A critical realist exploration of the implementation of a new curriculum in Swaziland
- Authors: Pereira, Liphie
- Date: 2012
- Subjects: Critical realism Education -- Philosophy Critical pedagogy -- Swaziland Curriculum change -- Swaziland Education -- Swaziland Education and state -- Swaziland Education -- Aims and objectives -- Swaziland Critical discourse analysis International General Certificate of Secondary Education
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1484 , http://hdl.handle.net/10962/d1003365
- Description: This study offers an in-depth exploration of the conditions from which the implementation of a curriculum called the International General Certificate of Secondary Education (IGCSE), later localised into Swaziland General Certificate of Secondary Education (SGCSE), emerged and the constraining and enabling conditions for the implementation of the new I/SGCSE curriculum. It derives its theoretical foundation from Roy Bhaskar’s critical realism and Margaret Archer’s concept of analytical separability. The study therefore offers explanations about the curriculum change and its implementation that are based on how structural, cultural, and agential mechanisms operating at a deeper level of reality (the intransitive layer of reality or the domain of the real) and existing independently of what we see, know or believe of them (the transitive layer of reality or domains of the actual and empirical) interacted to condition the emergence of I/SGCSE and the way it is implemented. I conduct a critical discourse analysis of relevant literature, I/SGCSE documents and interview data in order to identify those mechanisms that were cultural and also those that were structural and agential. Bernstein’s concepts of classification and framing are used to analyse observation data in order to explore the influence of these mechanisms on the teaching practices of the teachers who took part in the study. Analysis of the data suggests that the change from General Certificate of Education Ordinary Level (GCE O-level) to I/SGCSE was conditioned by inconsistencies between the cultural and structural mechanisms of the Swazi context. Many of the cultural elements of the Swazi context such as the discourses of good citizens, of competitive advantage, and of quality education draw from global discourses which view relations between people from a postmodernist position and therefore support weakly classified and framed pedagogic practices. In contrast, the discourse of morality and many of the structural elements of the Swazi context, such as the pre2006 education system and the Tinkhundla government system, all view reality from a modernist position, therefore supporting strong relations of power and control. The cultural system therefore exerted more influence in conditioning the change from the strongly classified and framed GCE O-level curriculum to the weakly classified and framed I/SGCSE curriculum. Furthermore, the analysis of interview and observation data suggests that inconsistencies between the global discourses and the discourses and structures that teachers confront in their day-to-day lives, together with the decisions teachers made in response to structural constraints, created constraining conditions for the change from GCE O-level to I/SGCSE. The study adds to knowledge on curriculum change and implementation through insights into the enabling and constraining effects of mechanisms operating at a deeper level of reality on curriculum-change decisions and on the ability of teachers to implement curriculum changes. The focus on the deeper level of reality may therefore contribute towards emancipatory knowledge which could be used not only by the Ministry of Education and Training and teachers in Swaziland but also elsewhere to inform future planning, decision making, and practice in relation to curriculum change and implementation.
- Full Text:
- Date Issued: 2012
- Authors: Pereira, Liphie
- Date: 2012
- Subjects: Critical realism Education -- Philosophy Critical pedagogy -- Swaziland Curriculum change -- Swaziland Education -- Swaziland Education and state -- Swaziland Education -- Aims and objectives -- Swaziland Critical discourse analysis International General Certificate of Secondary Education
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1484 , http://hdl.handle.net/10962/d1003365
- Description: This study offers an in-depth exploration of the conditions from which the implementation of a curriculum called the International General Certificate of Secondary Education (IGCSE), later localised into Swaziland General Certificate of Secondary Education (SGCSE), emerged and the constraining and enabling conditions for the implementation of the new I/SGCSE curriculum. It derives its theoretical foundation from Roy Bhaskar’s critical realism and Margaret Archer’s concept of analytical separability. The study therefore offers explanations about the curriculum change and its implementation that are based on how structural, cultural, and agential mechanisms operating at a deeper level of reality (the intransitive layer of reality or the domain of the real) and existing independently of what we see, know or believe of them (the transitive layer of reality or domains of the actual and empirical) interacted to condition the emergence of I/SGCSE and the way it is implemented. I conduct a critical discourse analysis of relevant literature, I/SGCSE documents and interview data in order to identify those mechanisms that were cultural and also those that were structural and agential. Bernstein’s concepts of classification and framing are used to analyse observation data in order to explore the influence of these mechanisms on the teaching practices of the teachers who took part in the study. Analysis of the data suggests that the change from General Certificate of Education Ordinary Level (GCE O-level) to I/SGCSE was conditioned by inconsistencies between the cultural and structural mechanisms of the Swazi context. Many of the cultural elements of the Swazi context such as the discourses of good citizens, of competitive advantage, and of quality education draw from global discourses which view relations between people from a postmodernist position and therefore support weakly classified and framed pedagogic practices. In contrast, the discourse of morality and many of the structural elements of the Swazi context, such as the pre2006 education system and the Tinkhundla government system, all view reality from a modernist position, therefore supporting strong relations of power and control. The cultural system therefore exerted more influence in conditioning the change from the strongly classified and framed GCE O-level curriculum to the weakly classified and framed I/SGCSE curriculum. Furthermore, the analysis of interview and observation data suggests that inconsistencies between the global discourses and the discourses and structures that teachers confront in their day-to-day lives, together with the decisions teachers made in response to structural constraints, created constraining conditions for the change from GCE O-level to I/SGCSE. The study adds to knowledge on curriculum change and implementation through insights into the enabling and constraining effects of mechanisms operating at a deeper level of reality on curriculum-change decisions and on the ability of teachers to implement curriculum changes. The focus on the deeper level of reality may therefore contribute towards emancipatory knowledge which could be used not only by the Ministry of Education and Training and teachers in Swaziland but also elsewhere to inform future planning, decision making, and practice in relation to curriculum change and implementation.
- Full Text:
- Date Issued: 2012
Farm level institutions in emergent communities in post fast track Zimbabwe: case of Mazowe district
- Authors: Chiweshe, Manase Kudzai
- Date: 2012
- Subjects: Land reform -- Zimbabwe -- History -- 21st century Land settlement -- Social aspects -- Zimbabwe Zimbabwe -- Social conditions -- 1980- Zimbabwe -- Economic conditions Zimbabwe -- Politics and government -- 1980-
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3308 , http://hdl.handle.net/10962/d1003096
- Description: The thesis seeks to understand how emerging communities borne out of the Fast Track Land Reform Programme in Zimbabwe have been able to ensure social cohesion and social service provision using farm level institutions. The Fast Track Programme brought together people from diverse backgrounds into new communities in the former commercial farming areas. The formation of new communities meant that, often, there were 'stranger households'living next to each other. Since 2000, these people have been involved in various processes aimed at turning clusters of homesteads into functioning communities through farm level institutions. Fast track land reform precipitated economic and political crisis in Zimbabwe characterised by a rapidly devaluating Zimbabwean dollar, enormous inflation and high unemployment figures. This economic crisis has impacted heavily on new farmers who find it increasingly difficult to afford inputs and access loans. They have formed social networks in response to these challenges, taking the form of farm level institutions such as farm committees, irrigation committees and health committees. The study uses case studies from small-scale 'A1 farmers‘ in Mazowe district which is in Mashonaland Central Province. It employs qualitative methodologies to enable a nuanced understanding of associational life in the new communities. Through focus group discussions, in-depth interviews, narratives, key informant interviews and institutional mapping the study outlines the formation, taxonomy, activities, roles, internal dynamics and social organisation of farm level institutions. The study also uses secondary data collected in 2007-08 by the Centre for Rural Development in the newly resettled areas in Mazowe. The major finding of the study is that farmers are organising in novel ways at grassroots levels to meet everyday challenges. These institutional forms however are internally weak, lacking leadership with a clear vision and they appear as if they are transitory in nature. They remain marginalised from national and global processes and isolated from critical connections to policy makers at all levels; thus A1 farmers remain voiceless and unable to have their interests addressed. Farm level institutions are at the forefront of the microeconomics of survival among these rural farmers. They are survivalist in nature and form, and this requires a major shift in focus if they are to be involved in developmental work. The institutions remain fragmented and compete amongst themselves for services from government without uniting as A1 farmers with similar interests and challenges.
