Cytokine properties of CD23 on human Eosinophilic cells
- Authors: Ferreira, Lauren
- Date: 2007
- Subjects: Cytokines , CD23 antigen , Eosinophil
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10333 , http://hdl.handle.net/10948/503 , http://hdl.handle.net/10948/d1012001 , Cytokines , CD23 antigen , Eosinophil
- Description: CD23, the low affinity IgE receptor, is expressed by various cell types and has numerous functions depending on the form of the protein, its interaction with various ligands and the type of cell involved. CD23 is pivotal in the regulation of IgE, with the soluble form involved in up-regulation, while the membrane bound form is involved in the down-regulation. It is clear why it is believed to be a central molecule in allergic responses, and a therapeutic target for the treatment of allergic disease. In this study a recombinant form of the entire extracellular domain of the protein, exCD23, was produced by PCR cloning and expressed in E. coli. His•Tag™s were introduced onto the C-terminus and N-terminus, respectively, in order to simplify the purification procedure. After renaturation and purification, the recombinant exCD23 bound IgE, indicating its activity. From the IgE binding studies it was established that the position of the tag did not influence the binding. GST•Tagged™ exCD23 was also produced in an attempt to increase the solubility of the recombinant protein, but this proved unsuccessful. Butyrate differentiated EoL-1 cells were treated with the Nterminal His•Tagged™ exCD23, and the protein appeared to suppress the secretion of the constitutively expressed cytokines, especially IL-8 and IFN- , when compared to untreated cells. In addition, treatment of the EoL-1 cells with exCD23 had a significant proliferative effect, but could not induce differentiation of this cell line into mature eosinophilic-like cells.
- Full Text:
- Date Issued: 2007
- Authors: Ferreira, Lauren
- Date: 2007
- Subjects: Cytokines , CD23 antigen , Eosinophil
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10333 , http://hdl.handle.net/10948/503 , http://hdl.handle.net/10948/d1012001 , Cytokines , CD23 antigen , Eosinophil
- Description: CD23, the low affinity IgE receptor, is expressed by various cell types and has numerous functions depending on the form of the protein, its interaction with various ligands and the type of cell involved. CD23 is pivotal in the regulation of IgE, with the soluble form involved in up-regulation, while the membrane bound form is involved in the down-regulation. It is clear why it is believed to be a central molecule in allergic responses, and a therapeutic target for the treatment of allergic disease. In this study a recombinant form of the entire extracellular domain of the protein, exCD23, was produced by PCR cloning and expressed in E. coli. His•Tag™s were introduced onto the C-terminus and N-terminus, respectively, in order to simplify the purification procedure. After renaturation and purification, the recombinant exCD23 bound IgE, indicating its activity. From the IgE binding studies it was established that the position of the tag did not influence the binding. GST•Tagged™ exCD23 was also produced in an attempt to increase the solubility of the recombinant protein, but this proved unsuccessful. Butyrate differentiated EoL-1 cells were treated with the Nterminal His•Tagged™ exCD23, and the protein appeared to suppress the secretion of the constitutively expressed cytokines, especially IL-8 and IFN- , when compared to untreated cells. In addition, treatment of the EoL-1 cells with exCD23 had a significant proliferative effect, but could not induce differentiation of this cell line into mature eosinophilic-like cells.
- Full Text:
- Date Issued: 2007
Rehabilitation of the Orange River Mouth Salt Marsh : seed, wind and sediment characteristics
- Authors: Shaw, Gregory Alan
- Date: 2007
- Subjects: Salt marshes -- Orange River , Rivers -- South Africa -- Environmental aspects , Orange River -- Ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10626 , http://hdl.handle.net/10948/603 , http://hdl.handle.net/10948/d1012010 , Salt marshes -- Orange River , Rivers -- South Africa -- Environmental aspects , Orange River -- Ecology
- Description: The Orange River is an important source of freshwater and like many other wetlands in semi-arid regions, supports various social (Spurgeon, 1998), economic (Spurgeon, 1998; Bornman et al., 2005) and ecological functions. The saltmarsh at the Orange River Mouth has become degraded over time following numerous anthropogenic impacts. As a result the Transboundary RAMSAR site was placed on the Montreux record emphasising the importance for rehabilitation. The potential of the marsh for natural rehabilitation was assessed through three physical factors which were considered to have the most influence on the saltmarsh i.e. 1) sediment 2) water 3) wind. Three sampling areas were chosen to investigate the sediment characteristics of the ORM saltmarsh and the suitability for seed germination and adult survival. Site A was representative of the general marsh area, Site B was thought to have favourable sediment conditions for saltmarsh growth because of the large numbers of seedlings and Site C was prone to inundation by wind blown sediment. The sites were sampled in 2005 (dry conditions) and in 2006 after high rainfall and river flooding. Electrical conductivity (EC) of the sediment throughout the marsh was hypersaline in many instances above the tolerance range for S. pillansii (> 80 mS.cm-1) The freshwater event in 2006 lowered salinity significantly in two of the three sites. Differences in sediment characteristics were also compared for three habitats i.e. driftlines, open sites and under vegetation. Driftlines (C. coronopifolia = 872 seedlings m-2; S. pillansii = 1296 seedlings m-2) and the microhabitat associated with adult plants (C. coronopifolia = 803 seedlings m-2; S. pillansii = 721 seedlings m-2) created favourable conditions for seedling growth, however open unvegetated (C. coronopifolia = 56 seedlings m-2; S. pillansii = 49 seedlings m-2) areas had significantly lower seedling density. Due to the marsh currently being in a desertified state this study aimed to establish whether the remaining vegetation could produce enough seed to revegetate the marsh. Laboratory studies indicated that seeds of both species germinated best in freshwater (0 psu). The germination of S. pillansii seeds was 40 percent at 0 psu compared to 5 percent at 35 psu. After storage under hypersaline conditions (35 psu) C. coronopifolia showed 100 percent seed germination when returned to freshwater whereas storage at 70 psu decreased the viability of S. pillansii seeds. The plants are producing adequate seed that will allow for regrowth and rehabilitation if sediment and groundwater characteristics are suitable for seed germination, seedling growth and adult survival. However the increase in bare areas at the Orange River mouth as a result of salt marsh dieback has increased the available sediment source. The wind blown sediment has covered large areas of the remaining adult salt marsh vegetation, particularly in the northern corner at Site C, causing further die-back.
- Full Text:
- Date Issued: 2007
- Authors: Shaw, Gregory Alan
- Date: 2007
- Subjects: Salt marshes -- Orange River , Rivers -- South Africa -- Environmental aspects , Orange River -- Ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10626 , http://hdl.handle.net/10948/603 , http://hdl.handle.net/10948/d1012010 , Salt marshes -- Orange River , Rivers -- South Africa -- Environmental aspects , Orange River -- Ecology
- Description: The Orange River is an important source of freshwater and like many other wetlands in semi-arid regions, supports various social (Spurgeon, 1998), economic (Spurgeon, 1998; Bornman et al., 2005) and ecological functions. The saltmarsh at the Orange River Mouth has become degraded over time following numerous anthropogenic impacts. As a result the Transboundary RAMSAR site was placed on the Montreux record emphasising the importance for rehabilitation. The potential of the marsh for natural rehabilitation was assessed through three physical factors which were considered to have the most influence on the saltmarsh i.e. 1) sediment 2) water 3) wind. Three sampling areas were chosen to investigate the sediment characteristics of the ORM saltmarsh and the suitability for seed germination and adult survival. Site A was representative of the general marsh area, Site B was thought to have favourable sediment conditions for saltmarsh growth because of the large numbers of seedlings and Site C was prone to inundation by wind blown sediment. The sites were sampled in 2005 (dry conditions) and in 2006 after high rainfall and river flooding. Electrical conductivity (EC) of the sediment throughout the marsh was hypersaline in many instances above the tolerance range for S. pillansii (> 80 mS.cm-1) The freshwater event in 2006 lowered salinity significantly in two of the three sites. Differences in sediment characteristics were also compared for three habitats i.e. driftlines, open sites and under vegetation. Driftlines (C. coronopifolia = 872 seedlings m-2; S. pillansii = 1296 seedlings m-2) and the microhabitat associated with adult plants (C. coronopifolia = 803 seedlings m-2; S. pillansii = 721 seedlings m-2) created favourable conditions for seedling growth, however open unvegetated (C. coronopifolia = 56 seedlings m-2; S. pillansii = 49 seedlings m-2) areas had significantly lower seedling density. Due to the marsh currently being in a desertified state this study aimed to establish whether the remaining vegetation could produce enough seed to revegetate the marsh. Laboratory studies indicated that seeds of both species germinated best in freshwater (0 psu). The germination of S. pillansii seeds was 40 percent at 0 psu compared to 5 percent at 35 psu. After storage under hypersaline conditions (35 psu) C. coronopifolia showed 100 percent seed germination when returned to freshwater whereas storage at 70 psu decreased the viability of S. pillansii seeds. The plants are producing adequate seed that will allow for regrowth and rehabilitation if sediment and groundwater characteristics are suitable for seed germination, seedling growth and adult survival. However the increase in bare areas at the Orange River mouth as a result of salt marsh dieback has increased the available sediment source. The wind blown sediment has covered large areas of the remaining adult salt marsh vegetation, particularly in the northern corner at Site C, causing further die-back.
- Full Text:
- Date Issued: 2007
The evaluation of a pedagogical-program development environment for Novice programmers : a comparative study
- Authors: Vogts, Dieter
- Date: 2007
- Subjects: Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10477 , http://hdl.handle.net/10948/638 , Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Description: It is an acknowledged fact that many novice programmers experience difficulty in the process of learning to program. One of the contributing factors to this difficulty is the Program Development Environment (PDE). Professional-PDEs are those developed specifically for professional programmers, but are often used by educational institutions in the instruction of programming. It has long been accepted that such environments are inappropriate in the instruction of programming due to unnecessary complexity and lack of support for novice programmers in the learning process. Numerous pedagogical-PDEs supporting the mechanics of programming have been developed in response to this. A review of literature, however, indicates that very limited empirical studies comparing pedagogical-PDEs and professional-PDEs have been conducted. The current study investigates whether there are measurable benefits to using a pedagogical-PDE supporting the mechanics of programming in the instruction of programming instead of a professional-PDE. A comparative study of this nature requires a representative pedagogical-PDE and representative professional-PDE be compared with one another. The first part of the current study determines a set of requirements that a pedagogical- PDE should adhere to based on literature. A set of representative features for a pedagogical-PDE is derived by examining the features of existing PDEs in conjunction with the set of requirements. Based on these features, a pedagogical-PDE, known as SimplifIDE, is developed that implements the representative set of features and that meets are the requirements for a pedagogical-PDE. The second part of the current study is the specification and administration of an empirical experiment in which SimplifIDE and Borland© DelphiTM are compared with one another. A holistic approach in determining the differences between the PDEs is taken and three main areas are examined, namely academic performance, perceptions and programming behavior.
