl alcohol reinforced with microfibres and nanocellulose from flax fibres and maize stalks
- Mtibe, Asanda, Linganiso, Linda
- Authors: Mtibe, Asanda , Linganiso, Linda
- Date: 2016
- Subjects: Textile chemistry Textile chemicals Cellulose -- Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12175 , vital:27041
- Description: This study is aimed at extracting cellulose and nanocelluloses (cellulose nanocrystals (CNCs) and cellulose nanofibres (CNFs)) from maize stalks and flax fibres. Both flax fibres and maize stalks are composed of cellulose, lignin, hemicellulose and extractives. The extraction of cellulose involves the removal of lignin, hemicellulose and extractives. The presence of these components in plant fibres hinders the extraction of cellulose and nanocelluloses. Prior to extraction of cellulose, the different concentrations (1 wt.%, 1.5 wt.% and 2 wt.%) of NaOH were optimised. However, chemical compositions and XRD results revealed that the treatment of flax fibres with 1.5 wt.% sodium hydroxide (NaOH) gives optimum results and this concentration was further selected for the extraction of cellulose. Cellulose was extracted by chemical treatments (sodium hydroxide (NaOH), sodium chlorite (NaClO2) and potassium hydroxide (KOH)) and a combination of chemical treatments and mechanical process (supermass colloider). The materials obtained after each treatment stage during the extraction process were characterised by different characterisation techniques such as Fourier transform infrared (FTIR) spectroscopy, environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The results from the aforementioned characterisation techniques confirmed that cellulose was successfully extracted from flax fibres and maize stalks. Cellulose nanocrystals (CNCs) were extracted by sulphuric acid hydrolysis accompanied with ultra-sonication from cellulose obtained from flax fibres and maize stalks. The extracted CNCs were rod-like material with diameters and lengths in nanoscale and microscale, respectively. On the other hand, cellulose nanofibres (CNFs) were extracted by mechanical process (supermass colloider). The extracted CNFs were web-like material with diameters and lengths in nanoscale and microscale, respectively. The dimensions of nanocelluloses were measured by atomic force microscopy (AFM). Their dispersion was investigated by light polarised microscopy. The extracted nanocelluloses and cellulose were used to produce nanopapers and micropaper. Nanopapers mimic the traditional paper, the only difference of the nanopapers is that they are produced from high aspect ratio nanomaterials. Both nanopapers and micropapers were prepared by solvent evaporating method. Their thermal, optical and mechanical properties were investigated and compared. The mechanical and thermal properties of nanopapers produced from CNFs were better than those produced from CNCs and micropapers. On the other hand, nanopapers produced from CNCs were more transparent in comparison to nanopapers produced from CNFs and micropapers. Cellulosic fibres have attracted a considerable attention in composite materials due to their high tensile strength and tensile modulus. This study is focused on the development of biocomposites of polyfurfuryl alcohol (PFA) by in-situ polymerisation in the presence of acid catalyst (p-toluene sulphonic acid). Biocomposites were produced by reinforcing PFA with flax fibres (untreated and treated), nanoparticles and CNCs. The biocomposites reinforced with CNCs and flax fibres showed an improvement in mechanical, thermal and thermo-mechanical properties. On the other hand, biocomposites reinforced with nanoparticles obtained from treated maize stalks showed an improvement in mechanical and thermal properties while biocomposites reinforced with nanoparticles obtained from untreated maize stalks showed lower mechanical properties and decreased thermal stability.
- Full Text:
- Date Issued: 2016
- Authors: Mtibe, Asanda , Linganiso, Linda
- Date: 2016
- Subjects: Textile chemistry Textile chemicals Cellulose -- Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12175 , vital:27041
- Description: This study is aimed at extracting cellulose and nanocelluloses (cellulose nanocrystals (CNCs) and cellulose nanofibres (CNFs)) from maize stalks and flax fibres. Both flax fibres and maize stalks are composed of cellulose, lignin, hemicellulose and extractives. The extraction of cellulose involves the removal of lignin, hemicellulose and extractives. The presence of these components in plant fibres hinders the extraction of cellulose and nanocelluloses. Prior to extraction of cellulose, the different concentrations (1 wt.%, 1.5 wt.% and 2 wt.%) of NaOH were optimised. However, chemical compositions and XRD results revealed that the treatment of flax fibres with 1.5 wt.% sodium hydroxide (NaOH) gives optimum results and this concentration was further selected for the extraction of cellulose. Cellulose was extracted by chemical treatments (sodium hydroxide (NaOH), sodium chlorite (NaClO2) and potassium hydroxide (KOH)) and a combination of chemical treatments and mechanical process (supermass colloider). The materials obtained after each treatment stage during the extraction process were characterised by different characterisation techniques such as Fourier transform infrared (FTIR) spectroscopy, environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The results from the aforementioned characterisation techniques confirmed that cellulose was successfully extracted from flax fibres and maize stalks. Cellulose nanocrystals (CNCs) were extracted by sulphuric acid hydrolysis accompanied with ultra-sonication from cellulose obtained from flax fibres and maize stalks. The extracted CNCs were rod-like material with diameters and lengths in nanoscale and microscale, respectively. On the other hand, cellulose nanofibres (CNFs) were extracted by mechanical process (supermass colloider). The extracted CNFs were web-like material with diameters and lengths in nanoscale and microscale, respectively. The dimensions of nanocelluloses were measured by atomic force microscopy (AFM). Their dispersion was investigated by light polarised microscopy. The extracted nanocelluloses and cellulose were used to produce nanopapers and micropaper. Nanopapers mimic the traditional paper, the only difference of the nanopapers is that they are produced from high aspect ratio nanomaterials. Both nanopapers and micropapers were prepared by solvent evaporating method. Their thermal, optical and mechanical properties were investigated and compared. The mechanical and thermal properties of nanopapers produced from CNFs were better than those produced from CNCs and micropapers. On the other hand, nanopapers produced from CNCs were more transparent in comparison to nanopapers produced from CNFs and micropapers. Cellulosic fibres have attracted a considerable attention in composite materials due to their high tensile strength and tensile modulus. This study is focused on the development of biocomposites of polyfurfuryl alcohol (PFA) by in-situ polymerisation in the presence of acid catalyst (p-toluene sulphonic acid). Biocomposites were produced by reinforcing PFA with flax fibres (untreated and treated), nanoparticles and CNCs. The biocomposites reinforced with CNCs and flax fibres showed an improvement in mechanical, thermal and thermo-mechanical properties. On the other hand, biocomposites reinforced with nanoparticles obtained from treated maize stalks showed an improvement in mechanical and thermal properties while biocomposites reinforced with nanoparticles obtained from untreated maize stalks showed lower mechanical properties and decreased thermal stability.