- Full Text:
- Date Issued: 2012
Farm level institutions in emergent communities in post fast track Zimbabwe: case of Mazowe district
- Authors: Chiweshe, Manase Kudzai
- Date: 2012
- Subjects: Land reform -- Zimbabwe -- History -- 21st century Land settlement -- Social aspects -- Zimbabwe Zimbabwe -- Social conditions -- 1980- Zimbabwe -- Economic conditions Zimbabwe -- Politics and government -- 1980-
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3308 , http://hdl.handle.net/10962/d1003096
- Description: The thesis seeks to understand how emerging communities borne out of the Fast Track Land Reform Programme in Zimbabwe have been able to ensure social cohesion and social service provision using farm level institutions. The Fast Track Programme brought together people from diverse backgrounds into new communities in the former commercial farming areas. The formation of new communities meant that, often, there were 'stranger households'living next to each other. Since 2000, these people have been involved in various processes aimed at turning clusters of homesteads into functioning communities through farm level institutions. Fast track land reform precipitated economic and political crisis in Zimbabwe characterised by a rapidly devaluating Zimbabwean dollar, enormous inflation and high unemployment figures. This economic crisis has impacted heavily on new farmers who find it increasingly difficult to afford inputs and access loans. They have formed social networks in response to these challenges, taking the form of farm level institutions such as farm committees, irrigation committees and health committees. The study uses case studies from small-scale 'A1 farmers‘ in Mazowe district which is in Mashonaland Central Province. It employs qualitative methodologies to enable a nuanced understanding of associational life in the new communities. Through focus group discussions, in-depth interviews, narratives, key informant interviews and institutional mapping the study outlines the formation, taxonomy, activities, roles, internal dynamics and social organisation of farm level institutions. The study also uses secondary data collected in 2007-08 by the Centre for Rural Development in the newly resettled areas in Mazowe. The major finding of the study is that farmers are organising in novel ways at grassroots levels to meet everyday challenges. These institutional forms however are internally weak, lacking leadership with a clear vision and they appear as if they are transitory in nature. They remain marginalised from national and global processes and isolated from critical connections to policy makers at all levels; thus A1 farmers remain voiceless and unable to have their interests addressed. Farm level institutions are at the forefront of the microeconomics of survival among these rural farmers. They are survivalist in nature and form, and this requires a major shift in focus if they are to be involved in developmental work. The institutions remain fragmented and compete amongst themselves for services from government without uniting as A1 farmers with similar interests and challenges.
- Full Text:
- Date Issued: 2012
Assessing the impacts of invasive non-native African sharptooth catfish Clarias Gariepinus
- Authors: Kadye, Wilbert Takawira
- Date: 2012
- Subjects: Catfishes -- South Africa -- Eastern Cape Biological invasions -- South Africa -- Great Fish River Biological invasions -- South Africa -- Sundays River Clarias gariepinus Freshwater ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5227 , http://hdl.handle.net/10962/d1005070
- Description: Invasive species are of particular concern as they have the potential to alter community structure and food web relationships within their invaded habitats. African sharptooth catfish Clarias gariepinus, a generalist predator, was introduced through an inter-basin water transfer scheme into the Great Fish and Sundays Rivers, Eastern Cape, South Africa, where it threatens the native riverine biota. This thesis assessed its impact from a trophic perspective. Patterns in catfish distribution and abundance revealed an upstream to downstream gradient that was associated with spatial distribution of most species within the mainstream, and a mainstream to tributary gradient that was associated with the spatial distribution of native minnows. The catfish was predicted to occur widely within the mainstem habitats and to decrease progressively along the mainstrem to tributary gradient with the physico-chemical environment being a good proxy for predicting both its occurrence and abundance. The results suggest the catfish proliferated within mainstem habitats where invasion resistance was possibly reduced due to alteration of flow. Population dynamics and size structuring of two native cyprinid minnows Pseudobarbus afer and Barbus anoplus, threatened by catfish, were examined within uninvaded headwater streams in relation to their proximate physical habitats. Their habitats were characterised by seasonal variation in physico-chemical conditions and a spatial variation in substrata compositions. No evidence of differences was found between seasons for density and capture probability for either species. The population size and density for P. afer was found to increase with increasing proportion of boulders. In comparison, B. anoplus population size and probability of capture increased with increasing proportion of bedrock and bank vegetation, respectively. Size structuring was explained predominantly by seasonality and habitat variables for P. afer and B. anoplus, respectively. Stable isotope ratios of carbon and nitrogen were used to compare the spatial variation in both the community-wide and catfish-specific niches and to estimate catfish prey sources from different habitats within the invaded systems. Aquatic community and catfish niches were statistically different among localities, suggesting that each locality had a distinct community-wide trophic structure. Dispersion metrics indicated no evidence of differences in the clustering among individuals, but provided evidence of differences in path trajectories for the comparisons of catfish populations that suggested dietary plasticity within different localities. Dietary studies revealed both ontogenetic shift and omnivory that suggested that catfish may exhibit less pronounced top-down effects within its invaded habitats. Manipulative experiments were used to test the response of benthic macroinvertebrates within two rivers that were differentially impacted by catfish as a presstype disturbance. Macroinvertebrates were non-responsive to catfish presence within a system where catfish had previously been established. In contrast, excluding catfish in this system indicated a response that suggested the importance of refuge within invaded habitats and the possible recovery pattern of certain macroinvertebrate taxa. By comparison, introduction of catfish within previously uninvaded localities provided evidence of direct catfish impact through elimination of conspicuous taxa. Acoustic telemetry was used to investigate catfish movement patterns within an invaded lentic habitat and provided evidence that habitat utilisation was non-random. The shallow and structured river mouth habitat, which was most utilised, was probably the most ideal for its breeding and feeding. This inferred potential overlap with native species and suggested the risk of predation and competitive interference. Catfish also exhibited both nocturnal and diurnal activity patterns that were probably related to feeding.