- Full Text:
- Date Issued: 2007
- Authors: Vogts, Dieter
- Date: 2007
- Subjects: Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10477 , http://hdl.handle.net/10948/638 , Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Description: It is an acknowledged fact that many novice programmers experience difficulty in the process of learning to program. One of the contributing factors to this difficulty is the Program Development Environment (PDE). Professional-PDEs are those developed specifically for professional programmers, but are often used by educational institutions in the instruction of programming. It has long been accepted that such environments are inappropriate in the instruction of programming due to unnecessary complexity and lack of support for novice programmers in the learning process. Numerous pedagogical-PDEs supporting the mechanics of programming have been developed in response to this. A review of literature, however, indicates that very limited empirical studies comparing pedagogical-PDEs and professional-PDEs have been conducted. The current study investigates whether there are measurable benefits to using a pedagogical-PDE supporting the mechanics of programming in the instruction of programming instead of a professional-PDE. A comparative study of this nature requires a representative pedagogical-PDE and representative professional-PDE be compared with one another. The first part of the current study determines a set of requirements that a pedagogical- PDE should adhere to based on literature. A set of representative features for a pedagogical-PDE is derived by examining the features of existing PDEs in conjunction with the set of requirements. Based on these features, a pedagogical-PDE, known as SimplifIDE, is developed that implements the representative set of features and that meets are the requirements for a pedagogical-PDE. The second part of the current study is the specification and administration of an empirical experiment in which SimplifIDE and Borland© DelphiTM are compared with one another. A holistic approach in determining the differences between the PDEs is taken and three main areas are examined, namely academic performance, perceptions and programming behavior.
- Full Text:
- Date Issued: 2007
A comparison between the game and hunting industries in KwaZulu-Natal and the Eastern Cape
- Authors: Kobus, Louann
- Date: 2007
- Subjects: Big game hunting -- South Africa -- KwaZulu-Natal , Big game hunting -- South Africa -- Eastern Cape , Hunting -- South Africa -- KwaZulu-Natal , Hunting -- South Africa -- Eastern Cape , Game farms -- South Africa -- KwaZulu-Natal , Game farms -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10590 , http://hdl.handle.net/10948/534 , http://hdl.handle.net/10948/d1011724 , Big game hunting -- South Africa -- KwaZulu-Natal , Big game hunting -- South Africa -- Eastern Cape , Hunting -- South Africa -- KwaZulu-Natal , Hunting -- South Africa -- Eastern Cape , Game farms -- South Africa -- KwaZulu-Natal , Game farms -- South Africa -- Eastern Cape
- Description: The objectives of this research, were to investigate the characteristics and develop a profile of the game and hunting industries of KwaZulu-Natal, and to undertake a comparison between the game and hunting industries in KwaZulu-Natal and the Eastern Cape. The comparative part of this study was completed using results obtained from a study done in 2002 in the Eastern Cape (van Niekerk, 2002). The main farming activities in KwaZulu-Natal are large livestock production and sugar cane production. In recent years, private landowners in KwaZulu-Natal have undergone a transition from livestock production to game ranching due to the problems faced and the cost implications of the HIV epidemic, stock theft, difficulties faced with changes in the labour laws and the increasing number of land claims against farmers. Although the game and hunting industries are relatively young industries in KwaZulu-Natal they contribute significantly to the economy of the province. Not only is greater conservation of the biodiversity more effective in game ranching but it is also proving to yield great economic returns. The increase in game ranching in recent years is namely due to the monetary value placed on wildlife, the increased value in ecotourism and its value as an earner of foreign exchange, less dependency on unskilled labour than that of livestock farming and lower rates of animal loss through theft compared to that of livestock farming. In KwaZulu-Natal game numbers indicate that impala have the greatest population amongst the respondents, followed by nyala, blesbok, common reedbuck, kudu and blue wildebeest, whilst other game species occur in smaller numbers. Respondents in KwaZulu-Natal indicate that nyala is the largest economic earner for them followed by buffalo, whereas in the Eastern Cape (2002), kudu and springbok provide the greatest income for the province. In KwaZulu-Natal income generated from hunting is second to that of live game sales compared to the Eastern Cape (2002) where hunting is the most important form of game utilisation in terms of income generated. At the time of this study, respondents in KwaZulu-Natal reported an income of R 15 382 397 generated from live sales and R 13 561 459 from hunting. These respondents also indicated that the total value of game utilised annually was in excess of R 30 million. Although game utilisation is occurring on a sustainable basis, there is room for greater utilisation of some game species which, if undertaken correctly, can increase the revenue for the province significantly and also contribute positively to further sustainability of the game populations. KwaZulu-Natal’s competitive advantage is derived from the fact that there is an abundance of game on the ranches, quality trophy animals are available, the number of game species available for hunting and quality of service rendered to hunters by the professional hunters and ranch owners. This study has clearly shown that there is a need for further investigation into the game and hunting industries in KwaZulu-Natal.
- Full Text:
- Date Issued: 2007
- Authors: Kobus, Louann
- Date: 2007
- Subjects: Big game hunting -- South Africa -- KwaZulu-Natal , Big game hunting -- South Africa -- Eastern Cape , Hunting -- South Africa -- KwaZulu-Natal , Hunting -- South Africa -- Eastern Cape , Game farms -- South Africa -- KwaZulu-Natal , Game farms -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10590 , http://hdl.handle.net/10948/534 , http://hdl.handle.net/10948/d1011724 , Big game hunting -- South Africa -- KwaZulu-Natal , Big game hunting -- South Africa -- Eastern Cape , Hunting -- South Africa -- KwaZulu-Natal , Hunting -- South Africa -- Eastern Cape , Game farms -- South Africa -- KwaZulu-Natal , Game farms -- South Africa -- Eastern Cape
- Description: The objectives of this research, were to investigate the characteristics and develop a profile of the game and hunting industries of KwaZulu-Natal, and to undertake a comparison between the game and hunting industries in KwaZulu-Natal and the Eastern Cape. The comparative part of this study was completed using results obtained from a study done in 2002 in the Eastern Cape (van Niekerk, 2002). The main farming activities in KwaZulu-Natal are large livestock production and sugar cane production. In recent years, private landowners in KwaZulu-Natal have undergone a transition from livestock production to game ranching due to the problems faced and the cost implications of the HIV epidemic, stock theft, difficulties faced with changes in the labour laws and the increasing number of land claims against farmers. Although the game and hunting industries are relatively young industries in KwaZulu-Natal they contribute significantly to the economy of the province. Not only is greater conservation of the biodiversity more effective in game ranching but it is also proving to yield great economic returns. The increase in game ranching in recent years is namely due to the monetary value placed on wildlife, the increased value in ecotourism and its value as an earner of foreign exchange, less dependency on unskilled labour than that of livestock farming and lower rates of animal loss through theft compared to that of livestock farming. In KwaZulu-Natal game numbers indicate that impala have the greatest population amongst the respondents, followed by nyala, blesbok, common reedbuck, kudu and blue wildebeest, whilst other game species occur in smaller numbers. Respondents in KwaZulu-Natal indicate that nyala is the largest economic earner for them followed by buffalo, whereas in the Eastern Cape (2002), kudu and springbok provide the greatest income for the province. In KwaZulu-Natal income generated from hunting is second to that of live game sales compared to the Eastern Cape (2002) where hunting is the most important form of game utilisation in terms of income generated. At the time of this study, respondents in KwaZulu-Natal reported an income of R 15 382 397 generated from live sales and R 13 561 459 from hunting. These respondents also indicated that the total value of game utilised annually was in excess of R 30 million. Although game utilisation is occurring on a sustainable basis, there is room for greater utilisation of some game species which, if undertaken correctly, can increase the revenue for the province significantly and also contribute positively to further sustainability of the game populations. KwaZulu-Natal’s competitive advantage is derived from the fact that there is an abundance of game on the ranches, quality trophy animals are available, the number of game species available for hunting and quality of service rendered to hunters by the professional hunters and ranch owners. This study has clearly shown that there is a need for further investigation into the game and hunting industries in KwaZulu-Natal.
- Full Text:
- Date Issued: 2007
Contributions to the use of microalgae in estuarine freshwater reserve determinations
- Authors: Snow, Gavin Charles
- Date: 2007
- Subjects: Microalgae -- South Africa , Estuarine ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10620 , http://hdl.handle.net/10948/709 , Microalgae -- South Africa , Estuarine ecology -- South Africa
- Description: The ecologist Garrett Hardin (1968) introduced a useful concept called the tragedy of the commons, which describes how ecological resources become threatened or lost. The term “commons” is based on the commons of old English villages and is symbolic of a resource that is shared by a group of people. If every person were to use each resource in a sustainable fashion it would be available in perpetuity. However, if people use more than their share they would only increase their personal wealth to the detriment of others. In addition, an increase in the population would mean that the size of each share would have to decrease to accommodate the larger number of people. As a result, resources are threatened by personal greed and uncontrolled population growth. Freshwater is an example of a common resource that is under threat in South Africa where the average annual rainfall is less than 60 percent of the global average (Mukheibir & Sparks 2006). The increasing demands for freshwater as well as its eutrophication are major concerns with regards to estuarine health, environmental resource management and human health. The correct management of water is necessary to ensure that it is utilised in a sustainable manner. The National Water Act (No. 36 of 1998) has provided the rights to water for basic human needs and for sustainable ecological function; the Basic Human Needs Reserve and Ecological Reserve are both provided as a right in law. The amount of water necessary for an estuary to retain an acceptable ecological status, known as the Estuarine Ecological Reserve, is determined through the implementation of procedures (rapid, intermediate or comprehensive) compiled by the Department of Water Affairs and Forestry (1999) in its Resource Directed Measures (RDM) for the Protection of Water Resources. The impact of restricted flow on estuaries can be reduced by manipulating the water released from impoundments, the regulation of water abstractions within the river catchment or both (Hirji et al. 2002). The reserve assessment method is designed to evaluate ecosystem requirements by employing groups of specialists from different disciplines. In South Africa, this includes hydrologists, sedimentologists, water chemists and biologists (including microalgae specialists). The use of microalgae in ecological assessments has largely been based on research that was initiated at the Nelson Mandela Metropolitan University (formerly University of Port Elizabeth) and subsequently at Rhodes University (Grahamstown) and the University of KwaZulu Natal (Durban). The microalgal research can be divided into two main focus areas; phytoplankton and benthic microalgae
- Full Text:
- Date Issued: 2007
- Authors: Snow, Gavin Charles
- Date: 2007
- Subjects: Microalgae -- South Africa , Estuarine ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10620 , http://hdl.handle.net/10948/709 , Microalgae -- South Africa , Estuarine ecology -- South Africa
- Description: The ecologist Garrett Hardin (1968) introduced a useful concept called the tragedy of the commons, which describes how ecological resources become threatened or lost. The term “commons” is based on the commons of old English villages and is symbolic of a resource that is shared by a group of people. If every person were to use each resource in a sustainable fashion it would be available in perpetuity. However, if people use more than their share they would only increase their personal wealth to the detriment of others. In addition, an increase in the population would mean that the size of each share would have to decrease to accommodate the larger number of people. As a result, resources are threatened by personal greed and uncontrolled population growth. Freshwater is an example of a common resource that is under threat in South Africa where the average annual rainfall is less than 60 percent of the global average (Mukheibir & Sparks 2006). The increasing demands for freshwater as well as its eutrophication are major concerns with regards to estuarine health, environmental resource management and human health. The correct management of water is necessary to ensure that it is utilised in a sustainable manner. The National Water Act (No. 36 of 1998) has provided the rights to water for basic human needs and for sustainable ecological function; the Basic Human Needs Reserve and Ecological Reserve are both provided as a right in law. The amount of water necessary for an estuary to retain an acceptable ecological status, known as the Estuarine Ecological Reserve, is determined through the implementation of procedures (rapid, intermediate or comprehensive) compiled by the Department of Water Affairs and Forestry (1999) in its Resource Directed Measures (RDM) for the Protection of Water Resources. The impact of restricted flow on estuaries can be reduced by manipulating the water released from impoundments, the regulation of water abstractions within the river catchment or both (Hirji et al. 2002). The reserve assessment method is designed to evaluate ecosystem requirements by employing groups of specialists from different disciplines. In South Africa, this includes hydrologists, sedimentologists, water chemists and biologists (including microalgae specialists). The use of microalgae in ecological assessments has largely been based on research that was initiated at the Nelson Mandela Metropolitan University (formerly University of Port Elizabeth) and subsequently at Rhodes University (Grahamstown) and the University of KwaZulu Natal (Durban). The microalgal research can be divided into two main focus areas; phytoplankton and benthic microalgae