- Full Text:
- Date Issued: 2016
Higher order modulation formats for high speed optical communication systems with digital signal processing aided receiver
- Chabata, Tichakunda Valentine
- Authors: Chabata, Tichakunda Valentine
- Date: 2016
- Subjects: Optical communications , Modulation (Electronics) , Signal processing
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/4775 , vital:20677
- Description: The drastic increase in the number of internet users and the general convergence of all other communication systems into an optical system have brought a sharp rise in demand for bandwidth and calls for high capacity transmission networks. Large unamplified transmission reach is another contributor in reducing deployment costs of an optical communication system. Spectrally efficient modulation formats are suggested as a solution to overcome the problems associated with limited channels and bandwidth of dense wavelength division multiplexing (DWDM) optical communication systems. Higher order modulation formats which are considered to be spectrally efficient and can increase the transmission capacity by transmitting more information in the amplitude, phase, polarization or a combination of all was studied. Different detection technologies are to be implemented to suit a particular higher order modulation format. In this research multilevel modulation formats, different detection technologies and a digital signal processing aided receiver were studied in a practical optical transmission system. The work in this thesis started with the implementation of the traditional amplitude shift keying (ASK) modulation and a differential phase shift keying (DPSK) modulation systems as they form the basic building block in the design of higher order modulation formats. Results obtained from using virtual photonics instruments (VPI)simulation software, receiver sensitivity for 10Gbpsnon-return-to-zero (NRZ), amplitude phase shift keying (ASK) and DPSK signals were measured to be -22.7 dBm and -22.0 dBm respectively. Performance comparison for the two modulation formats were done over different transmission distances. ASK also known as On-Off keying (OOK) performed better for shorter lengths whereas DPSK performed better for longer lengths of up to90km.Experimental results on a 10 Gbps NRZ- ASK signal gave a receiver sensitivity of -21.1 dBm from digital signal processing (DSP) aided receiver against -19.8 dBm from the commercial bit error ratio tester (BERT) yielding a small difference of 1.3 dB hence validating the reliability and accuracy of the digital signal processing (DSP) assisted receiver. Traditional direct detection scheme and coherent detection scheme performances were evaluated again on a 10 Gbps NRZ ASK signal. Coherent detection that can achieve a large unamplified transmission reach and has a higher passive optical splitting ratio was first evaluated using the VPI simulation software. Simulation results gave a receiver sensitivity of -30.4 dBm forcoherent detection and -18.3 dBm for direct detection, yielding a gain in receiver sensitivity of 12.1 dB. The complex coherently detected signal, from the experimental setup gave a receiver sensitivity of -20.6 dBm with a gain in receiver sensitivity of 3.5 dBm with respect to direct detection. A multilevel pulse amplitude modulation (4-PAM) that doubles the data rate per channel from10 Gbps to 20 Gbps by transmitting more information in the amplitude of the carrier signal was implemented. This was achieved by modulating the optical amplitude with an electrical four level amplitude shift keyed (ASK) signal. A receiver consisting of a single photodiode, three decision circuits and a decoding logic circuit was used to receive and extract the original transmitted data. A DSP aided receiver was used to evaluate the link performance. A receiver sensitivity of -12.8 dBm is attained with a dispersion penalty of about 7.2 dB after transmission through 25 km of G.652 fibre.
- Full Text:
- Date Issued: 2016
- Authors: Chabata, Tichakunda Valentine
- Date: 2016
- Subjects: Optical communications , Modulation (Electronics) , Signal processing
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/4775 , vital:20677
- Description: The drastic increase in the number of internet users and the general convergence of all other communication systems into an optical system have brought a sharp rise in demand for bandwidth and calls for high capacity transmission networks. Large unamplified transmission reach is another contributor in reducing deployment costs of an optical communication system. Spectrally efficient modulation formats are suggested as a solution to overcome the problems associated with limited channels and bandwidth of dense wavelength division multiplexing (DWDM) optical communication systems. Higher order modulation formats which are considered to be spectrally efficient and can increase the transmission capacity by transmitting more information in the amplitude, phase, polarization or a combination of all was studied. Different detection technologies are to be implemented to suit a particular higher order modulation format. In this research multilevel modulation formats, different detection technologies and a digital signal processing aided receiver were studied in a practical optical transmission system. The work in this thesis started with the implementation of the traditional amplitude shift keying (ASK) modulation and a differential phase shift keying (DPSK) modulation systems as they form the basic building block in the design of higher order modulation formats. Results obtained from using virtual photonics instruments (VPI)simulation software, receiver sensitivity for 10Gbpsnon-return-to-zero (NRZ), amplitude phase shift keying (ASK) and DPSK signals were measured to be -22.7 dBm and -22.0 dBm respectively. Performance comparison for the two modulation formats were done over different transmission distances. ASK also known as On-Off keying (OOK) performed better for shorter lengths whereas DPSK performed better for longer lengths of up to90km.Experimental results on a 10 Gbps NRZ- ASK signal gave a receiver sensitivity of -21.1 dBm from digital signal processing (DSP) aided receiver against -19.8 dBm from the commercial bit error ratio tester (BERT) yielding a small difference of 1.3 dB hence validating the reliability and accuracy of the digital signal processing (DSP) assisted receiver. Traditional direct detection scheme and coherent detection scheme performances were evaluated again on a 10 Gbps NRZ ASK signal. Coherent detection that can achieve a large unamplified transmission reach and has a higher passive optical splitting ratio was first evaluated using the VPI simulation software. Simulation results gave a receiver sensitivity of -30.4 dBm forcoherent detection and -18.3 dBm for direct detection, yielding a gain in receiver sensitivity of 12.1 dB. The complex coherently detected signal, from the experimental setup gave a receiver sensitivity of -20.6 dBm with a gain in receiver sensitivity of 3.5 dBm with respect to direct detection. A multilevel pulse amplitude modulation (4-PAM) that doubles the data rate per channel from10 Gbps to 20 Gbps by transmitting more information in the amplitude of the carrier signal was implemented. This was achieved by modulating the optical amplitude with an electrical four level amplitude shift keyed (ASK) signal. A receiver consisting of a single photodiode, three decision circuits and a decoding logic circuit was used to receive and extract the original transmitted data. A DSP aided receiver was used to evaluate the link performance. A receiver sensitivity of -12.8 dBm is attained with a dispersion penalty of about 7.2 dB after transmission through 25 km of G.652 fibre.
- Full Text:
- Date Issued: 2016
The ecology of hard substrate communities around Sardinia Bay in the warm-temperate Agulhas Bioregion
- Authors: Evans, Adrian G , Nel, Ronel
- Date: 2016
- Subjects: Aquatic biodiversity -- South Africa -- Nelson Mandela Bay Municipality , Marine ecology -- South Africa -- Nelson Mandela Bay Municipality , Seashore biology -- South Africa -- Nelson Mandela Bay Municipality
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6782 , vital:21141
- Description: Hard substrates in the marine environment are an important ecosystem of great scientific and economic value. Hard substrates provide suitable habitat for a diverse assemblage of benthic organisms. This thesis investigated the ecology of benthic hard substrate communities along a section of wave-exposed coastline, including the Sardinia Bay Marine Protected Area (MPA), in the warm-temperate Agulhas bioregion of South Africa. The effect of physical variables on benthic communities, including both the intertidal and shallow subtidal, was quantitatively assessed across (Chapter 3) and along (Chapter 4) the shore to provide a model of zonation for this bioregion and a baseline of community patters and biodiversity, as this information was lacking especially for the Sardinia Bay MPA. The zones described in Chapter 3 were in agreement with previous trends described for this bioregion with the addition of different biotopes in the upper Balanoid and deeper subtidal zones as well as the addition of an intermediate/transition zone in the subtidal between the algal dominated shallow subtidal and deeper subtidal, which has an increased abundance of sessile invertebrates. Disturbance is an important process in structuring benthic communities, and its role in structuring shallow benthic communities was investigated using a disturbance simulation experiment across a wave-exposure gradient (Chapter 5). Communities were found to change along the exposure gradient and monitoring the undisturbed communities showed that large waves caused disturbances across all the exposures. The recovery process was similar across all exposures mainly through lateral vegetative growth and regrowth from basal parts with communities in disturbed quadrats recovering to resemble the surrounding undisturbed community. Recruitment did not have a significant effect in the recovery process and community composition was therefore a result of the effects of the physical environment along the exposure gradient. Lastly this thesis investigated the indirect effects of protection in the small Sardinia Bay MPA (Chapter 6). Despite the small size of the MPA this study found differences in diversity and abundance between communities inside and outside the MPA. These differences in benthic biota infer indirect effects of protection that are probably due to the increase in abundance of exploited fish inside the MPA. Lower abundances of red algae, macroinvertebrates and diversity inside the MPA in the shallow depth category was attributed to the higher abundance of the generalist fish species that concentrate in the shallows. Significantly lower abundances of Chordata in the shallow and medium depth categories inside the MPA was attributed to predation by the benthic carnivorous species as ascidians are included in the diet of these species. This chapter also compared the effectiveness of destructive (scraped quadrats) and non-destructive (visually assessed quadrats) sampling methods. Scraped quadrats were found to be more effective in detecting changes across the MPA compared to visually assessed quadrats. Destructive methods sample the entire assemblage, to a higher taxonomic level, and measure abundance using biomass. It was concluded that biomass is a better metric when comparing communities across protection or other treatments as it provides better biological information of the community.