- Full Text:
- Date Issued: 2012
- Authors: Kadye, Wilbert Takawira
- Date: 2012
- Subjects: Catfishes -- South Africa -- Eastern Cape Biological invasions -- South Africa -- Great Fish River Biological invasions -- South Africa -- Sundays River Clarias gariepinus Freshwater ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5227 , http://hdl.handle.net/10962/d1005070
- Description: Invasive species are of particular concern as they have the potential to alter community structure and food web relationships within their invaded habitats. African sharptooth catfish Clarias gariepinus, a generalist predator, was introduced through an inter-basin water transfer scheme into the Great Fish and Sundays Rivers, Eastern Cape, South Africa, where it threatens the native riverine biota. This thesis assessed its impact from a trophic perspective. Patterns in catfish distribution and abundance revealed an upstream to downstream gradient that was associated with spatial distribution of most species within the mainstream, and a mainstream to tributary gradient that was associated with the spatial distribution of native minnows. The catfish was predicted to occur widely within the mainstem habitats and to decrease progressively along the mainstrem to tributary gradient with the physico-chemical environment being a good proxy for predicting both its occurrence and abundance. The results suggest the catfish proliferated within mainstem habitats where invasion resistance was possibly reduced due to alteration of flow. Population dynamics and size structuring of two native cyprinid minnows Pseudobarbus afer and Barbus anoplus, threatened by catfish, were examined within uninvaded headwater streams in relation to their proximate physical habitats. Their habitats were characterised by seasonal variation in physico-chemical conditions and a spatial variation in substrata compositions. No evidence of differences was found between seasons for density and capture probability for either species. The population size and density for P. afer was found to increase with increasing proportion of boulders. In comparison, B. anoplus population size and probability of capture increased with increasing proportion of bedrock and bank vegetation, respectively. Size structuring was explained predominantly by seasonality and habitat variables for P. afer and B. anoplus, respectively. Stable isotope ratios of carbon and nitrogen were used to compare the spatial variation in both the community-wide and catfish-specific niches and to estimate catfish prey sources from different habitats within the invaded systems. Aquatic community and catfish niches were statistically different among localities, suggesting that each locality had a distinct community-wide trophic structure. Dispersion metrics indicated no evidence of differences in the clustering among individuals, but provided evidence of differences in path trajectories for the comparisons of catfish populations that suggested dietary plasticity within different localities. Dietary studies revealed both ontogenetic shift and omnivory that suggested that catfish may exhibit less pronounced top-down effects within its invaded habitats. Manipulative experiments were used to test the response of benthic macroinvertebrates within two rivers that were differentially impacted by catfish as a presstype disturbance. Macroinvertebrates were non-responsive to catfish presence within a system where catfish had previously been established. In contrast, excluding catfish in this system indicated a response that suggested the importance of refuge within invaded habitats and the possible recovery pattern of certain macroinvertebrate taxa. By comparison, introduction of catfish within previously uninvaded localities provided evidence of direct catfish impact through elimination of conspicuous taxa. Acoustic telemetry was used to investigate catfish movement patterns within an invaded lentic habitat and provided evidence that habitat utilisation was non-random. The shallow and structured river mouth habitat, which was most utilised, was probably the most ideal for its breeding and feeding. This inferred potential overlap with native species and suggested the risk of predation and competitive interference. Catfish also exhibited both nocturnal and diurnal activity patterns that were probably related to feeding.
- Full Text:
- Date Issued: 2012
Narrating emergence in the curious terrain of academic development research: a realist perspective
- Authors: Niven, Penelope Mary
- Date: 2012
- Subjects: Education, Higher -- Aims and objectives -- South Africa Universities and colleges -- South Africa Educational change -- South Africa Black people -- Education (Higher) -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1675 , http://hdl.handle.net/10962/d1003558
- Description: This dissertation adopts a realist meta-perspective on a body of the scholar's own research papers written between 2005 and 2011, all either published or in press and offered for reference in the Appendices. The six papers represent the point of departure for the thesis; they are the phenomenon for further investigation into 'what must be the case' for the research events to have emerged as they did. One aspect of this study, therefore, is an auto ethnographic account of conducting research in the field of Academic Development within varied settings and over a given time frame. But alongside this personal history it narrates cycles in the Academic Development movement in South Africa over 30 years. Margaret Archer's Social Realist principle of analytical dualism (1995) is used to disaggregate the emergent properties within these histories and to enable an analysis of the underlying mechanisms that generated them. It refers to three social domains. Firstly, it describes the material structures - the institutional environments, policies, roles or professional conditions - in which the projects were conceived. Secondly, it identifies the cultural registers that the profession was drawing on - such as theories, beliefs or discourses. Thirdly, it draws attention to the agency of individuals and communities in the field as they independently activated or mediated these various conditioning structures and registers. So the study is a systematic examination of the parts and the people in research stories, of the complex interrelationship of structural and agential elements, and of how together they have generated particular forms of knowing and kinds of knowledge in Academic Development. Drawing from this 'history-within-a-history', the study makes some claims for 'what must be the case' for substantial knowledge to flourish in a newly emergent, hotly contested and relatively unstable field. It argues that Academic Development has few shared epistemological foundations and boundaries, and its roles and functions are shifting and diverse. It describes the tensions in the field between those who have been inclined to understand it as primarily concerned with redress or equity in the postapartheid state, and yet others who have prioritised Academic Development as an efficiency project within higher education. But there is a third discourse emanating from those in the profession who have consistently argued that neither of these approaches can succeed without drawing on stronger theoretical foundations. This study endorses the view that Academic Developers need to identify more coherent ontological and epistemological frames for their research work. This has important implications for building the kind of substantial knowledge base that could be more influential in addressing the troubled terrain of South African higher education. The study refers extensively to Lewis Carroll's Alice in Wonderland (1865) and Through the Looking-Glass (1871) and to Mervyn Peake's 1946 illustrations of these children's stories, finding in these texts powerful analogies and metaphors for principles in realist philosophy and theory, and for describing a researcher's journey towards a more assured identity in the curious field of Academic Development.