- Full Text:
- Date Issued: 2007
An analysis of the influence of phosphorus poisoning on the exhaust emission after treatement systems of light-duty diesel vehicles
- Authors: Toral del Rio, Maria Isabel
- Date: 2007
- Subjects: Diesel motor -- Alternative fuels , Automobiles -- Pollution control devices , Automobiles -- Motors -- Exhaust gas , Motor fuels
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10405 , http://hdl.handle.net/10948/697 , Diesel motor -- Alternative fuels , Automobiles -- Pollution control devices , Automobiles -- Motors -- Exhaust gas , Motor fuels
- Description: Climate change has become a discussion topic of exponentially increasing urgency and importance amoung world leaders of all disciplines. These changes are brought about by the emission of so-called Greenhouse gases from various human activities. The primary cause of CO2 emissions is the burning of the Earth’s supply of nonrenewable natural fossil fuels like coal, oil and natural gas. The world first agreed on the prevention of “dangerous” climatic changes at the Earth Summit in 1992. The Kyoto Protocol of 1997 was the first step toward protection of the atmosphere and prescribes restrictions on emission pollutants. Since then the vehicle gas emissions are being controlled by means of different gas emissions norms, like the European Union Norm in Europe. The automotive manufacturers and suppliers are collectively working on reducing overall vehicle emissions. They are focusing on several different emission limiting possibilities, for example improved engine design, special fuel development and exhaust gas treatment systems. The exhaust gas treatment process requires continuous controlling and management of the exhaust gas emissions while driving a vehicle. Certain factors such as high emission temperatures have a negative influence on the life span of these systems. Their functionality and durability is also known to be reduced by the presence of chemical poisoning species like sulphur, phosphorus, zinc and calcium. The chemical poisoning species are produced during combustion of fuel and engine oil. They are therefore contained in the exhaust emissions and can poison the catalyst when passing over it. Phosphorous poisoning is particularly problematic and should be reduced considerably. This study involves the investigation of the phosphorous poisoning process and aims to provide clarity regarding the influences of different fuel and oil compositions on the severity of the process. Engine oil and biodiesel are two major sources of phosphorous poisoning. The phosphorus contained in biodiesel fuel is a natural component and can be minimized during the refining procedure. In contrast to others studies, the biodiesel fuel used during this project was SME (Soya Methyl Ester) with a 20% biodiesel content. This choice of fuel was made because of the increasingly important role that this type of biodiesel is playing in the European market and the future tendency to increase the percentage of biodiesel in the mixture with standard diesel fuel. The phosphorus contained in engine oil is a necessary additive to retain the antioxidant and anti-wear properties of the oil. This study examined the poisoning influences from the most commonly used phosphorus containing oil additive, Zinc Dithiophosphates (ZDDP), as well as a Zn-free, phosphorus containing anti-wear oil additive. This formulation provides information about the phosphorus poisoning process as caused by the engine oil in the absence of Zn in the oil additives. The results show how the phosphorus content in biodiesel fuel affects the functionality of the exhaust gas treatment systems and the importance of reducing the permitted content of phosphorus contained in the fuel. Reducing the phosphorus content in the fuel will conserve the functionality of the exhaust gas treatment systems during their operational life and thereby protect the environmental from emission pollutants. It also provides insight into the differences in the poisoning processes when the phosphorus deposited on the catalyst comes from biodiesel fuel and when it comes from the engine oil. Finally the results also illustrate the influence of different phosphorous forms contained in engine oil additives on the catalyst poisoning process. This information could be used for the development of new oil additive formulations.
- Full Text:
- Date Issued: 2007
- Authors: Toral del Rio, Maria Isabel
- Date: 2007
- Subjects: Diesel motor -- Alternative fuels , Automobiles -- Pollution control devices , Automobiles -- Motors -- Exhaust gas , Motor fuels
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10405 , http://hdl.handle.net/10948/697 , Diesel motor -- Alternative fuels , Automobiles -- Pollution control devices , Automobiles -- Motors -- Exhaust gas , Motor fuels
- Description: Climate change has become a discussion topic of exponentially increasing urgency and importance amoung world leaders of all disciplines. These changes are brought about by the emission of so-called Greenhouse gases from various human activities. The primary cause of CO2 emissions is the burning of the Earth’s supply of nonrenewable natural fossil fuels like coal, oil and natural gas. The world first agreed on the prevention of “dangerous” climatic changes at the Earth Summit in 1992. The Kyoto Protocol of 1997 was the first step toward protection of the atmosphere and prescribes restrictions on emission pollutants. Since then the vehicle gas emissions are being controlled by means of different gas emissions norms, like the European Union Norm in Europe. The automotive manufacturers and suppliers are collectively working on reducing overall vehicle emissions. They are focusing on several different emission limiting possibilities, for example improved engine design, special fuel development and exhaust gas treatment systems. The exhaust gas treatment process requires continuous controlling and management of the exhaust gas emissions while driving a vehicle. Certain factors such as high emission temperatures have a negative influence on the life span of these systems. Their functionality and durability is also known to be reduced by the presence of chemical poisoning species like sulphur, phosphorus, zinc and calcium. The chemical poisoning species are produced during combustion of fuel and engine oil. They are therefore contained in the exhaust emissions and can poison the catalyst when passing over it. Phosphorous poisoning is particularly problematic and should be reduced considerably. This study involves the investigation of the phosphorous poisoning process and aims to provide clarity regarding the influences of different fuel and oil compositions on the severity of the process. Engine oil and biodiesel are two major sources of phosphorous poisoning. The phosphorus contained in biodiesel fuel is a natural component and can be minimized during the refining procedure. In contrast to others studies, the biodiesel fuel used during this project was SME (Soya Methyl Ester) with a 20% biodiesel content. This choice of fuel was made because of the increasingly important role that this type of biodiesel is playing in the European market and the future tendency to increase the percentage of biodiesel in the mixture with standard diesel fuel. The phosphorus contained in engine oil is a necessary additive to retain the antioxidant and anti-wear properties of the oil. This study examined the poisoning influences from the most commonly used phosphorus containing oil additive, Zinc Dithiophosphates (ZDDP), as well as a Zn-free, phosphorus containing anti-wear oil additive. This formulation provides information about the phosphorus poisoning process as caused by the engine oil in the absence of Zn in the oil additives. The results show how the phosphorus content in biodiesel fuel affects the functionality of the exhaust gas treatment systems and the importance of reducing the permitted content of phosphorus contained in the fuel. Reducing the phosphorus content in the fuel will conserve the functionality of the exhaust gas treatment systems during their operational life and thereby protect the environmental from emission pollutants. It also provides insight into the differences in the poisoning processes when the phosphorus deposited on the catalyst comes from biodiesel fuel and when it comes from the engine oil. Finally the results also illustrate the influence of different phosphorous forms contained in engine oil additives on the catalyst poisoning process. This information could be used for the development of new oil additive formulations.
- Full Text:
- Date Issued: 2007
Ionic liquids as media for electro-organic synthesis
- Authors: Kruger, Elna
- Date: 2007
- Subjects: Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10413 , http://hdl.handle.net/10948/538 , Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Description: The IL’s used in this study were either synthesized or commercially available. Preparation of the IL’s involved 2 step processes: firstly the heating of distilled 1-methylimidazole with distilled 1-chlorobutane under reflux to obtain 1-butyl-3- methylimidazolium chloride; secondly, the metathesis reaction of sodium tetrafluoroborate with 1-butyl-3-methylimidazolium chloride to obtain 1-butyl-3- methylimidazolium tetrafluoroborate. The addition of sodium tetrafluoroborate, sodium hexafluorophosphate and lithium trifluoromethane sulfonamide with 1-butyl-3-methylimidazolium chloride produced good yields of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide respectively. The IL’s are hygroscopic and must be stored under a nitrogen atmosphere. The IL’s were analyzed using 1H and 13C NMR analysis with CDCl3 as solvent. The physical and chemical properties of these IL’s were compared to commercial products. The physical and chemical properties compared well to reference values from the literature. The physical properties measured include the density, conductivity and electrochemical window. The electrochemical window is dependant primarily on the resistance of the cation to reduction and the resistance of the anion to oxidation. The electrochemical windows of the IL’s were very similar to the reference windows obtained from literature and it can be seen that some IL’s have a slightly lower window which can be due to water present. Water content in the IL’s was determined with the use of a Karl Fischer titrator, with Hydranal 5 Composite as titrant and HPLC grade methanol as the base. The concentration of halide in the IL’s was determined with a Perkin-Elmer ICP-MS.
- Full Text:
- Date Issued: 2007
- Authors: Kruger, Elna
- Date: 2007
- Subjects: Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10413 , http://hdl.handle.net/10948/538 , Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Description: The IL’s used in this study were either synthesized or commercially available. Preparation of the IL’s involved 2 step processes: firstly the heating of distilled 1-methylimidazole with distilled 1-chlorobutane under reflux to obtain 1-butyl-3- methylimidazolium chloride; secondly, the metathesis reaction of sodium tetrafluoroborate with 1-butyl-3-methylimidazolium chloride to obtain 1-butyl-3- methylimidazolium tetrafluoroborate. The addition of sodium tetrafluoroborate, sodium hexafluorophosphate and lithium trifluoromethane sulfonamide with 1-butyl-3-methylimidazolium chloride produced good yields of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide respectively. The IL’s are hygroscopic and must be stored under a nitrogen atmosphere. The IL’s were analyzed using 1H and 13C NMR analysis with CDCl3 as solvent. The physical and chemical properties of these IL’s were compared to commercial products. The physical and chemical properties compared well to reference values from the literature. The physical properties measured include the density, conductivity and electrochemical window. The electrochemical window is dependant primarily on the resistance of the cation to reduction and the resistance of the anion to oxidation. The electrochemical windows of the IL’s were very similar to the reference windows obtained from literature and it can be seen that some IL’s have a slightly lower window which can be due to water present. Water content in the IL’s was determined with the use of a Karl Fischer titrator, with Hydranal 5 Composite as titrant and HPLC grade methanol as the base. The concentration of halide in the IL’s was determined with a Perkin-Elmer ICP-MS.
- Full Text:
- Date Issued: 2007
Synthesis and characterization of symmetrical and unsymmetrical ferrocenyl ligands for use in the preparation of Redox Active Ruthenium Alkylidene Complexes
- Authors: Saku, Duduetsang
- Date: 2007
- Subjects: Ferrocene , Ligands , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10403 , http://hdl.handle.net/10948/701 , Ferrocene , Ligands , Asymmetric synthesis
- Description: Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.
- Full Text:
- Date Issued: 2007
- Authors: Saku, Duduetsang
- Date: 2007
- Subjects: Ferrocene , Ligands , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10403 , http://hdl.handle.net/10948/701 , Ferrocene , Ligands , Asymmetric synthesis
- Description: Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.