- Full Text:
- Date Issued: 2016
- Authors: Evans, Adrian G , Nel, Ronel
- Date: 2016
- Subjects: Aquatic biodiversity -- South Africa -- Nelson Mandela Bay Municipality , Marine ecology -- South Africa -- Nelson Mandela Bay Municipality , Seashore biology -- South Africa -- Nelson Mandela Bay Municipality
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6782 , vital:21141
- Description: Hard substrates in the marine environment are an important ecosystem of great scientific and economic value. Hard substrates provide suitable habitat for a diverse assemblage of benthic organisms. This thesis investigated the ecology of benthic hard substrate communities along a section of wave-exposed coastline, including the Sardinia Bay Marine Protected Area (MPA), in the warm-temperate Agulhas bioregion of South Africa. The effect of physical variables on benthic communities, including both the intertidal and shallow subtidal, was quantitatively assessed across (Chapter 3) and along (Chapter 4) the shore to provide a model of zonation for this bioregion and a baseline of community patters and biodiversity, as this information was lacking especially for the Sardinia Bay MPA. The zones described in Chapter 3 were in agreement with previous trends described for this bioregion with the addition of different biotopes in the upper Balanoid and deeper subtidal zones as well as the addition of an intermediate/transition zone in the subtidal between the algal dominated shallow subtidal and deeper subtidal, which has an increased abundance of sessile invertebrates. Disturbance is an important process in structuring benthic communities, and its role in structuring shallow benthic communities was investigated using a disturbance simulation experiment across a wave-exposure gradient (Chapter 5). Communities were found to change along the exposure gradient and monitoring the undisturbed communities showed that large waves caused disturbances across all the exposures. The recovery process was similar across all exposures mainly through lateral vegetative growth and regrowth from basal parts with communities in disturbed quadrats recovering to resemble the surrounding undisturbed community. Recruitment did not have a significant effect in the recovery process and community composition was therefore a result of the effects of the physical environment along the exposure gradient. Lastly this thesis investigated the indirect effects of protection in the small Sardinia Bay MPA (Chapter 6). Despite the small size of the MPA this study found differences in diversity and abundance between communities inside and outside the MPA. These differences in benthic biota infer indirect effects of protection that are probably due to the increase in abundance of exploited fish inside the MPA. Lower abundances of red algae, macroinvertebrates and diversity inside the MPA in the shallow depth category was attributed to the higher abundance of the generalist fish species that concentrate in the shallows. Significantly lower abundances of Chordata in the shallow and medium depth categories inside the MPA was attributed to predation by the benthic carnivorous species as ascidians are included in the diet of these species. This chapter also compared the effectiveness of destructive (scraped quadrats) and non-destructive (visually assessed quadrats) sampling methods. Scraped quadrats were found to be more effective in detecting changes across the MPA compared to visually assessed quadrats. Destructive methods sample the entire assemblage, to a higher taxonomic level, and measure abundance using biomass. It was concluded that biomass is a better metric when comparing communities across protection or other treatments as it provides better biological information of the community.
- Full Text:
- Date Issued: 2016
The effect of silica on the reduction of precipitated iron-based fischer-tropsch catalysts
- Authors: Coombes, Matthew
- Date: 2016
- Subjects: Fischer-Tropsch process Reduction (Chemistry) , Catalysts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/14873 , vital:27888
- Description: Iron Fischer-Tropsch (FT) catalysts are typically prepared as iron oxides which are reduced to FT-active iron metal and iron carbide prior to FT synthesis. The iron oxides contain a variety of different chemical and structural promoters to alter FT-activity. Silica is a common structural promoter which stabilises the formation of small crystallites and provides mechanical integrity to the catalyst. However, silica inhibits the reduction of the oxide precursor to the FT-active phases. This ultimately affects catalyst activity and product selectivity. It has been proposed that the silica interacts with the iron to form encapsulating shells of fayalite (Fe2SiO4), or fayalite rafts between the iron oxide and the silica support. In this study, six silica-promoted iron oxide samples were prepared using a simple co-precipitation technique. Samples contain varying amounts of silica, and the samples are named 100/x Fe/SiO2, where x is the weight of silica for 100 weight iron, with x taking on values of 0, 10, 25, 50, 100 and 200. The resulting iron oxides were characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRPD), M¨ossbauer spectroscopy (MS), magnetic susceptibility measurements (MM), Raman spectroscopy, thermal gravimetric analysis (TGA) and nitrogen physisorption. Their reduction in a hydrogen atmosphere was investigated using temperature programmed reduction (TPR), in situ XRPD and TEM. The reduction in hydrogen of 100/0 Fe/SiO2 and 100/10 Fe/SiO2 was also studied using in situ gas flow TEM cells. These cells allow the samples to be studied in the electron microscope at temperature and pressure conditions approaching those experienced in a real reactor environment. In the absence of a silica promoter (100/0 Fe/SiO2), hematite particles are formed with mean particle diameters of 39 ± 12 and 52.7 ± 0.2 nm determined using TEM and XRPD respectively. MM data reveals a magnetic transition (Morin transition) at≈230 K, consistent with a mean particle size of≈50 nm. In a hydrogen atmosphere, the hematite reduces to metallic iron via a two-step process viz. hematite → magnetite → iron. The final iron particles have an average crystallite size of 68.0 ± 0.2 nm. The presence of lower amounts of silica in the samples 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 results in the formation of silicasubstituted 2-line ferrihydrite particles. Bands in the Raman spectra of these samples shift on increasing silica content, which indicates an increasing number of Fe-O-Si bonds within the ferrihydrite framework. MM reveals typical superparamagnetic (SPM) behaviour above a blocking temperature in the range 39 - 68 K which gives mean particle sizes of 4.2, 3.6 and 3.5 nm for 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 respectively, in good agreement with particle sizes determined using TEM (3.1±0.4, 2.4±0.3 and 2.4±0.3 nm respectively). MS data at 300 K and 4.2 K were fitted with distributions of ∆EQ and Bhf respectively. The median values of Bhf decrease with increasing silica content, indicating greater degrees of distortion in the Fe3+ environments induced by increased silica substitution. The reduction to metallic iron occurs via a three-step process viz. hematite → magnetite → wu¨stite → iron, with the silica stabilising the wu¨stite phase. The increasing amount of Fe-O-Si bonds on increasing silica content shifts reduction to higher temperatures broadens each reduction step as a result of local Fe-O-Si concentration variations. Fractions of each sample are not completely reduced even at 1000°C, with the relative proportion increasing with increasing silica content. In situ gas flow TEM studies reveal that the mechanism of reduction involves the liberation of atomic iron atoms from the silica-substituted iron oxides which agglomerate and grow into final iron particles. This leaves a poorly crystalline Fe-O-Si bonded framework behind. STEM-EDS and STEM-EELS reveal low concentrations of silicon at the surface of the resulting iron particles, however they do not form encapsulating shells of fayalite as previously suggested. The majority of the silica remains in the Fe-O-Si material which may crystallise into separate fayalite particles at elevated temperature. The presence of silica in high proportions (100/100 Fe/SiO2 and 100/200 Fe/SiO2) results in the formation of a two-phase system consisting of silicasubstituted 2-line ferrihydrite particles which are encapsulated in an ironinfused amorphous silica network. As with the other silica-bearing samples, there is an increase in Fe-O-Si bonds and an increase in the degree of distortion at Fe3+ sites with increasing silica content. The large amount of silica suppresses the blocking temperature of the SPM crystallites. In a hydrogen atmosphere, the reduction to metallic iron follows the same three step process as the other silica-bearing samples. Reduction temperatures are further shifted to higher values and given reduction steps are considerably broader with increasing silica content. The fraction of iron not fully reduced also increases. Iron particle diameters are very small, since encapsulation by the silica matrix prevents growth of particles.