- Full Text:
- Date Issued: 2012
- Authors: Niven, Penelope Mary
- Date: 2012
- Subjects: Education, Higher -- Aims and objectives -- South Africa Universities and colleges -- South Africa Educational change -- South Africa Black people -- Education (Higher) -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1675 , http://hdl.handle.net/10962/d1003558
- Description: This dissertation adopts a realist meta-perspective on a body of the scholar's own research papers written between 2005 and 2011, all either published or in press and offered for reference in the Appendices. The six papers represent the point of departure for the thesis; they are the phenomenon for further investigation into 'what must be the case' for the research events to have emerged as they did. One aspect of this study, therefore, is an auto ethnographic account of conducting research in the field of Academic Development within varied settings and over a given time frame. But alongside this personal history it narrates cycles in the Academic Development movement in South Africa over 30 years. Margaret Archer's Social Realist principle of analytical dualism (1995) is used to disaggregate the emergent properties within these histories and to enable an analysis of the underlying mechanisms that generated them. It refers to three social domains. Firstly, it describes the material structures - the institutional environments, policies, roles or professional conditions - in which the projects were conceived. Secondly, it identifies the cultural registers that the profession was drawing on - such as theories, beliefs or discourses. Thirdly, it draws attention to the agency of individuals and communities in the field as they independently activated or mediated these various conditioning structures and registers. So the study is a systematic examination of the parts and the people in research stories, of the complex interrelationship of structural and agential elements, and of how together they have generated particular forms of knowing and kinds of knowledge in Academic Development. Drawing from this 'history-within-a-history', the study makes some claims for 'what must be the case' for substantial knowledge to flourish in a newly emergent, hotly contested and relatively unstable field. It argues that Academic Development has few shared epistemological foundations and boundaries, and its roles and functions are shifting and diverse. It describes the tensions in the field between those who have been inclined to understand it as primarily concerned with redress or equity in the postapartheid state, and yet others who have prioritised Academic Development as an efficiency project within higher education. But there is a third discourse emanating from those in the profession who have consistently argued that neither of these approaches can succeed without drawing on stronger theoretical foundations. This study endorses the view that Academic Developers need to identify more coherent ontological and epistemological frames for their research work. This has important implications for building the kind of substantial knowledge base that could be more influential in addressing the troubled terrain of South African higher education. The study refers extensively to Lewis Carroll's Alice in Wonderland (1865) and Through the Looking-Glass (1871) and to Mervyn Peake's 1946 illustrations of these children's stories, finding in these texts powerful analogies and metaphors for principles in realist philosophy and theory, and for describing a researcher's journey towards a more assured identity in the curious field of Academic Development.
- Full Text:
- Date Issued: 2012
The economics of converting a sheep farm into a springbuck (Antidorcas marsupialis) ranch in Graaff-Reinet: a simulation analysis
- Authors: Dlamini, Thula Sizwe
- Date: 2012
- Subjects: Livestock projects -- South Africa -- Eastern Cape Livestock productivity -- South Africa -- Eastern Cape Livestock -- Economic aspects -- South Africa -- Eastern Cape Sheep -- Breeding -- South Africa -- Eastern Cape Springbok -- Breeding -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1003 , http://hdl.handle.net/10962/d1002738
- Description: In Graaff-Reinet, domestic livestock farming and springbuck ranching are similar in that they both rely on the rangeland for their sustainability. However, as a consequence of repeated monotonous domestic livestock farming, resulting in compromised biological productivity and diversity, the rangelands have disintegrated. This, unfortunately, has placed the future sustainability of these rangelands and the livelihoods of the local people in an indeterminate state. In recent years, there has been an increasing interest in springbuck ranching for meat production as an alternative to domestic livestock farming in the area following (a) fears of worsening environmental challenges; (b) declining profitability in commercial domestic livestock farming and; (c) growing calls for the sustainable use of these rangelands for the benefit of future generations. The springbuck has emerged as a credible alternative to utilising the rangelands - as opposed to sheep - because of its promise to addressing the above challenges. This is in an attempt to tap into the multitude of benefits that the springbuck possesses (by virtue of being part of the natural capital of the area) that have a potential towards restoring ecological integrity by extenuating some of the detrimental effects of sheep farming on the rangelands and presenting opportunities for diversifying incomes. Yet, despite the general increase in interest, a resistance towards the uptake of springbuck ranching for meat production exists. The main contention is that springbuck meat production cannot out-perform the economic returns of wool sheep farming. This study attempts to address these concerns by investigating the profitability and economic sustainability of converting a sheep farm into a springbuck ranch in Graaff-Reinet. The study uses stochastic simulation to estimate the probability distribution of some key output variables, namely: net cash income, ending cash balance, real net worth and the net present value (NPV) in evaluating the profitability of converting a 5 000ha sheep-dominated farm into a springbuck-dominated ranch under three alternative scenarios. The use of stochastic simulation allows for the incorporation of downside risk associated with the production and marketing of wool, mutton and springbuck meat. The study uses stochastic prices and yields to calculate net returns variability. Incorporating scenario analysis helped to evaluate how alternative wool sheep-dominated and springbuck-dominated combinations would perform based on the probable outcomes of different assumptions in the various scenarios. By applying stochastic efficiency with respect to a function (SERF) criterion to the simulated NPVs, this study compares the profitability of alternative scenarios based on various risk aversion coefficients. The study finds that converting a 5 000ha wool sheep dominated farm into a springbuck dominated ranch could potentially be a more profitable investment than wool sheep farming over a 15 year planning horizon, in Graaff-Reinet. The SERF results indicate that for all scenarios tested, the best strategy of converting a wool sheep dominated farm into a springbuck ranch would be one which comprise a combination of 70% springbuck, 20% mutton and 10% wool production as the likely profitable enterprise mix. Using economic sustainability analysis, the study reveals that because of low costs in springbuck ranching, springbuck meat production enterprises are most likely to be more financially sustainable than wool sheep-dominated enterprises. This suggests that rangeland owners may be better off converting their wool sheep-dominated farms into springbuck-dominated ranches. Thus, as the call for more environmentally benign rangeland utilising economic-ecological systems intensifies, rangeland owners in the Eastern Cape Karoo have a practicable option. At the very least, there exists an option to broaden their incomes whilst promoting ecological restoration with springbuck meat production.
- Full Text:
- Date Issued: 2012
- Authors: Dlamini, Thula Sizwe
- Date: 2012
- Subjects: Livestock projects -- South Africa -- Eastern Cape Livestock productivity -- South Africa -- Eastern Cape Livestock -- Economic aspects -- South Africa -- Eastern Cape Sheep -- Breeding -- South Africa -- Eastern Cape Springbok -- Breeding -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1003 , http://hdl.handle.net/10962/d1002738
- Description: In Graaff-Reinet, domestic livestock farming and springbuck ranching are similar in that they both rely on the rangeland for their sustainability. However, as a consequence of repeated monotonous domestic livestock farming, resulting in compromised biological productivity and diversity, the rangelands have disintegrated. This, unfortunately, has placed the future sustainability of these rangelands and the livelihoods of the local people in an indeterminate state. In recent years, there has been an increasing interest in springbuck ranching for meat production as an alternative to domestic livestock farming in the area following (a) fears of worsening environmental challenges; (b) declining profitability in commercial domestic livestock farming and; (c) growing calls for the sustainable use of these rangelands for the benefit of future generations. The springbuck has emerged as a credible alternative to utilising the rangelands - as opposed to sheep - because of its promise to addressing the above challenges. This is in an attempt to tap into the multitude of benefits that the springbuck possesses (by virtue of being part of the natural capital of the area) that have a potential towards restoring ecological integrity by extenuating some of the detrimental effects of sheep farming on the rangelands and presenting opportunities for diversifying incomes. Yet, despite the general increase in interest, a resistance towards the uptake of springbuck ranching for meat production exists. The main contention is that springbuck meat production cannot out-perform the economic returns of wool sheep farming. This study attempts to address these concerns by investigating the profitability and economic sustainability of converting a sheep farm into a springbuck ranch in Graaff-Reinet. The study uses stochastic simulation to estimate the probability distribution of some key output variables, namely: net cash income, ending cash balance, real net worth and the net present value (NPV) in evaluating the profitability of converting a 5 000ha sheep-dominated farm into a springbuck-dominated ranch under three alternative scenarios. The use of stochastic simulation allows for the incorporation of downside risk associated with the production and marketing of wool, mutton and springbuck meat. The study uses stochastic prices and yields to calculate net returns variability. Incorporating scenario analysis helped to evaluate how alternative wool sheep-dominated and springbuck-dominated combinations would perform based on the probable outcomes of different assumptions in the various scenarios. By applying stochastic efficiency with respect to a function (SERF) criterion to the simulated NPVs, this study compares the profitability of alternative scenarios based on various risk aversion coefficients. The study finds that converting a 5 000ha wool sheep dominated farm into a springbuck dominated ranch could potentially be a more profitable investment than wool sheep farming over a 15 year planning horizon, in Graaff-Reinet. The SERF results indicate that for all scenarios tested, the best strategy of converting a wool sheep dominated farm into a springbuck ranch would be one which comprise a combination of 70% springbuck, 20% mutton and 10% wool production as the likely profitable enterprise mix. Using economic sustainability analysis, the study reveals that because of low costs in springbuck ranching, springbuck meat production enterprises are most likely to be more financially sustainable than wool sheep-dominated enterprises. This suggests that rangeland owners may be better off converting their wool sheep-dominated farms into springbuck-dominated ranches. Thus, as the call for more environmentally benign rangeland utilising economic-ecological systems intensifies, rangeland owners in the Eastern Cape Karoo have a practicable option. At the very least, there exists an option to broaden their incomes whilst promoting ecological restoration with springbuck meat production.