- Full Text:
- Date Issued: 2007
Isolation of bioactive metabolites with activity against HIV-1 target proteins from extracts of Sutherlandia frutescens and Lobostemon trigonus
- Authors: Dambuza, Ntokozo Shirley
- Date: 2007
- Subjects: Medicinal plants -- Africa, Southern , HIV infections -- Alternative treatment -- Africa, Southern , Plant bioactive compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10335 , http://hdl.handle.net/10948/492 , http://hdl.handle.net/10948/d1012003 , Medicinal plants -- Africa, Southern , HIV infections -- Alternative treatment -- Africa, Southern , Plant bioactive compounds
- Description: Acquired Immunodeficiency Syndrome (AIDS) is a human disease caused by the human immunodeficiency virus type 1 (HIV-1) and it is one of the biggest social, economic and health challenges in the world. The Joint United Nations Programme on HIV/AIDS (UNAIDS) and World Health Organization (WHO) estimated that between 33.4 to 46.0 million people around the world were living with HIV/AIDS in December 2005 and the highest estimates are in the Sub-Saharan Africa (around 25 million). In more developed countries a combined antiretroviral therapy called highly active antiretroviral therapy (HAART) is used, which results in reduced progression to AIDS in most patients. Despite the beneficial effects of HAART, significant side effects are experienced by treated patients. In addition, most infected people live in countries where the treatment is very expensive or, in many cases, not available at all. These people therefore rely on medicinal plants for health care. In this study, aqueous extracts from Sutherlandia frutescens and Lobostemon trigonus were screened for potential anti-HIV activities in a series of in vitro enzymatic assays, including reverse transcriptase, HIV-1 protease and glycohydrolases. Two extracts of Sutherlandia leaves (SFL-1 and SFL-2) were prepared that inhibited HIV reverse transcriptase and a Lobostemon leaf extract (LTL) was shown to also inhibit this enzyme. All extracts were assayed at 1.25mg/ml. Tannin content was determined for all active extracts using a tannic acid assay. SFL-1 and SFL-2 were found to contain about 6 percent and 7 percent tannins, respectively, and LTL contained 31% tannins by weight. Tannins were removed using polyamide columns and three fractions were collected for each. The extracts were also fractionated with Sephadex G-25, Amberlite IR 120 and Dowex 1-X8 as size exclusion, cation exchange and anion exchange, respectively. Extracts were also fractionated by preparative thin layer chromatography where two compounds were separated from S. frutescens extract with high activity against reverse transcriptase while showing insignificant inhibition towards other enzymes tested. SFL-BFW-10 and SFL-WEF-7 inhibited reverse transcriptase by almost 100 percent and the IC50 values calculated for these compounds were 0.34 and 0.23mg/ml, respectively. Cytotoxicity of these compounds was evaluated on Chang liver cells and peripheral blood mononuclear cells (PBMCs). None of these compounds showed any significant inhibition of cell proliferation. The purity of these compounds could not be confirmed because there was insufficient material to use in the techniques required to show purity and identification. Therefore, TLC was used to determine the nature of these compounds. SFL-BFW-10 was identified as an organic acid and SFL-WEF-7 was identified as flavonoid.
- Full Text:
- Date Issued: 2007
- Authors: Dambuza, Ntokozo Shirley
- Date: 2007
- Subjects: Medicinal plants -- Africa, Southern , HIV infections -- Alternative treatment -- Africa, Southern , Plant bioactive compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10335 , http://hdl.handle.net/10948/492 , http://hdl.handle.net/10948/d1012003 , Medicinal plants -- Africa, Southern , HIV infections -- Alternative treatment -- Africa, Southern , Plant bioactive compounds
- Description: Acquired Immunodeficiency Syndrome (AIDS) is a human disease caused by the human immunodeficiency virus type 1 (HIV-1) and it is one of the biggest social, economic and health challenges in the world. The Joint United Nations Programme on HIV/AIDS (UNAIDS) and World Health Organization (WHO) estimated that between 33.4 to 46.0 million people around the world were living with HIV/AIDS in December 2005 and the highest estimates are in the Sub-Saharan Africa (around 25 million). In more developed countries a combined antiretroviral therapy called highly active antiretroviral therapy (HAART) is used, which results in reduced progression to AIDS in most patients. Despite the beneficial effects of HAART, significant side effects are experienced by treated patients. In addition, most infected people live in countries where the treatment is very expensive or, in many cases, not available at all. These people therefore rely on medicinal plants for health care. In this study, aqueous extracts from Sutherlandia frutescens and Lobostemon trigonus were screened for potential anti-HIV activities in a series of in vitro enzymatic assays, including reverse transcriptase, HIV-1 protease and glycohydrolases. Two extracts of Sutherlandia leaves (SFL-1 and SFL-2) were prepared that inhibited HIV reverse transcriptase and a Lobostemon leaf extract (LTL) was shown to also inhibit this enzyme. All extracts were assayed at 1.25mg/ml. Tannin content was determined for all active extracts using a tannic acid assay. SFL-1 and SFL-2 were found to contain about 6 percent and 7 percent tannins, respectively, and LTL contained 31% tannins by weight. Tannins were removed using polyamide columns and three fractions were collected for each. The extracts were also fractionated with Sephadex G-25, Amberlite IR 120 and Dowex 1-X8 as size exclusion, cation exchange and anion exchange, respectively. Extracts were also fractionated by preparative thin layer chromatography where two compounds were separated from S. frutescens extract with high activity against reverse transcriptase while showing insignificant inhibition towards other enzymes tested. SFL-BFW-10 and SFL-WEF-7 inhibited reverse transcriptase by almost 100 percent and the IC50 values calculated for these compounds were 0.34 and 0.23mg/ml, respectively. Cytotoxicity of these compounds was evaluated on Chang liver cells and peripheral blood mononuclear cells (PBMCs). None of these compounds showed any significant inhibition of cell proliferation. The purity of these compounds could not be confirmed because there was insufficient material to use in the techniques required to show purity and identification. Therefore, TLC was used to determine the nature of these compounds. SFL-BFW-10 was identified as an organic acid and SFL-WEF-7 was identified as flavonoid.
- Full Text:
- Date Issued: 2007
A comparison of the vulcanisation of Polyisoprene by a range of Thiuram Diulfides
- Authors: Van Rooyen, Jason Leigh
- Date: 2007
- Subjects: Vulcanization , Vulcanization accelerators
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10399 , http://hdl.handle.net/10948/733 , Vulcanization , Vulcanization accelerators
- Description: This study was initiated in an attempt to investigate dithiocarbamic acid accelerated sulfur vulcanisation. This was, however, found impossible due to the innate instability of dithiocarbamic acids. The focus of the study was then shifted toward thiuram disulfide accelerated sulfur vulcanisation, with emphasis being placed on a rate comparison. Three groups of accelerators were investigated, namely the aromatic, linear aliphatic and cyclic aliphatic thiuram disulfide adducts. The analysis methods that were employed were conventional rubber (cis-1,4-polyisoprene) techniques coupled to model (squalene) compound investigations. The data that was collected consisted of rheometrical torque vs. time data in the rubber system while the data obtained in the model compound study consisted of sulfur and accelerator concentration data as determined by means of high performance liquid chromatography (HPLC). The aromatic accelerators were synthesised in our labs by means of an addition reaction between the aromatic amine and CS2 in basic medium and subsequent oxidation with K3Fe(CN)6, all in a 1:1 molar ratio. The reaction yield was low due to the instability of the dithiocarbamate intermediates and a sluggish oxidation reaction. In the rate constant determination a first order mathematical approach was used for the rubber system as crosslinking is considered to roughly obey first order kinetics. The model compound data was also found to more accurately fit the first order rate law, with an initial slopes method also being applied to the system to determine secondary rate constants and relative rates for the system. The determination of vulcanisation rate constants in the cis-1,4-polyisoprene system was a success, while the rate data determined by means of the squalene model was more related to the rate of accelerator and sulfur consumption as opposed to the rate of crosslinking as is the case with the rubber rate data. The sulfur first order rate data mirrored the rate data derived from the rubber system more closely than the corresponding accelerator rate data, the relative rate data determined by means of initial slopes method, proved that the homolytic cleavage of thiuram disulfides and the subsequent formation of accelerator polysulfides were not limiting steps. This is seen in the similar relative rate data derived from both the raw sulfur and accelerator data in systems that exhibit vastly different vulcanisation rates. Squalene was deemed a suitable model for the cis-1,4-polyisoprene system, although one should consider the extent of charring and solution effects in the individual systems to account for possible incongruities that may be observed between the rubber and simulated system. The lack of agreement between the rubber and model compound rate constant data lies in the fact that the rate of crosslinking is not simplistically related to the rate at which accelerator and sulfur is consumed, this being especially true for the rate at which the accelerator is consumed. Thus the discussion over the acceleratory rates in the various accelerator systems was limited to observations made in the rubber system, with the model compound data was used exclusively to elucidate mechanistic processes. It was discovered that the groups of accelerators examined, namely linear, cyclic and aromatic thiuram disulfide adducts, produced vastly varied rate data. The aromatic thiuram disulfide adducts had only a slight acceleratory effect on the rate of vulcanisation as compared to the unaccelerated sulfur system. The morpholine adduct had a moderately larger rate of acceleration followed by tetramethyl and tetrethylthiuram disulfide, with N’N-dicyclopentamethylenethiuram disulfide having the fastest rate of acceleration.
- Full Text:
- Date Issued: 2007
- Authors: Van Rooyen, Jason Leigh
- Date: 2007
- Subjects: Vulcanization , Vulcanization accelerators
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10399 , http://hdl.handle.net/10948/733 , Vulcanization , Vulcanization accelerators
- Description: This study was initiated in an attempt to investigate dithiocarbamic acid accelerated sulfur vulcanisation. This was, however, found impossible due to the innate instability of dithiocarbamic acids. The focus of the study was then shifted toward thiuram disulfide accelerated sulfur vulcanisation, with emphasis being placed on a rate comparison. Three groups of accelerators were investigated, namely the aromatic, linear aliphatic and cyclic aliphatic thiuram disulfide adducts. The analysis methods that were employed were conventional rubber (cis-1,4-polyisoprene) techniques coupled to model (squalene) compound investigations. The data that was collected consisted of rheometrical torque vs. time data in the rubber system while the data obtained in the model compound study consisted of sulfur and accelerator concentration data as determined by means of high performance liquid chromatography (HPLC). The aromatic accelerators were synthesised in our labs by means of an addition reaction between the aromatic amine and CS2 in basic medium and subsequent oxidation with K3Fe(CN)6, all in a 1:1 molar ratio. The reaction yield was low due to the instability of the dithiocarbamate intermediates and a sluggish oxidation reaction. In the rate constant determination a first order mathematical approach was used for the rubber system as crosslinking is considered to roughly obey first order kinetics. The model compound data was also found to more accurately fit the first order rate law, with an initial slopes method also being applied to the system to determine secondary rate constants and relative rates for the system. The determination of vulcanisation rate constants in the cis-1,4-polyisoprene system was a success, while the rate data determined by means of the squalene model was more related to the rate of accelerator and sulfur consumption as opposed to the rate of crosslinking as is the case with the rubber rate data. The sulfur first order rate data mirrored the rate data derived from the rubber system more closely than the corresponding accelerator rate data, the relative rate data determined by means of initial slopes method, proved that the homolytic cleavage of thiuram disulfides and the subsequent formation of accelerator polysulfides were not limiting steps. This is seen in the similar relative rate data derived from both the raw sulfur and accelerator data in systems that exhibit vastly different vulcanisation rates. Squalene was deemed a suitable model for the cis-1,4-polyisoprene system, although one should consider the extent of charring and solution effects in the individual systems to account for possible incongruities that may be observed between the rubber and simulated system. The lack of agreement between the rubber and model compound rate constant data lies in the fact that the rate of crosslinking is not simplistically related to the rate at which accelerator and sulfur is consumed, this being especially true for the rate at which the accelerator is consumed. Thus the discussion over the acceleratory rates in the various accelerator systems was limited to observations made in the rubber system, with the model compound data was used exclusively to elucidate mechanistic processes. It was discovered that the groups of accelerators examined, namely linear, cyclic and aromatic thiuram disulfide adducts, produced vastly varied rate data. The aromatic thiuram disulfide adducts had only a slight acceleratory effect on the rate of vulcanisation as compared to the unaccelerated sulfur system. The morpholine adduct had a moderately larger rate of acceleration followed by tetramethyl and tetrethylthiuram disulfide, with N’N-dicyclopentamethylenethiuram disulfide having the fastest rate of acceleration.