- Full Text:
- Date Issued: 2016
- Authors: Coombes, Matthew
- Date: 2016
- Subjects: Fischer-Tropsch process Reduction (Chemistry) , Catalysts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/14873 , vital:27888
- Description: Iron Fischer-Tropsch (FT) catalysts are typically prepared as iron oxides which are reduced to FT-active iron metal and iron carbide prior to FT synthesis. The iron oxides contain a variety of different chemical and structural promoters to alter FT-activity. Silica is a common structural promoter which stabilises the formation of small crystallites and provides mechanical integrity to the catalyst. However, silica inhibits the reduction of the oxide precursor to the FT-active phases. This ultimately affects catalyst activity and product selectivity. It has been proposed that the silica interacts with the iron to form encapsulating shells of fayalite (Fe2SiO4), or fayalite rafts between the iron oxide and the silica support. In this study, six silica-promoted iron oxide samples were prepared using a simple co-precipitation technique. Samples contain varying amounts of silica, and the samples are named 100/x Fe/SiO2, where x is the weight of silica for 100 weight iron, with x taking on values of 0, 10, 25, 50, 100 and 200. The resulting iron oxides were characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRPD), M¨ossbauer spectroscopy (MS), magnetic susceptibility measurements (MM), Raman spectroscopy, thermal gravimetric analysis (TGA) and nitrogen physisorption. Their reduction in a hydrogen atmosphere was investigated using temperature programmed reduction (TPR), in situ XRPD and TEM. The reduction in hydrogen of 100/0 Fe/SiO2 and 100/10 Fe/SiO2 was also studied using in situ gas flow TEM cells. These cells allow the samples to be studied in the electron microscope at temperature and pressure conditions approaching those experienced in a real reactor environment. In the absence of a silica promoter (100/0 Fe/SiO2), hematite particles are formed with mean particle diameters of 39 ± 12 and 52.7 ± 0.2 nm determined using TEM and XRPD respectively. MM data reveals a magnetic transition (Morin transition) at≈230 K, consistent with a mean particle size of≈50 nm. In a hydrogen atmosphere, the hematite reduces to metallic iron via a two-step process viz. hematite → magnetite → iron. The final iron particles have an average crystallite size of 68.0 ± 0.2 nm. The presence of lower amounts of silica in the samples 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 results in the formation of silicasubstituted 2-line ferrihydrite particles. Bands in the Raman spectra of these samples shift on increasing silica content, which indicates an increasing number of Fe-O-Si bonds within the ferrihydrite framework. MM reveals typical superparamagnetic (SPM) behaviour above a blocking temperature in the range 39 - 68 K which gives mean particle sizes of 4.2, 3.6 and 3.5 nm for 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 respectively, in good agreement with particle sizes determined using TEM (3.1±0.4, 2.4±0.3 and 2.4±0.3 nm respectively). MS data at 300 K and 4.2 K were fitted with distributions of ∆EQ and Bhf respectively. The median values of Bhf decrease with increasing silica content, indicating greater degrees of distortion in the Fe3+ environments induced by increased silica substitution. The reduction to metallic iron occurs via a three-step process viz. hematite → magnetite → wu¨stite → iron, with the silica stabilising the wu¨stite phase. The increasing amount of Fe-O-Si bonds on increasing silica content shifts reduction to higher temperatures broadens each reduction step as a result of local Fe-O-Si concentration variations. Fractions of each sample are not completely reduced even at 1000°C, with the relative proportion increasing with increasing silica content. In situ gas flow TEM studies reveal that the mechanism of reduction involves the liberation of atomic iron atoms from the silica-substituted iron oxides which agglomerate and grow into final iron particles. This leaves a poorly crystalline Fe-O-Si bonded framework behind. STEM-EDS and STEM-EELS reveal low concentrations of silicon at the surface of the resulting iron particles, however they do not form encapsulating shells of fayalite as previously suggested. The majority of the silica remains in the Fe-O-Si material which may crystallise into separate fayalite particles at elevated temperature. The presence of silica in high proportions (100/100 Fe/SiO2 and 100/200 Fe/SiO2) results in the formation of a two-phase system consisting of silicasubstituted 2-line ferrihydrite particles which are encapsulated in an ironinfused amorphous silica network. As with the other silica-bearing samples, there is an increase in Fe-O-Si bonds and an increase in the degree of distortion at Fe3+ sites with increasing silica content. The large amount of silica suppresses the blocking temperature of the SPM crystallites. In a hydrogen atmosphere, the reduction to metallic iron follows the same three step process as the other silica-bearing samples. Reduction temperatures are further shifted to higher values and given reduction steps are considerably broader with increasing silica content. The fraction of iron not fully reduced also increases. Iron particle diameters are very small, since encapsulation by the silica matrix prevents growth of particles.