- Full Text:
- Date Issued: 2012
Hydrological uncertainty analysis and scenario-based streamflow modelling for the Congo River Basin
- Authors: Tshimanga, Raphael Muamba
- Date: 2012
- Subjects: Congo River -- Regulation Hydrological surveys -- Congo River Watershed Water resources development -- Congo River Watershed Water resources development -- Environmental aspects -- Congo River Watershed Water supply -- Congo River Watershed River engineering -- Congo River Watershed
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6029 , http://hdl.handle.net/10962/d1006158
- Description: The effects of climate and environmental change are likely to exacerbate water stress in Africa over the next five decades. It appears obvious, therefore, that large river basins with considerable total renewable water resources will play a prominent role in regional cooperation to alleviate the pressure of water scarcity within Africa. However, managing water resources in the large river basins of Africa involves problems of data paucity, lack of technical resources and the sheer scale of the problem. These river basins are located in regions that are characterized by poverty, low levels of economic development and little food security. The rivers provide multiple goods and services that include hydro-power, water supply, fisheries, agriculture, transportation, and maintenance of aquatic ecosystems. Sustainable water resources management is a critical issue, but there is almost always insufficient data available to formulate adequate management strategies. These basins therefore represent some of the best test cases for the practical application of the science associated with the Predictions in Ungauged Basins (PUB). The thesis presents the results of a process-based hydrological modelling study in the Congo Basin. One of the primary objectives of this study was to establish a hydrological model for the whole Congo Basin, using available historical data. The secondary objective of the study was to use the model and assess the impacts of future environmental change on water resources of the Congo Basin. Given the lack of adequate data on the basin physical characteristics, the preliminary work consisted of assessing available global datasets and building a database of the basin physical characteristics. The database was used for both assessing relationships of similarities between features of physiographic settings in the basin (Chapters 3 and 4), and establishing models that adequately represent the basin hydrology (Chapters 5, 6, and 7). The representative model of the Congo Basin hydrology was then used to assess the impacts of future environmental changes on water resources availability of the Congo Basin (Chapter 8). Through assessment of the physical characteristics of the basin, relationships of similarities were used to determine homogenous regions with regard to rainfall variability, physiographic settings, and hydrological responses. The first observation that comes from this study is that these three categories of regional groups of homogenous characteristics are sensible with regards to their geographical settings, but the overlap and apparent relationships between them are weak. An explanation of this observation is that there are insufficient data, particularly associated with defining sub-surface processes, and it is possible that additional data would have assisted in the discrimination of more homogenous groups and better links between the different datasets. The model application in this study consisted of two phases: model calibration, using a manual approach, and the application of a physically-based a priori parameter estimation approach. While the first approach was designed to assess the general applicability of the model and identify major errors with regard to input data and model structure, the second approach aimed to establish an understanding of the processes and identify useful relationships between the model parameters and the variations in real hydrological processes. The second approach was also designed to quantify the sensitivity of the model outputs to the parameters of the model and to encompass information sharing between the basin physical characteristics and quantifying the parameters of the model. Collectively, the study’s findings show that these two approaches work well and are appropriate to represent the real hydrological processes of Congo Basin. The secondary objective of this study was achieved by forcing the hydrological model developed for the Congo Basin with downscaled Global Climate Model (GCMs) data in order to assess scenarios of change and future possible impacts on water resources availability within the basin. The results provide useful lessons in terms of basin-wide adaptation measures to future climates. The lessons suggest that there is a risk of developing inappropriate adaptation measures to future climate change based on large scale hydrological response, as the response at small scales shows a completely different picture from that which is based on large scale predictions. While the study has concluded that the application of the hydrological model has been successful and can be used with some degree of confidence for enhanced decision making, there remain a number of uncertainties and opportunities to improve the methods used for water resources assessment within the basin. The focus of future activities from the perspective of practical application should be on improved access to data collection to increase confidence in model predictions, on dissemination of the knowledge generated by this study, and on training in the use of the developed water resources assessment techniques.