- Full Text:
- Date Issued: 2007
Towards knowing through doing : improving the societal relevance of systematic conservation assessments
- Authors: Knight, Andrew Thomas
- Date: 2007
- Subjects: Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10598 , http://hdl.handle.net/10948/711 , Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Description: Systematic conservation assessments are spatially-explicit techniques for prioritising areas for the implementation of conservation action. There has been considerable reference in the peer-reviewed literature as to the usefulness of these tools, which appear to be primarily used by academics for theoretical research. A literature review and author survey reveals the peer-reviewed literature is largely theoretical, although conservation action results more frequently than reported. The effectiveness of these interventions is generally described as only ‘fairly effective’. This general trend, coupled with previous personal failures in translating systematic conservation assessments into effective conservation action triggered an explicit process of social learning implemented as action research. It examined the workings of the Subtropical Thicket Ecosystem Planning (STEP) project, which included development of a systematic conservation assessment. Systematic conservations assessments simply provide information on where action should be implemented, and so are only useful if situated within broader operational models for conservation planning. Most operational models presented in the peer-reviewed literature are primarily focused upon the testing ecological data, not upon the delivery of conservation action. A new operational model for conservation planning is presented which more accurately reflects the ‘real-world’ process of conservation planning. An implementation strategy is an essential complement to a systematic conservation assessment. It describes how specific, explicitly-stated goals will be achieved, who is accountable for undertaking these activities, and the resources required. As the Implementation Specialist for the STEP Project, I co-lead the collaborative development of an implementation strategy with stakeholders that aimed to mobilise resources towards achieving common goals. Whilst the development and initial uptake of the strategy was good, subsequent implementation has flounder. The reasons for this are explored. The ultimate pragmatic goal of a conservation planning process is the establishment of effective social learning institutions. These develop common visions, mobilise collective action, and adaptively learn and refine their conservation activities. Thicket Forum is one xi such institution established through the STEP Project. My involvement with Thicket Forum since 2004 in implementing an adaptive learning approach facilitates collaboration between land managers, government and research organisations. Systematic conservation assessments evolved in response to the ad hoc way in which protected areas were implemented, leaving unrepresentative, biased protected area networks. Most research is theoretical and without an intimate understanding of the social-ecological system of a planning region, notably opportunities and constraints for implementing conservation action. Highlighting the importance of an approach which is flexible, not only in space, but in time, which can capitalise upon implementation opportunities, is important for stemming the myth that opportunism is the nemesis of systematic conservation assessments. To this end, conservation planners have been slow to include factors influencing effective implementation in systematic conservation assessments. Many studies which identify candidate protected area networks, first, fail to identify the specific instrument(s) to be applied, and second, assume all intact land is available. Having mapped the willingness of land managers in the Albany District, South Africa, to sell their land, it is demonstrated the majority of targets fail to be achieved because land managers will not sell. Knowing this, the current focus of gathering ever-more ecological data is misplaced. Human, social and economic factors influence target achievement, efficiency and spatial configuration of priority areas. Selecting important areas for conservation, particularly at the local-scale, requires the mapping of factors which define opportunities for conservation. Land manager willingness to collaborate and participate, entrepreneurial orientation, conservation knowledge, social capital, and local champions were applied using a method of hierarchical clustering to identify land managers who represent conservation opportunities for private land conservation initiatives.
- Full Text:
- Date Issued: 2007
- Authors: Knight, Andrew Thomas
- Date: 2007
- Subjects: Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10598 , http://hdl.handle.net/10948/711 , Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Description: Systematic conservation assessments are spatially-explicit techniques for prioritising areas for the implementation of conservation action. There has been considerable reference in the peer-reviewed literature as to the usefulness of these tools, which appear to be primarily used by academics for theoretical research. A literature review and author survey reveals the peer-reviewed literature is largely theoretical, although conservation action results more frequently than reported. The effectiveness of these interventions is generally described as only ‘fairly effective’. This general trend, coupled with previous personal failures in translating systematic conservation assessments into effective conservation action triggered an explicit process of social learning implemented as action research. It examined the workings of the Subtropical Thicket Ecosystem Planning (STEP) project, which included development of a systematic conservation assessment. Systematic conservations assessments simply provide information on where action should be implemented, and so are only useful if situated within broader operational models for conservation planning. Most operational models presented in the peer-reviewed literature are primarily focused upon the testing ecological data, not upon the delivery of conservation action. A new operational model for conservation planning is presented which more accurately reflects the ‘real-world’ process of conservation planning. An implementation strategy is an essential complement to a systematic conservation assessment. It describes how specific, explicitly-stated goals will be achieved, who is accountable for undertaking these activities, and the resources required. As the Implementation Specialist for the STEP Project, I co-lead the collaborative development of an implementation strategy with stakeholders that aimed to mobilise resources towards achieving common goals. Whilst the development and initial uptake of the strategy was good, subsequent implementation has flounder. The reasons for this are explored. The ultimate pragmatic goal of a conservation planning process is the establishment of effective social learning institutions. These develop common visions, mobilise collective action, and adaptively learn and refine their conservation activities. Thicket Forum is one xi such institution established through the STEP Project. My involvement with Thicket Forum since 2004 in implementing an adaptive learning approach facilitates collaboration between land managers, government and research organisations. Systematic conservation assessments evolved in response to the ad hoc way in which protected areas were implemented, leaving unrepresentative, biased protected area networks. Most research is theoretical and without an intimate understanding of the social-ecological system of a planning region, notably opportunities and constraints for implementing conservation action. Highlighting the importance of an approach which is flexible, not only in space, but in time, which can capitalise upon implementation opportunities, is important for stemming the myth that opportunism is the nemesis of systematic conservation assessments. To this end, conservation planners have been slow to include factors influencing effective implementation in systematic conservation assessments. Many studies which identify candidate protected area networks, first, fail to identify the specific instrument(s) to be applied, and second, assume all intact land is available. Having mapped the willingness of land managers in the Albany District, South Africa, to sell their land, it is demonstrated the majority of targets fail to be achieved because land managers will not sell. Knowing this, the current focus of gathering ever-more ecological data is misplaced. Human, social and economic factors influence target achievement, efficiency and spatial configuration of priority areas. Selecting important areas for conservation, particularly at the local-scale, requires the mapping of factors which define opportunities for conservation. Land manager willingness to collaborate and participate, entrepreneurial orientation, conservation knowledge, social capital, and local champions were applied using a method of hierarchical clustering to identify land managers who represent conservation opportunities for private land conservation initiatives.
- Full Text:
- Date Issued: 2007
Consistent testing for lag length in cointegrated relationships
- Authors: Liu, Limin
- Date: 2007
- Subjects: Cointegration -- South Africa , Econometrics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10575 , http://hdl.handle.net/10948/547 , http://hdl.handle.net/10948/d1011715 , Cointegration -- South Africa , Econometrics
- Description: In the past few decades the theory of cointegration has been widely used in the empirical analysis of economic data. The reason is that, it captures the economic notion of a long-run economic relation. One of the problems experienced when applying cointegrated techniques to econometric modelling is the determination of lag lengths for the modelled variables. Applied studies have resulted in contradictory choices for lag length selection. This study reviews and compares some of the well-known information criteria using simulation techniques for bivariate models.
- Full Text:
- Date Issued: 2007
- Authors: Liu, Limin
- Date: 2007
- Subjects: Cointegration -- South Africa , Econometrics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10575 , http://hdl.handle.net/10948/547 , http://hdl.handle.net/10948/d1011715 , Cointegration -- South Africa , Econometrics
- Description: In the past few decades the theory of cointegration has been widely used in the empirical analysis of economic data. The reason is that, it captures the economic notion of a long-run economic relation. One of the problems experienced when applying cointegrated techniques to econometric modelling is the determination of lag lengths for the modelled variables. Applied studies have resulted in contradictory choices for lag length selection. This study reviews and compares some of the well-known information criteria using simulation techniques for bivariate models.
- Full Text:
- Date Issued: 2007
An investigation of statistical methodologies for evaluating natural herbicides for the control of yellow nutsedge (Cyperus esculentus)
- Authors: Asquith, Ilse Bernadette
- Date: 2007
- Subjects: Chemometrics , Weeds
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: vital:10376 , Chemometrics , Weeds
- Description: The present study was undertaken with the view to evaluate methodologies based on traditional Scheffé experimental designs that study mixtures as a tool for discovery research particularly when seeking new and or improved uses of existing mixtures. For the purpose of this study, the topic of controlling the problematic weed known as Yellow Nutsedge (Cyperus esculentus L. var. esculentus) or “Geel Uintjie”, was selected on a rather ad hoc basis. Yellow Nutsedge is a troublesome perennial weed found in most agricultural countries in the world. Herbicidal control is often difficult because of the weeds’ ability to propagate via tubers, which can remain dormant for a number of years and are also resistant to most synthetic herbicide controls. As a first step the study involved the selection of a group of chemical compounds that would be used in suppressing the germination of Yellow Nutsedge tubers. Treatment with various combinations of these chemical compounds as determined by statistical experimental designs was carried out. A review of the literature, particularly literature concerned with the study of the phenomenon of allelopathy, suggested that various phenolic-D-glucopyranosides could show promise in the suppressing the germination of Yellow Nutsedge tubers. This led to the selection of this group of compounds as the target group of “active” substances for the study. Since the group of phenolic-D-glucopyranosides is quite large, and in order to keep the study to a reasonable size, only four phenolic-D-glucopyranosides were selected namely: 4-nitrophenyl-D-glucopyranoside, 4-chlorophenyl--Dglucopyranoside, arbutin and salicin. This selection was based firstly based on a particular phenolic-D-glucopyranoside being a suspected allelochemical, and secondly the ease of technical synthesis using a catalytic process. In addition to the four selected phenolic-D-glucopyranosides, their aglycones (4,nitrophenol, 4,chlorophenol, hydroquinone and salicyl alcohol) were also included as potential “active” substances in order to discern any potential activity between the phenolic-D-glucopyranosides and the aglycones. iii The selected “active substances” were combined in various combinations according to various mixture designs in such a manner that the sum of the proportions of the various actives in any one mixture was always equal to 1. The mixtures of actives were then used in various germination experiments and three experimental responses were measured namely the germination, average dry mass and length of longest shoot. From the results of these germination studies the canonical form of the polynomial equation describing the variation in each of the three germination responses was calculated and evaluated statistically. These equations were then used to estimate the presence of, and the magnitude of synergism between the various active substances. The results from these screening experiments and their detailed statistical analysis indicated that the response surface model for the germination response contains three synergistic blends (4-nitrophenyl--D-glucopyranoside + arbutin; 4-nitrophenyl--Dglucopyranoside + hydroquinone; and 4-chlorophenyl--D-glucopyranoside + salicin) and one antagonistic blend (4-nitrophenyl--D-glucopyranoside + 4- chlorophenol--D-glucopyranoside). The response surface model for the average dry mass response contains two synergistic blends (4-nitrophenyl--Dglucopyranoside + hydroquinone; and 4-chlorophenol--D-glucopyranoside + salicin) and the same antagonistic blend as for germination response. For both germination and average dry mass responses, the most synergistic blend was found to be the combination of 4-chlorophenyl--D-glucopyranoside and salicin. Two additional tests were conducted and both confirmed the results obtained from the screening designs. These tests involved the identification of the two components responsible for the synergistic activity that resulted in the suppression of the germination of the tubers and growth of the seedlings. The experimental response measuring the longest shoot proved to be erroneous and was excluded from the statistical analysis. In summary, this study has clearly shown that statistically designed experiments based on mixture designs can be used as a powerful tool in identifying and quantifying synergistic (or antagonistic) effects of chemicals on the germination ability of plant seeds.