- Full Text:
- Date Issued: 2016
Effects of lethal management on black-backed jackal population structure and source-sink dynamics
- Authors: Minnie, Liaan
- Date: 2016
- Subjects: Black-backed jackal Carnivorous animals
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12658 , vital:27104
- Description: Lethal carnivore management, aimed at reducing carnivore impacts, threatens the persistence of carnivores globally. The effects of killing carnivores will depend on their life histories and social structures. Smaller canids, like black-backed jackals (Canis mesomelas), are highly adaptable and display variable population-level responses to mortality sources, which may contribute to their success in fragmented landscapes. Jackals, the dominant predator of livestock in South Africa, are widely hunted to reduce this predation. This hunting is heterogeneous across the landscape, focussed on livestock and game farms, with nature reserves acting as refuges. The aim of this research was to investigate the ecology and population dynamics of jackals in response to heterogeneous anthropogenic mortality. I hypothesized that the spatial variation in hunting results in the formation of a source-sink population structure, which contributes to the persistence of jackals. I addressed this hypothesis by evaluating two criteria, essential for the formation of a source-sink system in larger mammals. Firstly, I confirm that hunting pressures result in the formation of distinct subpopulations with asymmetrical dispersal (i.e. compensatory immigration) from unhunted reserves to neighbouring hunted farms. Secondly, I show that jackal subpopulation display asynchronous demographics, with farm populations displaying a relatively younger age structure and an associated increase in reproductive output (i.e. compensatory reproduction). This confirms the formation of a hunting-induced source-sink system. additionally, I show that jackals have a catholic diet, which confers a level of adaptability to direct (anthropogenic mortality, prey provisioning) and indirect (alteration in prey base) habitat modifications. This dietary flexibility allows jackals to obtain the appropriate resources to achieve reproductive condition. The relatively better body condition of younger jackals in sink habitats allows for compensatory reproduction which contributes to the success of jackals on hunted farms. Based on my findings, I hypothesize that the compensatory life history responses of jackals to anthropogenic mortality may be ascribed to two interconnected mechanism. Dispersal is presumably driven by density-dependent interference competition, as dominant territorial pairs outcompete subordinates in high-density reserve areas, forcing them to disperse onto low-density farms (i.e. ideal despotic model). Additionally, farms likely represent attractive habitats, owing to a reduction in conspecifics and a concomitant increase in resource availability (including anthropogenic resource provisioning). Therefore, dispersing subordinates presumably select for farms which are perceived as good quality habitats, as the high risks of anthropogenic mortality cannot be perceived by dispersing individuals. This results in the formation of an attractive sink or ecological trap. These compensatory processes will continue to counter population management actions as long as recruitment from unmanaged areas persists. This hypothesis provides a conceptual framework for future research directions in understanding jackal persistence and management (i.e. specifically focussing on controlling dispersal) of jackal populations.
- Full Text:
- Date Issued: 2016
- Authors: Minnie, Liaan
- Date: 2016
- Subjects: Black-backed jackal Carnivorous animals
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12658 , vital:27104
- Description: Lethal carnivore management, aimed at reducing carnivore impacts, threatens the persistence of carnivores globally. The effects of killing carnivores will depend on their life histories and social structures. Smaller canids, like black-backed jackals (Canis mesomelas), are highly adaptable and display variable population-level responses to mortality sources, which may contribute to their success in fragmented landscapes. Jackals, the dominant predator of livestock in South Africa, are widely hunted to reduce this predation. This hunting is heterogeneous across the landscape, focussed on livestock and game farms, with nature reserves acting as refuges. The aim of this research was to investigate the ecology and population dynamics of jackals in response to heterogeneous anthropogenic mortality. I hypothesized that the spatial variation in hunting results in the formation of a source-sink population structure, which contributes to the persistence of jackals. I addressed this hypothesis by evaluating two criteria, essential for the formation of a source-sink system in larger mammals. Firstly, I confirm that hunting pressures result in the formation of distinct subpopulations with asymmetrical dispersal (i.e. compensatory immigration) from unhunted reserves to neighbouring hunted farms. Secondly, I show that jackal subpopulation display asynchronous demographics, with farm populations displaying a relatively younger age structure and an associated increase in reproductive output (i.e. compensatory reproduction). This confirms the formation of a hunting-induced source-sink system. additionally, I show that jackals have a catholic diet, which confers a level of adaptability to direct (anthropogenic mortality, prey provisioning) and indirect (alteration in prey base) habitat modifications. This dietary flexibility allows jackals to obtain the appropriate resources to achieve reproductive condition. The relatively better body condition of younger jackals in sink habitats allows for compensatory reproduction which contributes to the success of jackals on hunted farms. Based on my findings, I hypothesize that the compensatory life history responses of jackals to anthropogenic mortality may be ascribed to two interconnected mechanism. Dispersal is presumably driven by density-dependent interference competition, as dominant territorial pairs outcompete subordinates in high-density reserve areas, forcing them to disperse onto low-density farms (i.e. ideal despotic model). Additionally, farms likely represent attractive habitats, owing to a reduction in conspecifics and a concomitant increase in resource availability (including anthropogenic resource provisioning). Therefore, dispersing subordinates presumably select for farms which are perceived as good quality habitats, as the high risks of anthropogenic mortality cannot be perceived by dispersing individuals. This results in the formation of an attractive sink or ecological trap. These compensatory processes will continue to counter population management actions as long as recruitment from unmanaged areas persists. This hypothesis provides a conceptual framework for future research directions in understanding jackal persistence and management (i.e. specifically focussing on controlling dispersal) of jackal populations.
- Full Text:
- Date Issued: 2016
Anti-diabetic and phytochemical analysis of sutherlandia frutescens extracts
- Authors: Adefuye, Ogheneochuko Janet
- Date: 2016
- Subjects: Medicinal plants -- Africa , Traditional medicine -- Africa , Herbs -- Therapeutic use -- Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/3549 , vital:20441
- Description: In Africa, the importance of medicinal plants in folklore medicine and their contribution to primary healthcare is well recognized. Across the continent, local herbal mixtures still provide the only therapeutic option for about 80% of the population. The vast floral diversity and the intrinsic ethnobotanical knowledge has been the backbone of localized traditional herbal medical practices. In Africa, an estimated 5400 of the 60000 described plant taxa possess over 16300 therapeutic uses. Similarly, with a therapeutic flora comprising of approximately 650 species, herbal medical practitioners in South Africa, make use of a plethora of plants to treat different human diseases and infections. Over the years, studies have identified numerous plant species with potential against chronic metabolic diseases including type 2 diabetes mellitus (T2DM). Globally, the incidence and prevalence of T2DM have reached epidemic proportions affecting people of all ages, nationalities and ethnicity. Considered the fourth leading cause of deaths by disease, T2DM is a global health crisis with an estimated diagnosis and mortality frequency of 1 every 5 seconds and 1 every 7 seconds respectively. Though the exact pathophysiology of T2DM is not entirely understood, initial peripheral insulin resistance in adipose tissue, liver, and skeletal muscle with subsequent pancreatic β-cell dysfunction resulting from an attempt to compensate for insulin resistance is a common feature of the disease. The current approach to treating T2DM is the use of oral antidiabetic agents (OAAs), insulin, and incretin-based drugs in an attempt to achieve glycaemic control and maintain glucose homeostasis. However, conventional anti-T2DM drugs have been shown to have limited efficacies and serious adverse effects. Hence, the need for newer, more efficacious and safer anti-T2DM agents. Sutherlandia frutescens subsp. microphylla is a flowering shrub of the pea family (Fabaceae/Leguminaceae) found mainly in the Western Cape and Karoo regions of Southern Africa. Concoctions of various parts of the plant are used in the management of different ailments including T2DM. However, despite extensive biological and pharmacological studies, few analyses exist of the chemical constituents of S. frutescens and no Triple Time of Flight Liquid Chromatography with Mass Spectrometry (Triple TOF LC/MS/MS) analysis has been performed. The initial aim of this study was to investigate the phytochemical