- Full Text:
- Date Issued: 2012
- Authors: Tshimanga, Raphael Muamba
- Date: 2012
- Subjects: Congo River -- Regulation Hydrological surveys -- Congo River Watershed Water resources development -- Congo River Watershed Water resources development -- Environmental aspects -- Congo River Watershed Water supply -- Congo River Watershed River engineering -- Congo River Watershed
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6029 , http://hdl.handle.net/10962/d1006158
- Description: The effects of climate and environmental change are likely to exacerbate water stress in Africa over the next five decades. It appears obvious, therefore, that large river basins with considerable total renewable water resources will play a prominent role in regional cooperation to alleviate the pressure of water scarcity within Africa. However, managing water resources in the large river basins of Africa involves problems of data paucity, lack of technical resources and the sheer scale of the problem. These river basins are located in regions that are characterized by poverty, low levels of economic development and little food security. The rivers provide multiple goods and services that include hydro-power, water supply, fisheries, agriculture, transportation, and maintenance of aquatic ecosystems. Sustainable water resources management is a critical issue, but there is almost always insufficient data available to formulate adequate management strategies. These basins therefore represent some of the best test cases for the practical application of the science associated with the Predictions in Ungauged Basins (PUB). The thesis presents the results of a process-based hydrological modelling study in the Congo Basin. One of the primary objectives of this study was to establish a hydrological model for the whole Congo Basin, using available historical data. The secondary objective of the study was to use the model and assess the impacts of future environmental change on water resources of the Congo Basin. Given the lack of adequate data on the basin physical characteristics, the preliminary work consisted of assessing available global datasets and building a database of the basin physical characteristics. The database was used for both assessing relationships of similarities between features of physiographic settings in the basin (Chapters 3 and 4), and establishing models that adequately represent the basin hydrology (Chapters 5, 6, and 7). The representative model of the Congo Basin hydrology was then used to assess the impacts of future environmental changes on water resources availability of the Congo Basin (Chapter 8). Through assessment of the physical characteristics of the basin, relationships of similarities were used to determine homogenous regions with regard to rainfall variability, physiographic settings, and hydrological responses. The first observation that comes from this study is that these three categories of regional groups of homogenous characteristics are sensible with regards to their geographical settings, but the overlap and apparent relationships between them are weak. An explanation of this observation is that there are insufficient data, particularly associated with defining sub-surface processes, and it is possible that additional data would have assisted in the discrimination of more homogenous groups and better links between the different datasets. The model application in this study consisted of two phases: model calibration, using a manual approach, and the application of a physically-based a priori parameter estimation approach. While the first approach was designed to assess the general applicability of the model and identify major errors with regard to input data and model structure, the second approach aimed to establish an understanding of the processes and identify useful relationships between the model parameters and the variations in real hydrological processes. The second approach was also designed to quantify the sensitivity of the model outputs to the parameters of the model and to encompass information sharing between the basin physical characteristics and quantifying the parameters of the model. Collectively, the study’s findings show that these two approaches work well and are appropriate to represent the real hydrological processes of Congo Basin. The secondary objective of this study was achieved by forcing the hydrological model developed for the Congo Basin with downscaled Global Climate Model (GCMs) data in order to assess scenarios of change and future possible impacts on water resources availability within the basin. The results provide useful lessons in terms of basin-wide adaptation measures to future climates. The lessons suggest that there is a risk of developing inappropriate adaptation measures to future climate change based on large scale hydrological response, as the response at small scales shows a completely different picture from that which is based on large scale predictions. While the study has concluded that the application of the hydrological model has been successful and can be used with some degree of confidence for enhanced decision making, there remain a number of uncertainties and opportunities to improve the methods used for water resources assessment within the basin. The focus of future activities from the perspective of practical application should be on improved access to data collection to increase confidence in model predictions, on dissemination of the knowledge generated by this study, and on training in the use of the developed water resources assessment techniques.
- Full Text:
- Date Issued: 2012
An investigation into the antidiabetic and catalytic properties of oxovanadium(IV) complexes
- Authors: Walmsley, Ryan Steven
- Date: 2012
- Subjects: Hypoglycemic agents Ligands (Biochemistry) Complex compounds Potentiometry Proton transfer reactions Stability Imidazoles Vanadium catalysts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4320 , http://hdl.handle.net/10962/d1004978
- Description: In part 1 of this thesis, the antidiabetic activity of a series of novel oxovanadium(IV) complexes was investigated. A range of bidentate N,O-donor ligands, which partially mimic naturally occurring bioligands, were prepared and reacted with the vanadyl ion to form the corresponding bis-coordinated complexes. Initially, 2-(2ˊ-hydroxyphenyl)-1R-imidazoline (where R = H, ethyl and ethanol) ligands were prepared. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave an indication of how the complexes might behave across the broad pH range experienced in the digestive and circulatory systems. This information was used to create an improved 2nd generation of ligands that were constructed by combining the imidazole and carboxylic acid functionalities. These corresponding bis[(imidazolyl)carboxylato]-oxovanadium(IV) complexes displayed a broader pH-metric stability. Both sets of complexes improved glucose uptake and reduced coagulation in vitro. In part 2 of this thesis, a range of homogeneous and heterogeneous oxovanadium(IV) catalysts were prepared. Firstly, Merrifield beads were functionalized with ligands from Part 1 and then reacted with vanadyl sulfate to afford the corresponding heterogeneous catalysts. These displayed promising catalytic activity for the peroxide facilitated oxidation of thioanisole, styrene and ethylbenzene as well as the oxidative bromination of phenol red. Smaller imidazole-containing beads with higher surface areas than the Merrifield beads were prepared by suspension polymerization. These beads similarly demonstrated excellent catalytic activity for the oxidation of thioanisole and were highly recyclable. In attempt to increase the exposed catalytic surface area, while retaining the ease of separation achieved in the before mentioned systems, micron to nano sized electrospun fibers containing coordinating ligands were fabricated. The corresponding oxovanadium(IV) functionalized fibers were applied to the oxidation of thioanisole using a continuous flow system. The flexible and porous nature of the fiber mats was well suited to this approach. After optimization of the reactant flow rate and catalyst amount, near quantitative (> 99%) oxidation was achieved for an extended period. In addition, leaching of vanadium was mitigated by modification of the attached ligand or polymer material.
- Full Text:
- Date Issued: 2012
- Authors: Walmsley, Ryan Steven
- Date: 2012
- Subjects: Hypoglycemic agents Ligands (Biochemistry) Complex compounds Potentiometry Proton transfer reactions Stability Imidazoles Vanadium catalysts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4320 , http://hdl.handle.net/10962/d1004978
- Description: In part 1 of this thesis, the antidiabetic activity of a series of novel oxovanadium(IV) complexes was investigated. A range of bidentate N,O-donor ligands, which partially mimic naturally occurring bioligands, were prepared and reacted with the vanadyl ion to form the corresponding bis-coordinated complexes. Initially, 2-(2ˊ-hydroxyphenyl)-1R-imidazoline (where R = H, ethyl and ethanol) ligands were prepared. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave an indication of how the complexes might behave across the broad pH range experienced in the digestive and circulatory systems. This information was used to create an improved 2nd generation of ligands that were constructed by combining the imidazole and carboxylic acid functionalities. These corresponding bis[(imidazolyl)carboxylato]-oxovanadium(IV) complexes displayed a broader pH-metric stability. Both sets of complexes improved glucose uptake and reduced coagulation in vitro. In part 2 of this thesis, a range of homogeneous and heterogeneous oxovanadium(IV) catalysts were prepared. Firstly, Merrifield beads were functionalized with ligands from Part 1 and then reacted with vanadyl sulfate to afford the corresponding heterogeneous catalysts. These displayed promising catalytic activity for the peroxide facilitated oxidation of thioanisole, styrene and ethylbenzene as well as the oxidative bromination of phenol red. Smaller imidazole-containing beads with higher surface areas than the Merrifield beads were prepared by suspension polymerization. These beads similarly demonstrated excellent catalytic activity for the oxidation of thioanisole and were highly recyclable. In attempt to increase the exposed catalytic surface area, while retaining the ease of separation achieved in the before mentioned systems, micron to nano sized electrospun fibers containing coordinating ligands were fabricated. The corresponding oxovanadium(IV) functionalized fibers were applied to the oxidation of thioanisole using a continuous flow system. The flexible and porous nature of the fiber mats was well suited to this approach. After optimization of the reactant flow rate and catalyst amount, near quantitative (> 99%) oxidation was achieved for an extended period. In addition, leaching of vanadium was mitigated by modification of the attached ligand or polymer material.