- Full Text:
- Date Issued: 2007
- Authors: Asquith, Ilse Bernadette
- Date: 2007
- Subjects: Chemometrics , Weeds
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: vital:10376 , Chemometrics , Weeds
- Description: The present study was undertaken with the view to evaluate methodologies based on traditional Scheffé experimental designs that study mixtures as a tool for discovery research particularly when seeking new and or improved uses of existing mixtures. For the purpose of this study, the topic of controlling the problematic weed known as Yellow Nutsedge (Cyperus esculentus L. var. esculentus) or “Geel Uintjie”, was selected on a rather ad hoc basis. Yellow Nutsedge is a troublesome perennial weed found in most agricultural countries in the world. Herbicidal control is often difficult because of the weeds’ ability to propagate via tubers, which can remain dormant for a number of years and are also resistant to most synthetic herbicide controls. As a first step the study involved the selection of a group of chemical compounds that would be used in suppressing the germination of Yellow Nutsedge tubers. Treatment with various combinations of these chemical compounds as determined by statistical experimental designs was carried out. A review of the literature, particularly literature concerned with the study of the phenomenon of allelopathy, suggested that various phenolic-D-glucopyranosides could show promise in the suppressing the germination of Yellow Nutsedge tubers. This led to the selection of this group of compounds as the target group of “active” substances for the study. Since the group of phenolic-D-glucopyranosides is quite large, and in order to keep the study to a reasonable size, only four phenolic-D-glucopyranosides were selected namely: 4-nitrophenyl-D-glucopyranoside, 4-chlorophenyl--Dglucopyranoside, arbutin and salicin. This selection was based firstly based on a particular phenolic-D-glucopyranoside being a suspected allelochemical, and secondly the ease of technical synthesis using a catalytic process. In addition to the four selected phenolic-D-glucopyranosides, their aglycones (4,nitrophenol, 4,chlorophenol, hydroquinone and salicyl alcohol) were also included as potential “active” substances in order to discern any potential activity between the phenolic-D-glucopyranosides and the aglycones. iii The selected “active substances” were combined in various combinations according to various mixture designs in such a manner that the sum of the proportions of the various actives in any one mixture was always equal to 1. The mixtures of actives were then used in various germination experiments and three experimental responses were measured namely the germination, average dry mass and length of longest shoot. From the results of these germination studies the canonical form of the polynomial equation describing the variation in each of the three germination responses was calculated and evaluated statistically. These equations were then used to estimate the presence of, and the magnitude of synergism between the various active substances. The results from these screening experiments and their detailed statistical analysis indicated that the response surface model for the germination response contains three synergistic blends (4-nitrophenyl--D-glucopyranoside + arbutin; 4-nitrophenyl--Dglucopyranoside + hydroquinone; and 4-chlorophenyl--D-glucopyranoside + salicin) and one antagonistic blend (4-nitrophenyl--D-glucopyranoside + 4- chlorophenol--D-glucopyranoside). The response surface model for the average dry mass response contains two synergistic blends (4-nitrophenyl--Dglucopyranoside + hydroquinone; and 4-chlorophenol--D-glucopyranoside + salicin) and the same antagonistic blend as for germination response. For both germination and average dry mass responses, the most synergistic blend was found to be the combination of 4-chlorophenyl--D-glucopyranoside and salicin. Two additional tests were conducted and both confirmed the results obtained from the screening designs. These tests involved the identification of the two components responsible for the synergistic activity that resulted in the suppression of the germination of the tubers and growth of the seedlings. The experimental response measuring the longest shoot proved to be erroneous and was excluded from the statistical analysis. In summary, this study has clearly shown that statistically designed experiments based on mixture designs can be used as a powerful tool in identifying and quantifying synergistic (or antagonistic) effects of chemicals on the germination ability of plant seeds.
- Full Text:
- Date Issued: 2007
MOCVD growth and electrical characterisation of InAs thin films
- Authors: Shamba, Precious
- Date: 2007
- Subjects: Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10527 , http://hdl.handle.net/10948/706 , Metal organic chemical vapor deposition
- Description: In this work, a systematic study relating the surface morphologies, electrical and structural properties of both doped and undoped InAs and InAsSb epitaxial films grown by metalorganic chemical vapour deposition (MOCVD) was undertaken. A comparative study using TBAs and AsH3 as the group V source in the growth of InAs revealed a considerable improvement, primarily in the electrical properties of InAs grown using TBAs with no significant difference in the surface morphology. InAs layers grown using TBAs, exhibited superior 77 K mobilities of up to 46 000 cm2/Vs, exceeding the best MOCVD data to date. The feasibility of tetraethyl tin (TESn) as an n-type dopant in InAs was to our knowledge investigated for the first time. The incorporation efficiency of this dopant was extensively studied as a function of substrate temperature, V/III ratio, substrate orientation and TESn flow rate. Results from this study show that the doping efficiency is temperature dependent and is not influenced by a variation of the V/III ratio or substrate orientation. Furthermore, Sn doping concentrations could be controlled over 2 orders of magnitude ranging between 2.7 x 1017 and 4.7 x 1019 cm-3 with 77 K mobilities ranging from 12 000 to 1300 cm2/Vs. The electrical properties of zinc doped InAs employing dimethyl zinc (DMZn) as the ptype dopant, were studied as a function of V/III ratio and substrate orientation. The effect of a variation of these parameters on the structural properties and surface morphology of InAs is also reported. The substrate orientation appears to have no influence on the Zn incorporation. An increase in Zn incorporation resulted in a deterioration of both the surface morphology and structural quality of the InAs layers. The incorporation efficiency of DMZn in InAsSb was studied as a function of growth temperature, V/III ratio and DMZn flow rate. A higher Zn incorporation was observed in InAsSb epitaxial layers grown at a lower temperature and V/III ratio as opposed to the layers grown at a higher temperature and V/III ratio. This study also revealed that the use of DMZn caused a dopant memory effect. A two-layer model proposed by Nedoluha and Koch (1952) was used to simulate the Hall measurements of Zn doped InAs and InAsSb in order to correct the shortcomings of conventional Hall measurements in determining the electrical properties exhibited by these materials.
- Full Text:
- Date Issued: 2007
- Authors: Shamba, Precious
- Date: 2007
- Subjects: Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10527 , http://hdl.handle.net/10948/706 , Metal organic chemical vapor deposition
- Description: In this work, a systematic study relating the surface morphologies, electrical and structural properties of both doped and undoped InAs and InAsSb epitaxial films grown by metalorganic chemical vapour deposition (MOCVD) was undertaken. A comparative study using TBAs and AsH3 as the group V source in the growth of InAs revealed a considerable improvement, primarily in the electrical properties of InAs grown using TBAs with no significant difference in the surface morphology. InAs layers grown using TBAs, exhibited superior 77 K mobilities of up to 46 000 cm2/Vs, exceeding the best MOCVD data to date. The feasibility of tetraethyl tin (TESn) as an n-type dopant in InAs was to our knowledge investigated for the first time. The incorporation efficiency of this dopant was extensively studied as a function of substrate temperature, V/III ratio, substrate orientation and TESn flow rate. Results from this study show that the doping efficiency is temperature dependent and is not influenced by a variation of the V/III ratio or substrate orientation. Furthermore, Sn doping concentrations could be controlled over 2 orders of magnitude ranging between 2.7 x 1017 and 4.7 x 1019 cm-3 with 77 K mobilities ranging from 12 000 to 1300 cm2/Vs. The electrical properties of zinc doped InAs employing dimethyl zinc (DMZn) as the ptype dopant, were studied as a function of V/III ratio and substrate orientation. The effect of a variation of these parameters on the structural properties and surface morphology of InAs is also reported. The substrate orientation appears to have no influence on the Zn incorporation. An increase in Zn incorporation resulted in a deterioration of both the surface morphology and structural quality of the InAs layers. The incorporation efficiency of DMZn in InAsSb was studied as a function of growth temperature, V/III ratio and DMZn flow rate. A higher Zn incorporation was observed in InAsSb epitaxial layers grown at a lower temperature and V/III ratio as opposed to the layers grown at a higher temperature and V/III ratio. This study also revealed that the use of DMZn caused a dopant memory effect. A two-layer model proposed by Nedoluha and Koch (1952) was used to simulate the Hall measurements of Zn doped InAs and InAsSb in order to correct the shortcomings of conventional Hall measurements in determining the electrical properties exhibited by these materials.
- Full Text:
- Date Issued: 2007
Characterisation of InAs-based epilayers by FTIR spectroscopy
- Authors: Baisitse, Tshepiso Revonia
- Date: 2007
- Subjects: Fourier transform infrared spectroscopy , Gallium arsenide semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10534 , http://hdl.handle.net/10948/474 , Fourier transform infrared spectroscopy , Gallium arsenide semiconductors
- Description: This study focuses on the characterization of InAs and InAs1-xSbx epitaxial layers by infrared reflectance and transmittance spectroscopy and Hall measurements. Reflectance measurements were performed in order to obtain the dielectric parameters and to extract from these information about the electrical properties (mobility and carrier concentration) of this important III-V material system. The transmittance measurements were used to determine the bandgap of InAsSb. Infrared reflectivity and transmittance measurements were performed in the wavelength range 200 – 2000 cm-1 on InAs and InAsSb layers grown on three types of substrates. A classical two oscillator model that takes into account both the free carriers and the lattice, was used to analyse the reflectance data using the BMDP® computer curve fitting software. The dielectric parameters and the electrical properties (carrier concentration and mobility) were extracted from the simulations. Due to the low free carrier concentration in the epitaxial structures, the plasma resonance frequency (ωp) values obtained from the simulations of reflectance spectra measured above 200 cm-1, were in the order of 20-30 cm-1. These low values were confirmed by direct measurements of ωp in reflectance spectra obtained in the range 15-200 cm-1. The simulated carrier concentration and mobility values determined optically were compared to the values determined by Hall measurements at room temperature and previously reported values by other researchers. The simulated values obtained were in reasonable agreement with the Hall values. The simulated and measured carrier concentrations obtained for InAs layers were significantly higher than the intrinsic carrier concentration for InAs at room temperature, indicating notable concentrations of donors resulting from the growth process.
- Full Text:
- Date Issued: 2007
- Authors: Baisitse, Tshepiso Revonia
- Date: 2007
- Subjects: Fourier transform infrared spectroscopy , Gallium arsenide semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10534 , http://hdl.handle.net/10948/474 , Fourier transform infrared spectroscopy , Gallium arsenide semiconductors
- Description: This study focuses on the characterization of InAs and InAs1-xSbx epitaxial layers by infrared reflectance and transmittance spectroscopy and Hall measurements. Reflectance measurements were performed in order to obtain the dielectric parameters and to extract from these information about the electrical properties (mobility and carrier concentration) of this important III-V material system. The transmittance measurements were used to determine the bandgap of InAsSb. Infrared reflectivity and transmittance measurements were performed in the wavelength range 200 – 2000 cm-1 on InAs and InAsSb layers grown on three types of substrates. A classical two oscillator model that takes into account both the free carriers and the lattice, was used to analyse the reflectance data using the BMDP® computer curve fitting software. The dielectric parameters and the electrical properties (carrier concentration and mobility) were extracted from the simulations. Due to the low free carrier concentration in the epitaxial structures, the plasma resonance frequency (ωp) values obtained from the simulations of reflectance spectra measured above 200 cm-1, were in the order of 20-30 cm-1. These low values were confirmed by direct measurements of ωp in reflectance spectra obtained in the range 15-200 cm-1. The simulated carrier concentration and mobility values determined optically were compared to the values determined by Hall measurements at room temperature and previously reported values by other researchers. The simulated values obtained were in reasonable agreement with the Hall values. The simulated and measured carrier concentrations obtained for InAs layers were significantly higher than the intrinsic carrier concentration for InAs at room temperature, indicating notable concentrations of donors resulting from the growth process.