profile of hot aqueous, cold aqueous, 80% ethanolic, 100% ethanolic, 80% methanolic and 100% methanolic extracts of a single source S. frutescens plant material using colorimetric and spectrophotometric analysis. The hot aqueous extractant was found to be the best extractant for S. frutescens, yielding 1.99 g of crude extract from 16 g fresh powdered plant material. This data suggests that application of heat and water as the extractant (hot aqueous) could play a vital role in extraction of bioactive compounds from S. frutescens and also justifies the traditional use of a tea infusion of S. frutescens. Colorimetric analysis revealed the presence of flavonoids, flavonols, tannins, and phenols in all extracts with varying intensity. The organic extracts 100% methanol, 80% and 100% ethanol exhibited high color intensity (+++) for flavonoids and flavonols respectively, while all the extracts exhibited a moderate color intensity (++) for tannins and phenols. Spectrophotometric analysis of S. frutescens extracts revealed that all the organic extracts contained a significantly higher concentration (in mg/g of extract) of flavonols and tannins when compared to the aqueous extracts. All extracts contained approximately equal levels of phenols. These data confirm the presence of all four groups of bioactive phytocompounds in the S. frutescens extracts used in this study, and also confirm that different solvent extractants possess the capability to differentially extract specific groups of phytocompounds. in individual extracts. Further comparison of these compounds with online databases of anti-diabetic phytocompounds led to the preliminary identification of 10 possible anti-diabetic compounds; α-Pinene, Limonene, Sabinene, Carvone, Myricetin, Rutin, Stigmasterol, Emodin, Sarpagine and Hypoglycin B in crude and solid phase extraction (SPE) fractions of S. frutesecens. Furthermore, using two hepatic cell lines (Chang and HepG2) as an in-vtro model system, the anti-T2DM properties of crude aqueous and organic extracts of S. frutescents was investigated and compared. Both aqueous and organic extracts of S. frutescens were found to decrease gluconeogenesis, increase glucose uptake and decrease lipid accumulation (Triacylglycerol, Diacylglycerol, and Monoacylglycerol) in Chang and HepG2 hepatic cell cultures made insulin resistant (IR) following exposure to high concentration of insulin and fructose. Using real-time quantitative reverse transcriptase polymerase chain reaction (qRT-PCR), the aqueous and organic extracts of S. frutescens were confirmed to regulate the expression of Vesicle-associated membrane protein 3 (VAMP3), Mitogen-activated protein kinase 8 (MAPK8), and Insulin receptor substrate 1 (IRS1) in insulin resistant hepatic cells. IR-mediated downregulation of VAMP3, MAPK8, and IRS1 mRNA in IR HepG2 hepatic cell cultures was reversed in the presence of aqueous and organic extracts of S. frutescens. The hot aqueous extract displayed the highest activity in all the assays, while all the organic extracts displayed similar potency. In conclusion, this study reports that aqueous and organic extracts of S. frutescens possess numerous anti-diabetic compounds that can be further investigated for the development of new, more efficacious and less toxic anti-diabetic agents. The presence of multiple compounds in a single extract does suggest a synergistic or combinatorial therapeutic effect. These findings support the burgeoning body of in-vivo and in-vitro literature evidence on the anti-diabetic properties of S. frutescens and its use in folklore medicine.
- Full Text:
- Date Issued: 2016
- Authors: Adefuye, Ogheneochuko Janet
- Date: 2016
- Subjects: Medicinal plants -- Africa , Traditional medicine -- Africa , Herbs -- Therapeutic use -- Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/3549 , vital:20441
- Description: In Africa, the importance of medicinal plants in folklore medicine and their contribution to primary healthcare is well recognized. Across the continent, local herbal mixtures still provide the only therapeutic option for about 80% of the population. The vast floral diversity and the intrinsic ethnobotanical knowledge has been the backbone of localized traditional herbal medical practices. In Africa, an estimated 5400 of the 60000 described plant taxa possess over 16300 therapeutic uses. Similarly, with a therapeutic flora comprising of approximately 650 species, herbal medical practitioners in South Africa, make use of a plethora of plants to treat different human diseases and infections. Over the years, studies have identified numerous plant species with potential against chronic metabolic diseases including type 2 diabetes mellitus (T2DM). Globally, the incidence and prevalence of T2DM have reached epidemic proportions affecting people of all ages, nationalities and ethnicity. Considered the fourth leading cause of deaths by disease, T2DM is a global health crisis with an estimated diagnosis and mortality frequency of 1 every 5 seconds and 1 every 7 seconds respectively. Though the exact pathophysiology of T2DM is not entirely understood, initial peripheral insulin resistance in adipose tissue, liver, and skeletal muscle with subsequent pancreatic β-cell dysfunction resulting from an attempt to compensate for insulin resistance is a common feature of the disease. The current approach to treating T2DM is the use of oral antidiabetic agents (OAAs), insulin, and incretin-based drugs in an attempt to achieve glycaemic control and maintain glucose homeostasis. However, conventional anti-T2DM drugs have been shown to have limited efficacies and serious adverse effects. Hence, the need for newer, more efficacious and safer anti-T2DM agents. Sutherlandia frutescens subsp. microphylla is a flowering shrub of the pea family (Fabaceae/Leguminaceae) found mainly in the Western Cape and Karoo regions of Southern Africa. Concoctions of various parts of the plant are used in the management of different ailments including T2DM. However, despite extensive biological and pharmacological studies, few analyses exist of the chemical constituents of S. frutescens and no Triple Time of Flight Liquid Chromatography with Mass Spectrometry (Triple TOF LC/MS/MS) analysis has been performed. The initial aim of this study was to investigate the phytochemical profile of hot aqueous, cold aqueous, 80% ethanolic, 100% ethanolic, 80% methanolic and 100% methanolic extracts of a single source S. frutescens plant material using colorimetric and spectrophotometric analysis. The hot aqueous extractant was found to be the best extractant for S. frutescens, yielding 1.99 g of crude extract from 16 g fresh powdered plant material. This data suggests that application of heat and water as the extractant (hot aqueous) could play a vital role in extraction of bioactive compounds from S. frutescens and also justifies the traditional use of a tea infusion of S. frutescens. Colorimetric analysis revealed the presence of flavonoids, flavonols, tannins, and phenols in all extracts with varying intensity. The organic extracts 100% methanol, 80% and 100% ethanol exhibited high color intensity (+++) for flavonoids and flavonols respectively, while all the extracts exhibited a moderate color intensity (++) for tannins and phenols. Spectrophotometric analysis of S. frutescens extracts revealed that all the organic extracts contained a significantly higher concentration (in mg/g of extract) of flavonols and tannins when compared to the aqueous extracts. All extracts contained approximately equal levels of phenols. These data confirm the presence of all four groups of bioactive phytocompounds in the S. frutescens extracts used in this study, and also confirm that different solvent extractants possess the capability to differentially extract specific groups of phytocompounds. in individual extracts. Further comparison of these compounds with online databases of anti-diabetic phytocompounds led to the preliminary identification of 10 possible anti-diabetic compounds; α-Pinene, Limonene, Sabinene, Carvone, Myricetin, Rutin, Stigmasterol, Emodin, Sarpagine and Hypoglycin B in crude and solid phase extraction (SPE) fractions of S. frutesecens. Furthermore, using two hepatic cell lines (Chang and HepG2) as an in-vtro model system, the anti-T2DM properties of crude aqueous and organic extracts of S. frutescents was investigated and compared. Both aqueous and organic extracts of S. frutescens were found to decrease gluconeogenesis, increase glucose uptake and decrease lipid accumulation (Triacylglycerol, Diacylglycerol, and Monoacylglycerol) in Chang and HepG2 hepatic cell cultures made insulin resistant (IR) following exposure to high concentration of insulin and fructose. Using real-time quantitative reverse transcriptase polymerase chain reaction (qRT-PCR), the aqueous and organic extracts of S. frutescens were confirmed to regulate the expression of Vesicle-associated membrane protein 3 (VAMP3), Mitogen-activated protein kinase 8 (MAPK8), and Insulin receptor substrate 1 (IRS1) in insulin resistant hepatic cells. IR-mediated downregulation of VAMP3, MAPK8, and IRS1 mRNA in IR HepG2 hepatic cell cultures was reversed in the presence of aqueous and organic extracts of S. frutescens. The hot aqueous extract displayed the highest activity in all the assays, while all the organic extracts displayed similar potency. In conclusion, this study reports that aqueous and organic extracts of S. frutescens possess numerous anti-diabetic compounds that can be further investigated for the development of new, more efficacious and less toxic anti-diabetic agents. The presence of multiple compounds in a single extract does suggest a synergistic or combinatorial therapeutic effect. These findings support the burgeoning body of in-vivo and in-vitro literature evidence on the anti-diabetic properties of S. frutescens and its use in folklore medicine.