- Full Text:
- Date Issued: 2012
Systematic marine spatial planning and monitoring in a data poor environment: a case study of Algoa Bay, South Africa
- Authors: Chalmers, Russell
- Date: 2012
- Subjects: Spatial ecology -- South Africa -- Algoa Bay , Coastal zone management -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5373 , http://hdl.handle.net/10962/d1015695
- Description: Globally the failure of traditional fisheries management approaches is evident through the increasing number of overexploited or depleted marine stocks. Past sectoral management has failed to address cumulative impacts of fisheries activities on ecosystem health. Ecosystem based approaches have been advocated as a viable alternative for sustainable management of marine ecosystems as they present a holistic and precautionary approach, which integrates management of multiple activities with that of maintaining ecological health. Although conceptually advanced, implementation has been poor due to the complexities of competing ecological and socio-economic management objectives. Marine spatial planning can facilitate the implementation of ecosystem based management as it is able to address the spatial heterogeneity of biological communities and anthropogenic activities. Ecosystem based management approaches aim to address the full range of anthropogenic drivers on the marine environment, including but not limited to fisheries, tourism, coastal development, and land and marine based pollution sources amongst others. Fisheries activities have a direct impact on the local marine environment and were therefore the focus of this study which forms a starting point for implementing ecosystem based management in Algoa Bay. It is envisaged that future research will build on this foundation and include additional anthropogenic drivers into the management and monitoring strategies developed in this study in order to achieve a truly holistic ecosystem approach to management in Algoa Bay. Algoa Bay is situated centrally within the warm-temperate Agulhas bioregion along the east coast of South Africa and is the largest and best formed logarithmic spiral bay along this section of coastline. A large city, two commercial ports and several coastal settlements are located within Algoa Bay and a wide range of marine based activities occur within the area. A large section of the coastline is proclaimed as a National Park yet only two small offshore marine areas are formally protected. The development of a large marine protected area (MPA) adjoining the terrestrial section was proposed in the mid-1990s but a lack of adequate spatial data with which to quantify the fishery costs and conservation benefits led to wide scale public opposition and halted the declaration process. The primary goal of this study was to obtain and analyse baseline data to understand spatial and temporal trends in the distribution and abundance of fish populations and fisheries activities in order to develop a spatial framework for marine conservation and management in a data limited situation using Algoa Bay, South Africa as a case study. Furthermore, it aims to contribute to the development of a monitoring framework to evaluate the success of implementation and the resultant changes in biological and socio-economic environments. This information will be used to re-initiate the stakeholder engagement process in the future.
- Full Text:
- Date Issued: 2012
- Authors: Chalmers, Russell
- Date: 2012
- Subjects: Spatial ecology -- South Africa -- Algoa Bay , Coastal zone management -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5373 , http://hdl.handle.net/10962/d1015695
- Description: Globally the failure of traditional fisheries management approaches is evident through the increasing number of overexploited or depleted marine stocks. Past sectoral management has failed to address cumulative impacts of fisheries activities on ecosystem health. Ecosystem based approaches have been advocated as a viable alternative for sustainable management of marine ecosystems as they present a holistic and precautionary approach, which integrates management of multiple activities with that of maintaining ecological health. Although conceptually advanced, implementation has been poor due to the complexities of competing ecological and socio-economic management objectives. Marine spatial planning can facilitate the implementation of ecosystem based management as it is able to address the spatial heterogeneity of biological communities and anthropogenic activities. Ecosystem based management approaches aim to address the full range of anthropogenic drivers on the marine environment, including but not limited to fisheries, tourism, coastal development, and land and marine based pollution sources amongst others. Fisheries activities have a direct impact on the local marine environment and were therefore the focus of this study which forms a starting point for implementing ecosystem based management in Algoa Bay. It is envisaged that future research will build on this foundation and include additional anthropogenic drivers into the management and monitoring strategies developed in this study in order to achieve a truly holistic ecosystem approach to management in Algoa Bay. Algoa Bay is situated centrally within the warm-temperate Agulhas bioregion along the east coast of South Africa and is the largest and best formed logarithmic spiral bay along this section of coastline. A large city, two commercial ports and several coastal settlements are located within Algoa Bay and a wide range of marine based activities occur within the area. A large section of the coastline is proclaimed as a National Park yet only two small offshore marine areas are formally protected. The development of a large marine protected area (MPA) adjoining the terrestrial section was proposed in the mid-1990s but a lack of adequate spatial data with which to quantify the fishery costs and conservation benefits led to wide scale public opposition and halted the declaration process. The primary goal of this study was to obtain and analyse baseline data to understand spatial and temporal trends in the distribution and abundance of fish populations and fisheries activities in order to develop a spatial framework for marine conservation and management in a data limited situation using Algoa Bay, South Africa as a case study. Furthermore, it aims to contribute to the development of a monitoring framework to evaluate the success of implementation and the resultant changes in biological and socio-economic environments. This information will be used to re-initiate the stakeholder engagement process in the future.
- Full Text:
- Date Issued: 2012
Quality of work and work life: understanding the work ethic of medical professionals in selected hospitals in the Eastern Cape region of South Africa
- Authors: Kwizera, Alice Stella
- Date: 2012
- Subjects: Hospitals -- Medical staff -- South Africa -- Eastern Cape Work ethic -- South Africa -- Eastern Cape Medical personnel -- Job satisfaction -- South Africa -- Eastern Cape Protestant work ethic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3323 , http://hdl.handle.net/10962/d1003111
- Description: This thesis reports a study of work ethic values, beliefs and attitudes held by medical professionals in selected hospitals in the Eastern Cape, South Africa. The study was in response to the public outcry about the declining work ethic and poor service delivery in South Africa’s healthcare sector. Scholarly interest in the work ethic and its role in economic development dates back to Max Weber’s classical work, which was the starting point for my study. The German economic sociologist published his seminal essay on The Protestant Ethic and the Spirit of Capitalism in 1904/1905. Since that time, Weber’s ideas on the Protestant work ethic continue to inform and influence studies of the contemporary work ethic, which is thought to have become secularised. My study was informed by data collected in 2009 through a questionnaire survey and personal interviews. A total of 174 doctors and nurses, working in four urban, periurban and rural hospitals near East London, completed a self-administered questionnaire. The questionnaire replicated the Multi-Dimensional Work Ethic Profile (MWEP) developed by Miller, Woehr and Hudspeth in 2001/2002. The instrument examines seven critical dimensions of the work ethic, namely self-reliance, morality, (foregoing) leisure, hard work, centrality of work in life, not wasting time, and delay of gratification. In addition, I conducted personal interviews in the same four hospitals with 41 hospital managers, doctors, nurses, and patients to discuss their understanding of the work ethic and its practical application. The study found that both doctors’ and nurses’ overall work ethic scores on the MWEP scale were above average. Although there was no significant difference between the overall work ethic scores of the two professions, doctors scored significantly higher than nurses on the ‘hard work’ and ‘self reliance’ dimensions of the work ethic scale. In the qualitative study, the doctors’ work ethic was rated much more highly than the nurses’ by their superiors and patients; and the work ethic of nurses in the urban hospitals was rated much lower than that of their rural colleagues. In contradiction to the idea of the secularization of the contemporary work ethic, religiosity and religious beliefs were influential in the endorsement of work ethic principles. In line with the notion that ‘happy’ workers are more productive, job and life satisfaction were found to be strong correlates of the work ethic of medical professionals.