- Full Text:
- Date Issued: 2007
Micellar-enhanced ultrafiltration of palladium and platinum anions
- Authors: Gwicana, Sakumzi
- Date: 2007
- Subjects: Micelles , Ultrafiltration , Palladium catalysts
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10414 , http://hdl.handle.net/10948/518 , Micelles , Ultrafiltration , Palladium catalysts
- Description: The project was concerned with studying the capability of a micellar-enhanced ultrafiltration system (MEUF) to remove platinum group metal ions namely Pt (lV) and Pd (ll) chloro anions from aqueous industrial waste effluents. South Africa has the world’s largest reserves of platinum group metals (PGMs) and other valuable metals such as manganese, chrome ores, titanium minerals etc. which are required for new automotive and other technologies, including fuel cells, catalytic converters and lighter components. The consistent loss with the industrial waste stream and the toxicological effects of these precious metals led to the need to develop new and effective methods to recover them from industrial waste effluents. With such a wide variety of fields where these PGMs are used and the failure of the traditional techniques namely sedimentation, fermentation etc. to effectively reduce or recover these highly toxic and precious metal ions prior to discharging industrial waste effluents, it is necessary to explore other techniques such as membrane technology that can be used to recover these valuable species from industrial waste streams. The present study involved the use of a cationic surfactant, viz cetylpyridinium chloride, which was introduced into an aqueous solution containing palladium and platinum metal anions. The surfactant forms charged micelles above a certain critical concentration value. The metal anions adsorb onto the available oppositely charged sites on the micelle surfaces and are then able to be retained by a suitable membrane. Hollow fibre ultrafiltration membranes with the MWCO of +/- 10 kD and +/-30nm pore size were used as a filter component in this study. For this MEUF system to be effective, it was vital that the anionic metal ion species adsorbed sufficiently onto the available oppositely charged sites of the micelles and that the micelles were retained efficiently by the membrane. Results obtained during the investigation made it possible to make certain predictions about the micellisation process. It was also found that, it was not only the metal ion: surfactant (M:S) ratio that was critical, but the presence of other electrolytes in the aqueous stream proved to have a huge impact on the capability of the MEUF system. Findings of this research study showed that the MEUF system using cetylpyridinium chloride (CPC) can be used to recover or retain Pt (lV) and Pd (ll) anions from industrial waste effluents. It was also found that PtCl6 2-, due to its greater adsorption capabilities onto the micelle surface than PdCl4 2- or PdCl3(H2O)-, was preferentially retained in neutral medium. This may be exploited as a possible means of separating the two metal ions. The developed system offers the following advantages over some traditional and current methods: simplified unit operation line flow process, smaller amounts of chemical usage and no solid toxic sludge to be disposed of. Applications of this work could be of vital importance in catalytic converter recycling, especially in Port Elizabeth where extensive automobile parts manufacturing occurs.
- Full Text:
- Date Issued: 2007
- Authors: Gwicana, Sakumzi
- Date: 2007
- Subjects: Micelles , Ultrafiltration , Palladium catalysts
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10414 , http://hdl.handle.net/10948/518 , Micelles , Ultrafiltration , Palladium catalysts
- Description: The project was concerned with studying the capability of a micellar-enhanced ultrafiltration system (MEUF) to remove platinum group metal ions namely Pt (lV) and Pd (ll) chloro anions from aqueous industrial waste effluents. South Africa has the world’s largest reserves of platinum group metals (PGMs) and other valuable metals such as manganese, chrome ores, titanium minerals etc. which are required for new automotive and other technologies, including fuel cells, catalytic converters and lighter components. The consistent loss with the industrial waste stream and the toxicological effects of these precious metals led to the need to develop new and effective methods to recover them from industrial waste effluents. With such a wide variety of fields where these PGMs are used and the failure of the traditional techniques namely sedimentation, fermentation etc. to effectively reduce or recover these highly toxic and precious metal ions prior to discharging industrial waste effluents, it is necessary to explore other techniques such as membrane technology that can be used to recover these valuable species from industrial waste streams. The present study involved the use of a cationic surfactant, viz cetylpyridinium chloride, which was introduced into an aqueous solution containing palladium and platinum metal anions. The surfactant forms charged micelles above a certain critical concentration value. The metal anions adsorb onto the available oppositely charged sites on the micelle surfaces and are then able to be retained by a suitable membrane. Hollow fibre ultrafiltration membranes with the MWCO of +/- 10 kD and +/-30nm pore size were used as a filter component in this study. For this MEUF system to be effective, it was vital that the anionic metal ion species adsorbed sufficiently onto the available oppositely charged sites of the micelles and that the micelles were retained efficiently by the membrane. Results obtained during the investigation made it possible to make certain predictions about the micellisation process. It was also found that, it was not only the metal ion: surfactant (M:S) ratio that was critical, but the presence of other electrolytes in the aqueous stream proved to have a huge impact on the capability of the MEUF system. Findings of this research study showed that the MEUF system using cetylpyridinium chloride (CPC) can be used to recover or retain Pt (lV) and Pd (ll) anions from industrial waste effluents. It was also found that PtCl6 2-, due to its greater adsorption capabilities onto the micelle surface than PdCl4 2- or PdCl3(H2O)-, was preferentially retained in neutral medium. This may be exploited as a possible means of separating the two metal ions. The developed system offers the following advantages over some traditional and current methods: simplified unit operation line flow process, smaller amounts of chemical usage and no solid toxic sludge to be disposed of. Applications of this work could be of vital importance in catalytic converter recycling, especially in Port Elizabeth where extensive automobile parts manufacturing occurs.
- Full Text:
- Date Issued: 2007
A model for adaptive multimodal mobile notification
- Authors: Brander, William
- Date: 2007
- Subjects: Mobile computing , Context-aware computing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10473 , http://hdl.handle.net/10948/699 , Mobile computing , Context-aware computing
- Description: Information is useless unless it is used whilst still applicable. Having a system that notifies the user of important messages using the most appropriate medium and device will benefit users that rely on time critical information. There are several existing systems and models for mobile notification as well as for adaptive mobile notification using context awareness. Current models and systems are typically designed for a specific set of mobile devices, modes and services. Communication however, can take place in many different modes, across many different devices and may originate from many different sources. The aim of this research was to develop a model for adaptive mobile notification using context awareness. An extensive literature study was performed into existing models for adaptive mobile notification systems using context awareness. The literature study identified several potential models but no way to evaluate and compare the models. A set of requirements to evaluate these models was developed and the models were evaluated against these criteria. The model satisfying the most requirements was adapted so as to satisfy the remaining criteria. The proposed model is extensible in terms of the modes, devices and notification sources supported. The proposed model determines the importance of a message, the appropriate device and mode (or modes) of communication based on the user‘s context, and alerts the user of the message using these modes. A prototype was developed as a proof-of-concept of the proposed model and evaluated by conducting an extensive field study. The field study highlighted the fact that most users did not choose the most suitable mode for the context during their initial subscription to the service. The field study also showed that more research needs to be done on an appropriate filtering mechanism for notifications. Users found that the notifications became intrusive and less useful the longer they used them.
- Full Text:
- Date Issued: 2007
- Authors: Brander, William
- Date: 2007
- Subjects: Mobile computing , Context-aware computing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10473 , http://hdl.handle.net/10948/699 , Mobile computing , Context-aware computing
- Description: Information is useless unless it is used whilst still applicable. Having a system that notifies the user of important messages using the most appropriate medium and device will benefit users that rely on time critical information. There are several existing systems and models for mobile notification as well as for adaptive mobile notification using context awareness. Current models and systems are typically designed for a specific set of mobile devices, modes and services. Communication however, can take place in many different modes, across many different devices and may originate from many different sources. The aim of this research was to develop a model for adaptive mobile notification using context awareness. An extensive literature study was performed into existing models for adaptive mobile notification systems using context awareness. The literature study identified several potential models but no way to evaluate and compare the models. A set of requirements to evaluate these models was developed and the models were evaluated against these criteria. The model satisfying the most requirements was adapted so as to satisfy the remaining criteria. The proposed model is extensible in terms of the modes, devices and notification sources supported. The proposed model determines the importance of a message, the appropriate device and mode (or modes) of communication based on the user‘s context, and alerts the user of the message using these modes. A prototype was developed as a proof-of-concept of the proposed model and evaluated by conducting an extensive field study. The field study highlighted the fact that most users did not choose the most suitable mode for the context during their initial subscription to the service. The field study also showed that more research needs to be done on an appropriate filtering mechanism for notifications. Users found that the notifications became intrusive and less useful the longer they used them.
- Full Text:
- Date Issued: 2007
An intelligent user interface model for contact centre operations
- Authors: Singh, Akash
- Date: 2007
- Subjects: User interfaces (Computer systems) , Human-computer interaction , Mobile computing , Customer services -- Management , Call centers -- Customer services
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10475 , http://hdl.handle.net/10948/d1011399 , User interfaces (Computer systems) , Human-computer interaction , Mobile computing , Customer services -- Management , Call centers -- Customer services
- Description: Contact Centres (CCs) are at the forefront of interaction between an organisation and its customers. Currently, 17 percent of all inbound calls are not resolved on the first call by the first agent attending to that call. This is due to the inability of the contact centre agents (CCAs) to diagnose customer queries and find adequate solutions in an effective and efficient manner. The aim of this research is to develop an intelligent user interface (IUI) model to support and improve CC operations. A literature review of existing IUI architectures, modelbased design and existing CC software together with a field study of CCs has resulted in the design of an IUI model for CCs. The proposed IUI model is described in terms of its architecture, component-level design and interface design. An IUI prototype has been developed as a proof of concept of the proposed IUI model. The IUI prototype was evaluated in order to determine to what extent it supports problem identification and query resolution. User testing, incorporating the use of eye tracking and a post-test questionnaire, was used in order to determine the usability and usefulness of the prototype. The results of this evaluation show that the users were highly satisfied with the task support and query resolution assistance provided by the IUI prototype. This research resulted in the design of an IUI model for the domain of CCs. This model can be used to assist the development of CC applications incorporating IUIs. Use of the proposed IUI model is expected to support and enhance the effectiveness and efficiency of CC operations. Further research is needed to conduct a longitudinal study to determine the impact of IUIs in the CC domain.