- Full Text:
- Date Issued: 2016
Rhenium complexes with multidentate imine-, amine-, thione-, thiol-, hydroxy- and carboxamide chelates
- Authors: Habarurema, Gratien
- Date: 2016
- Subjects: Rhenium Metal complexes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12679 , vital:27106
- Description: This study entails the synthesis, spectroscopic and structural characterization of new rhenium complexes with multidentate imine-, amine-, thione-, thiol-, hydroxy- and carboxamide chelates in various oxidation states. Rhenium(I) and (V) complexes with imidazolidine, pyrimidine and bridging pyridyl derivatives are reported in Chapter 3. The reactions of the potential tridentate N,N,Odonor ligand 2,2'-dipyridylketone (dpk) with trans-[ReOCl3(PPh3)2], (n-Bu4N)[ReOCl4] and trans-[ReOI2(OEt)(PPh3)2] led to the isolation of cis-[ReOCl2(edpm)], cis-[ReOCl2(dpk.OH)] and [ReO3(dpk.OH)] respectively (see Scheme 1). The reaction of (E)-N-((pyridine-2-yl)methylene)benzo[d]thiazol-2-amine (pbt) with trans- [ReOCl3(PPh3)2] produced a mononuclear oxorhenium(V) complex cis- [ReOCl2(epm)(PPh3)]. Both dpk and pbt exhibited a nucleophilic attack by acetonitrile (for Hedpm), water (for dpk) and ethanol (for pbt) leading to chelates that act as uninegative tridentate N,N,O- and bidentate N,O-donor chelates respectively. The reaction of [Re(CO)5Cl] with 2,3-dihydro-2,2-di(pyridin-2-yl)-1H-benzo[d]imidazole (H2dpb), (2,6-diaza-cyclohex-1-enylolonium)2-aza-benzoate (H2den) and 2-(2-(pyridine-2-yl)imidazolidin-2-yl)pyridine (H2pip) (see Scheme 1) gave rise to novel rhenium(I) complexes fac-[Re(CO)3(H2dmb)Cl], fac-[Re(CO)3(Hhdm)] and fac-[Re(CO)3(H2pip)]Cl respectively. The monomeric cationic salt fac-[Re(CO)3(H2salbam)]Br and ligand-bridged dimer fac- (μ-H2salet)[Re(CO)3]2 complexes were formed by the reactions of [Re(CO)5X] (X = Br or Cl) with the potentially heptadentate Schiff base 2,2,2-tris (salicylideneimino)- triethylamine (H3salet; Scheme 2) respectively. The reactions of the potentially hexadentate ligands acting as tridentate monoanionic N,N,O- or N,O,O-donor chelates N1-(3-(2-hydroxy enzylideneamino) propylamino) ethyl)benzylidenepropane-1,3-diamine (H2salpd) and N,N -bis(salicylidene) -3,6-dioxa-1,8-diaminooctane (H2saldane) (Scheme 2) with [Re(CO)5Cl] led to the isolation of the mononuclear and dinuclear complexes fac-[Re(CO)3(Hsaldane)] and fac-(μ-salpd)[Re(CO)3]2 respectively. The reactions of [Re(CO)5Cl] with the tetradentate ligands 2-{[2-hydroxy-3-{[(E)-(2- hydroxyphenyl)-methylidene]amino}propyl)imino]methyl}phenol (H2hmp), 6-((6E)- ((3E)-3-((oxocyclohexa-2,4-dienyl)methyleneamino)-2-hydroxypropylimino)methyl)- cyclohexa-2,4-dienone (H2hcd.H2O) zwitterion and 2-((1E)-1-((E)-3-(2-hydoxyphenylmethylideneamino)propylimino)methyl)phenol (H2hdp) (see Scheme 2) resulted in the formation of the neutral fac-[Re(CO)3(Hamp)], fac-[Re(CO)3(Hhetp)] and fac- [Re(CO)3(Happ)] respectively. The treatment of 2-((3-(2-hydroxybenzylamino)-propylamino)methyl)phenol (H2hbp) with [Re(CO)3Cl] and trans-[ReOCl3(PPh3)2] gave the fac-[Re(CO)3(Hhbp)] and (μ-O)[ReO(hbp)]2 complexes. The reactions of the ligands H2hmp, H2hdp and H2hap (see Scheme 2) with trans-[ReOBr3(PPh3)2] and trans-[ReOI2(OEt)(PPh3)2] produced dinuclear oxo-bridged rhenium(V) complexes (μ-O)[ReO(hmp)]2, [(μ-O)[ReO(hdp)]2 and (μ-O)[ReO(hap)]2 respectively. The neutral and anionic binding modes of thiosemicarbazones to the fac-[Re(CO)3]+, cis- [ReO2]+ and trans-[ReO2]+ cores have been investigated in Chapter 6. The reactions of the potentially tridentate ligand 1-{1-(2- hydroxyphenyl)ethylidene}-4- phenylthiosemicarbazide (H2hpt) (see Scheme 3) with [Re(CO)5Cl], cis-[ReO2I(PPh3)2]cand trans-[ReO2(py)4]Cl led to the isolation of the complexes fac-[Re(CO)3(H2hpt)2]Cl, [Re(hipt)(Hipht)(PPh3)] and trans-[ReO(hpt)(Hhpt)] respectively. The X-ray crystal analysis of the complexes show that the ligand H2hpt exhibits decomposition, thiol-enol tautomerism and a thiolate-iminium zwitterionic process, and coordinates in the neutral form via its thione sulfur and nitrogen and anionic through the azo nitrogen, thiolate sulfur and acetophenolic oxygen. A series of nitrogen-heterocyclic amide-, acid-, thiol- and diol-based ligands as well as their related monomeric rhenium(III) and (V) complexes have also been studied (see Chapter 7). The reaction of N-(2-(pyrazine-2-carboxamido)phenyl)pyrazine-2- carboxamide (H2ppc) (Scheme 3) with trans-[ReOBr3(PPh3)2] yielded the complex trans- [ReBr2(Hppca)(PPh3)2]. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with pyridine-2,6-dicarboxylic acid (H2pda) produced the neutral oxorhenium(V) complexes [ReOX2(epca)(PPh3)]. The treatment of trans-[ReOBr3(PPh3)2] with 2-mercaptopyridine- 3-carboxylic acid (H2mpc) gave rise to the rhenium(III) complex [Re(empc)3(PPh3)]. The reaction of 2,6-bis(hydroxymethyl)pyridine (H2bhp) with trans-[ReOI2(EOt)(PPh3)2], trans-[ReOBr3(PPh3)2] and [Re(CO)5Cl] gave the complexes [ReO(Hbhp)2(PPh3)]I.PPh3, cis-[ReOBr2(Hbhp)(PPh3)] and fac-(μ- O)2[Re(CO)3(Hbhp)]2 respectively. Their X-ray crystal structures indicate that the ligand acts as a bidentate monoanionic N,O-donor chelate leaving a free aliphatic hydroxyl group.