- Full Text:
- Date Issued: 2007
- Authors: Singh, Akash
- Date: 2007
- Subjects: User interfaces (Computer systems) , Human-computer interaction , Mobile computing , Customer services -- Management , Call centers -- Customer services
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10475 , http://hdl.handle.net/10948/d1011399 , User interfaces (Computer systems) , Human-computer interaction , Mobile computing , Customer services -- Management , Call centers -- Customer services
- Description: Contact Centres (CCs) are at the forefront of interaction between an organisation and its customers. Currently, 17 percent of all inbound calls are not resolved on the first call by the first agent attending to that call. This is due to the inability of the contact centre agents (CCAs) to diagnose customer queries and find adequate solutions in an effective and efficient manner. The aim of this research is to develop an intelligent user interface (IUI) model to support and improve CC operations. A literature review of existing IUI architectures, modelbased design and existing CC software together with a field study of CCs has resulted in the design of an IUI model for CCs. The proposed IUI model is described in terms of its architecture, component-level design and interface design. An IUI prototype has been developed as a proof of concept of the proposed IUI model. The IUI prototype was evaluated in order to determine to what extent it supports problem identification and query resolution. User testing, incorporating the use of eye tracking and a post-test questionnaire, was used in order to determine the usability and usefulness of the prototype. The results of this evaluation show that the users were highly satisfied with the task support and query resolution assistance provided by the IUI prototype. This research resulted in the design of an IUI model for the domain of CCs. This model can be used to assist the development of CC applications incorporating IUIs. Use of the proposed IUI model is expected to support and enhance the effectiveness and efficiency of CC operations. Further research is needed to conduct a longitudinal study to determine the impact of IUIs in the CC domain.
- Full Text:
- Date Issued: 2007
In vitro testing to investigate the anticoagulant/antithrombotic and antidiabetic biological activity of Leonotis Leonurus
- Authors: Mnonopi, Nandipha Olivia
- Date: 2007
- Subjects: Leonotis leonurus -- Physiological aspects , Medicinal plants -- South Africa , Materia medica, Vegetable -- South Africa , Plant bioactive compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10331 , http://hdl.handle.net/10948/693 , Leonotis leonurus -- Physiological aspects , Medicinal plants -- South Africa , Materia medica, Vegetable -- South Africa , Plant bioactive compounds
- Description: The rising costs of prescription drugs in the maintenance of personal health and wellbeing have increased the interest in medicinal plants. The World Health Organization estimates that 65 percent-80 percent of the world’s population use traditional medicine as their primary form of health care. In this project the focus has been on the use of Leonotis leonurus extracts as a traditional medicine. The major chemical constituent of this plant is marrubiin, which is a diterpenoid labdane lactone formed from a precursor called premarrubiin. Aqueous and acetone extract (AL and OL extract, respectively) of this plant has been found to have an antithrombotic effect, with IC50 values of 3mg/ml and 6mg/ml, respectively. The extracts also have an effect on fibrinolysis, where the lysis time was decreased by more than 50 percent by the organic extract and standard marrubiin. In whole blood ADP-induced platelet aggregation, the organic extract inhibited aggregation by 68 percent at a final concentration of 138μg/ml (equivalent to 7.2μg/ml marrubiin). Marrubiin has also been screened for antithrombotic/anticoagulant activity; no antithrombotic activity has been observed but it increased the rate of fibrinolysis, by decreasing lysis time by 64 percent and also decreasing fibrin formation. From these findings it can be concluded that marrubiin has a fibrinolytic effect and antiplatelet aggregation effect. In the diabetic studies, in hyperglycemic condition, the OL (10μg/ml) extract and standard marrubiin significantly increased insulin secretion by 200 percent (2-fold) and 400 percent (4-fold), respectively, with respect to the control. The OL extract and standard marrubiin stimulated the release of insulin, the stimulatory index was significantly increased by 450 percent (4.5-fold) and 500 percent (5-fold), respectively, with respect to the control. In the apoptotic studies, in the normoglycemic and hyperglycemic conditions, the OL extract decreased the occurrence of apoptosis, in a dose-dependent manner, with the lower concentrations inducing apoptosis significantly higher than the relevant controls. Standard marrubiin did not have an effect on apoptosis in hyperglycemic condition, but it decreased the occurrence of apoptosis by 200 percent (2-fold) under normoglycemic conditions. The OL extract increased proliferation by 148 percent (1.48- fold) and 155 percent (1.55-fold) in normoglycemic and hyperglycemic conditions, respectively. The same effect was observed for standard marrubiin, where, proliferation was increased by 180 percent (1.8-fold) and 200 percent (2.0-fold) in normoglycemic and hyperglycemic conditions, respectively. RT-PCR displayed that standard marrubiin inhibited the expression of insulin by 50 percent under normoglycemic conditions.
- Full Text:
- Date Issued: 2007
- Authors: Mnonopi, Nandipha Olivia
- Date: 2007
- Subjects: Leonotis leonurus -- Physiological aspects , Medicinal plants -- South Africa , Materia medica, Vegetable -- South Africa , Plant bioactive compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10331 , http://hdl.handle.net/10948/693 , Leonotis leonurus -- Physiological aspects , Medicinal plants -- South Africa , Materia medica, Vegetable -- South Africa , Plant bioactive compounds
- Description: The rising costs of prescription drugs in the maintenance of personal health and wellbeing have increased the interest in medicinal plants. The World Health Organization estimates that 65 percent-80 percent of the world’s population use traditional medicine as their primary form of health care. In this project the focus has been on the use of Leonotis leonurus extracts as a traditional medicine. The major chemical constituent of this plant is marrubiin, which is a diterpenoid labdane lactone formed from a precursor called premarrubiin. Aqueous and acetone extract (AL and OL extract, respectively) of this plant has been found to have an antithrombotic effect, with IC50 values of 3mg/ml and 6mg/ml, respectively. The extracts also have an effect on fibrinolysis, where the lysis time was decreased by more than 50 percent by the organic extract and standard marrubiin. In whole blood ADP-induced platelet aggregation, the organic extract inhibited aggregation by 68 percent at a final concentration of 138μg/ml (equivalent to 7.2μg/ml marrubiin). Marrubiin has also been screened for antithrombotic/anticoagulant activity; no antithrombotic activity has been observed but it increased the rate of fibrinolysis, by decreasing lysis time by 64 percent and also decreasing fibrin formation. From these findings it can be concluded that marrubiin has a fibrinolytic effect and antiplatelet aggregation effect. In the diabetic studies, in hyperglycemic condition, the OL (10μg/ml) extract and standard marrubiin significantly increased insulin secretion by 200 percent (2-fold) and 400 percent (4-fold), respectively, with respect to the control. The OL extract and standard marrubiin stimulated the release of insulin, the stimulatory index was significantly increased by 450 percent (4.5-fold) and 500 percent (5-fold), respectively, with respect to the control. In the apoptotic studies, in the normoglycemic and hyperglycemic conditions, the OL extract decreased the occurrence of apoptosis, in a dose-dependent manner, with the lower concentrations inducing apoptosis significantly higher than the relevant controls. Standard marrubiin did not have an effect on apoptosis in hyperglycemic condition, but it decreased the occurrence of apoptosis by 200 percent (2-fold) under normoglycemic conditions. The OL extract increased proliferation by 148 percent (1.48- fold) and 155 percent (1.55-fold) in normoglycemic and hyperglycemic conditions, respectively. The same effect was observed for standard marrubiin, where, proliferation was increased by 180 percent (1.8-fold) and 200 percent (2.0-fold) in normoglycemic and hyperglycemic conditions, respectively. RT-PCR displayed that standard marrubiin inhibited the expression of insulin by 50 percent under normoglycemic conditions.
- Full Text:
- Date Issued: 2007
On the microstructure and physical properties of hot pressed (Hf, Ti) C
- Authors: Heiligers, Christiané
- Date: 2007
- Subjects: Transition metal carbides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10532 , http://hdl.handle.net/10948/523 , http://hdl.handle.net/10948/d1011722 , Transition metal carbides
- Description: The microstructure and physical properties of hot pressed (Hf, Ti) C have been investigated with the aim of producing a cutting tool material with similar hardness to that of WC-Co and TiC-based cermets. Sintered samples were hot pressed from HfC0.7 and TiC0.9 powders using powder metallurgical techniques and the processing cycle was optimized for this system. Ni was used as a binder in selected samples and C black was added to compensate for sub-stoichiometry and to aid in the reduction of oxides formed during milling. Microstructural analyses were performed by scanning and transmission electron microscopy (SEM and TEM) and the composition was determined from X-ray diffraction (XRD) and energy dispersive X-ray spectrometry (EDS). The physical properties measured are density and Vickers hardness, and the indentation fracture toughness was determined using the Shetty formula. The fundamental interactions between HfC, TiC and Ni during hot pressing were investigated and the results obtained used to explain the microstructure that develops in samples made from powder mixtures. The interactions studied are the inter-diffusion of HfC and TiC through the solid state, and the dissolution and re-precipitation rate of the carbides in a liquid Ni binder. EDS analysis revealed that the rate at which Ti diffuses into HfC is higher than the rate at which Hf diffuses into TiC. Upper limits to the diffusion coefficients for these processes are determined and show that solid solution carbides will form from HfC + TiC powder mixtures at 2000 ºC in 1 hour if the average powder particle size is less than 5 μm. The diffusion rates decrease with a decrease in hot pressing temperature but mass transport between the phases can be enhanced by addition of a metallic binder. TEM and EDS analysis shows that Ni wets TiC more efficiently than HfC and that the solubility of TiC in Ni is also higher than that of HfC. The grain size of the carbide phases increases with an increase in the rate at which they dissolve into and re-precipitate from the liquid binder. The crystal structure of the binder phase depends on the concentration of Ti and Hf that remain in the binder after cooling and the carbide phase in which the binder is embedded. Analysis of TEM electron diffraction patterns show that the binder phase consists of cubic solid solutions as well as intermetallic and cubic phases in which atomic ordering is observed.
- Full Text:
- Date Issued: 2007
- Authors: Heiligers, Christiané
- Date: 2007
- Subjects: Transition metal carbides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10532 , http://hdl.handle.net/10948/523 , http://hdl.handle.net/10948/d1011722 , Transition metal carbides
- Description: The microstructure and physical properties of hot pressed (Hf, Ti) C have been investigated with the aim of producing a cutting tool material with similar hardness to that of WC-Co and TiC-based cermets. Sintered samples were hot pressed from HfC0.7 and TiC0.9 powders using powder metallurgical techniques and the processing cycle was optimized for this system. Ni was used as a binder in selected samples and C black was added to compensate for sub-stoichiometry and to aid in the reduction of oxides formed during milling. Microstructural analyses were performed by scanning and transmission electron microscopy (SEM and TEM) and the composition was determined from X-ray diffraction (XRD) and energy dispersive X-ray spectrometry (EDS). The physical properties measured are density and Vickers hardness, and the indentation fracture toughness was determined using the Shetty formula. The fundamental interactions between HfC, TiC and Ni during hot pressing were investigated and the results obtained used to explain the microstructure that develops in samples made from powder mixtures. The interactions studied are the inter-diffusion of HfC and TiC through the solid state, and the dissolution and re-precipitation rate of the carbides in a liquid Ni binder. EDS analysis revealed that the rate at which Ti diffuses into HfC is higher than the rate at which Hf diffuses into TiC. Upper limits to the diffusion coefficients for these processes are determined and show that solid solution carbides will form from HfC + TiC powder mixtures at 2000 ºC in 1 hour if the average powder particle size is less than 5 μm. The diffusion rates decrease with a decrease in hot pressing temperature but mass transport between the phases can be enhanced by addition of a metallic binder. TEM and EDS analysis shows that Ni wets TiC more efficiently than HfC and that the solubility of TiC in Ni is also higher than that of HfC. The grain size of the carbide phases increases with an increase in the rate at which they dissolve into and re-precipitate from the liquid binder. The crystal structure of the binder phase depends on the concentration of Ti and Hf that remain in the binder after cooling and the carbide phase in which the binder is embedded. Analysis of TEM electron diffraction patterns show that the binder phase consists of cubic solid solutions as well as intermetallic and cubic phases in which atomic ordering is observed.
- Full Text:
- Date Issued: 2007