- Full Text:
- Date Issued: 2016
- Authors: Habarurema, Gratien
- Date: 2016
- Subjects: Rhenium Metal complexes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12679 , vital:27106
- Description: This study entails the synthesis, spectroscopic and structural characterization of new rhenium complexes with multidentate imine-, amine-, thione-, thiol-, hydroxy- and carboxamide chelates in various oxidation states. Rhenium(I) and (V) complexes with imidazolidine, pyrimidine and bridging pyridyl derivatives are reported in Chapter 3. The reactions of the potential tridentate N,N,Odonor ligand 2,2'-dipyridylketone (dpk) with trans-[ReOCl3(PPh3)2], (n-Bu4N)[ReOCl4] and trans-[ReOI2(OEt)(PPh3)2] led to the isolation of cis-[ReOCl2(edpm)], cis-[ReOCl2(dpk.OH)] and [ReO3(dpk.OH)] respectively (see Scheme 1). The reaction of (E)-N-((pyridine-2-yl)methylene)benzo[d]thiazol-2-amine (pbt) with trans- [ReOCl3(PPh3)2] produced a mononuclear oxorhenium(V) complex cis- [ReOCl2(epm)(PPh3)]. Both dpk and pbt exhibited a nucleophilic attack by acetonitrile (for Hedpm), water (for dpk) and ethanol (for pbt) leading to chelates that act as uninegative tridentate N,N,O- and bidentate N,O-donor chelates respectively. The reaction of [Re(CO)5Cl] with 2,3-dihydro-2,2-di(pyridin-2-yl)-1H-benzo[d]imidazole (H2dpb), (2,6-diaza-cyclohex-1-enylolonium)2-aza-benzoate (H2den) and 2-(2-(pyridine-2-yl)imidazolidin-2-yl)pyridine (H2pip) (see Scheme 1) gave rise to novel rhenium(I) complexes fac-[Re(CO)3(H2dmb)Cl], fac-[Re(CO)3(Hhdm)] and fac-[Re(CO)3(H2pip)]Cl respectively. The monomeric cationic salt fac-[Re(CO)3(H2salbam)]Br and ligand-bridged dimer fac- (μ-H2salet)[Re(CO)3]2 complexes were formed by the reactions of [Re(CO)5X] (X = Br or Cl) with the potentially heptadentate Schiff base 2,2,2-tris (salicylideneimino)- triethylamine (H3salet; Scheme 2) respectively. The reactions of the potentially hexadentate ligands acting as tridentate monoanionic N,N,O- or N,O,O-donor chelates N1-(3-(2-hydroxy enzylideneamino) propylamino) ethyl)benzylidenepropane-1,3-diamine (H2salpd) and N,N -bis(salicylidene) -3,6-dioxa-1,8-diaminooctane (H2saldane) (Scheme 2) with [Re(CO)5Cl] led to the isolation of the mononuclear and dinuclear complexes fac-[Re(CO)3(Hsaldane)] and fac-(μ-salpd)[Re(CO)3]2 respectively. The reactions of [Re(CO)5Cl] with the tetradentate ligands 2-{[2-hydroxy-3-{[(E)-(2- hydroxyphenyl)-methylidene]amino}propyl)imino]methyl}phenol (H2hmp), 6-((6E)- ((3E)-3-((oxocyclohexa-2,4-dienyl)methyleneamino)-2-hydroxypropylimino)methyl)- cyclohexa-2,4-dienone (H2hcd.H2O) zwitterion and 2-((1E)-1-((E)-3-(2-hydoxyphenylmethylideneamino)propylimino)methyl)phenol (H2hdp) (see Scheme 2) resulted in the formation of the neutral fac-[Re(CO)3(Hamp)], fac-[Re(CO)3(Hhetp)] and fac- [Re(CO)3(Happ)] respectively. The treatment of 2-((3-(2-hydroxybenzylamino)-propylamino)methyl)phenol (H2hbp) with [Re(CO)3Cl] and trans-[ReOCl3(PPh3)2] gave the fac-[Re(CO)3(Hhbp)] and (μ-O)[ReO(hbp)]2 complexes. The reactions of the ligands H2hmp, H2hdp and H2hap (see Scheme 2) with trans-[ReOBr3(PPh3)2] and trans-[ReOI2(OEt)(PPh3)2] produced dinuclear oxo-bridged rhenium(V) complexes (μ-O)[ReO(hmp)]2, [(μ-O)[ReO(hdp)]2 and (μ-O)[ReO(hap)]2 respectively. The neutral and anionic binding modes of thiosemicarbazones to the fac-[Re(CO)3]+, cis- [ReO2]+ and trans-[ReO2]+ cores have been investigated in Chapter 6. The reactions of the potentially tridentate ligand 1-{1-(2- hydroxyphenyl)ethylidene}-4- phenylthiosemicarbazide (H2hpt) (see Scheme 3) with [Re(CO)5Cl], cis-[ReO2I(PPh3)2]cand trans-[ReO2(py)4]Cl led to the isolation of the complexes fac-[Re(CO)3(H2hpt)2]Cl, [Re(hipt)(Hipht)(PPh3)] and trans-[ReO(hpt)(Hhpt)] respectively. The X-ray crystal analysis of the complexes show that the ligand H2hpt exhibits decomposition, thiol-enol tautomerism and a thiolate-iminium zwitterionic process, and coordinates in the neutral form via its thione sulfur and nitrogen and anionic through the azo nitrogen, thiolate sulfur and acetophenolic oxygen. A series of nitrogen-heterocyclic amide-, acid-, thiol- and diol-based ligands as well as their related monomeric rhenium(III) and (V) complexes have also been studied (see Chapter 7). The reaction of N-(2-(pyrazine-2-carboxamido)phenyl)pyrazine-2- carboxamide (H2ppc) (Scheme 3) with trans-[ReOBr3(PPh3)2] yielded the complex trans- [ReBr2(Hppca)(PPh3)2]. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with pyridine-2,6-dicarboxylic acid (H2pda) produced the neutral oxorhenium(V) complexes [ReOX2(epca)(PPh3)]. The treatment of trans-[ReOBr3(PPh3)2] with 2-mercaptopyridine- 3-carboxylic acid (H2mpc) gave rise to the rhenium(III) complex [Re(empc)3(PPh3)]. The reaction of 2,6-bis(hydroxymethyl)pyridine (H2bhp) with trans-[ReOI2(EOt)(PPh3)2], trans-[ReOBr3(PPh3)2] and [Re(CO)5Cl] gave the complexes [ReO(Hbhp)2(PPh3)]I.PPh3, cis-[ReOBr2(Hbhp)(PPh3)] and fac-(μ- O)2[Re(CO)3(Hbhp)]2 respectively. Their X-ray crystal structures indicate that the ligand acts as a bidentate monoanionic N,O-donor chelate leaving a free aliphatic hydroxyl group.
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- Date Issued: 2016
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