- Full Text:
- Date Issued: 2012
- Authors: Kwizera, Alice Stella
- Date: 2012
- Subjects: Hospitals -- Medical staff -- South Africa -- Eastern Cape Work ethic -- South Africa -- Eastern Cape Medical personnel -- Job satisfaction -- South Africa -- Eastern Cape Protestant work ethic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3323 , http://hdl.handle.net/10962/d1003111
- Description: This thesis reports a study of work ethic values, beliefs and attitudes held by medical professionals in selected hospitals in the Eastern Cape, South Africa. The study was in response to the public outcry about the declining work ethic and poor service delivery in South Africa’s healthcare sector. Scholarly interest in the work ethic and its role in economic development dates back to Max Weber’s classical work, which was the starting point for my study. The German economic sociologist published his seminal essay on The Protestant Ethic and the Spirit of Capitalism in 1904/1905. Since that time, Weber’s ideas on the Protestant work ethic continue to inform and influence studies of the contemporary work ethic, which is thought to have become secularised. My study was informed by data collected in 2009 through a questionnaire survey and personal interviews. A total of 174 doctors and nurses, working in four urban, periurban and rural hospitals near East London, completed a self-administered questionnaire. The questionnaire replicated the Multi-Dimensional Work Ethic Profile (MWEP) developed by Miller, Woehr and Hudspeth in 2001/2002. The instrument examines seven critical dimensions of the work ethic, namely self-reliance, morality, (foregoing) leisure, hard work, centrality of work in life, not wasting time, and delay of gratification. In addition, I conducted personal interviews in the same four hospitals with 41 hospital managers, doctors, nurses, and patients to discuss their understanding of the work ethic and its practical application. The study found that both doctors’ and nurses’ overall work ethic scores on the MWEP scale were above average. Although there was no significant difference between the overall work ethic scores of the two professions, doctors scored significantly higher than nurses on the ‘hard work’ and ‘self reliance’ dimensions of the work ethic scale. In the qualitative study, the doctors’ work ethic was rated much more highly than the nurses’ by their superiors and patients; and the work ethic of nurses in the urban hospitals was rated much lower than that of their rural colleagues. In contradiction to the idea of the secularization of the contemporary work ethic, religiosity and religious beliefs were influential in the endorsement of work ethic principles. In line with the notion that ‘happy’ workers are more productive, job and life satisfaction were found to be strong correlates of the work ethic of medical professionals.
- Full Text:
- Date Issued: 2012
Force of habit the mystical foundations of the narcotic
- Authors: Howell, Simon Peter
- Date: 2012
- Subjects: Drug addiction -- Philosophy -- Research Drug addiction -- Political aspects -- Research Cocaine abuse -- Legal status, laws, etc. -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2784 , http://hdl.handle.net/10962/d1002994
- Description: This thesis aims to investigate and deconstruct the relationship between the narcotic, its narrative, and western modernity. To reveal the relationship, this thesis argues that it is possible to understand the philosophical, political, cultural and ethical dimensions of western modernity through the ulterior lens of the narcotic. As such, this thesis investigates western modernity's relationship to (a) cocaine as a specific narcotic, and (b) the concept of the narcotic with all its attendant connotations of addictions, illegitimacy, transgression, illegality, and so on. Accordingly, the thesis is both interpretive of the historical narrative of the narcotic of cocaine, and generative in its deconstruction of the relationship between western modernity and the concept of the narcotic. The deconstruction of this relationship ultimately reveals both prior narratives not as oppositional, but as supplementary. This has radical consequences for the manner in which we engage with narcotic use and the user - if the narcotic is supplement to the logic of western modernity, at each attempt to expel the use and user of the narcotic, rather then create difference, we self implicate ourselves in that expulsion and distance. To seek a new and more just means of dealing with the concept of the narcotic, and its use, therefore requires a new epistemological framework which can at once contemplate both narratives at the same time. To this end, the thesis suggests the use of critical complexity theory as one such methodological tool, if supplemented by the thoughts and strategies of Derridian deconstruction and Foucauldian discourse analysis.
- Full Text:
- Date Issued: 2012
- Authors: Howell, Simon Peter
- Date: 2012
- Subjects: Drug addiction -- Philosophy -- Research Drug addiction -- Political aspects -- Research Cocaine abuse -- Legal status, laws, etc. -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2784 , http://hdl.handle.net/10962/d1002994
- Description: This thesis aims to investigate and deconstruct the relationship between the narcotic, its narrative, and western modernity. To reveal the relationship, this thesis argues that it is possible to understand the philosophical, political, cultural and ethical dimensions of western modernity through the ulterior lens of the narcotic. As such, this thesis investigates western modernity's relationship to (a) cocaine as a specific narcotic, and (b) the concept of the narcotic with all its attendant connotations of addictions, illegitimacy, transgression, illegality, and so on. Accordingly, the thesis is both interpretive of the historical narrative of the narcotic of cocaine, and generative in its deconstruction of the relationship between western modernity and the concept of the narcotic. The deconstruction of this relationship ultimately reveals both prior narratives not as oppositional, but as supplementary. This has radical consequences for the manner in which we engage with narcotic use and the user - if the narcotic is supplement to the logic of western modernity, at each attempt to expel the use and user of the narcotic, rather then create difference, we self implicate ourselves in that expulsion and distance. To seek a new and more just means of dealing with the concept of the narcotic, and its use, therefore requires a new epistemological framework which can at once contemplate both narratives at the same time. To this end, the thesis suggests the use of critical complexity theory as one such methodological tool, if supplemented by the thoughts and strategies of Derridian deconstruction and Foucauldian discourse analysis.
- Full Text:
- Date Issued: 2012
Synthesis, characterization and antimicrobial activity of copper (II) complexes of some hydroxybenzaldimines and their derivatives
- Authors: Sobola, Abdullahi Owolabi
- Date: 2012
- Subjects: Copper , Schiff bases , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4534 , http://hdl.handle.net/10962/d1016258
- Description: This study focuses on the antimicrobial activity of Cu(II) complexes of some orthohydroxybenzaldimines and its derivatives. Four different categories of Schiff base ligands were prepared by condensing salicylaldehyde, o-vanillin, p-vanillin and vanillin with p- and osubstituted anilines; 1-aminonaphthalene; 2- and 3-aminopyridine; 2- and 3- aminomethylpyridine as well as 2-aminobenzimidazole. The last category was prepared from ophenylenediamine and o-vanillin. The Schiff base ligands have been characterized by a combination of elemental analysis and spectral (¹H- and ¹³C-NMR, UV/Visible, infrared and Raman) data. The existence of strong intramolecular hydrogen bonding in the orthohydoxybenzaldimines was evident from the chemical shift values of the hydroxyl proton in the ¹H-NMR spectra of the Schiff base ligands. The hydroxyl proton resonates at high frequency and thus absorbed far downfield at 13.46-11.83 ppm, reflecting the presence of hydrogen bonding between the hydroxyl proton and the imine nitrogen. In the p-substituted aniline analogues of the Schiff base, a plot of the chemical shift values of the hydroxyl proton against the Hammett's substituent parameters gave a linear correlation between the electronegativities of the substituents and the chemical shift values. The nitro group with the highest electronegativity caused the least deshielding of the hydroxyl proton and thus absorbed upfield compared to the less electronegative substituents such as the CH3 and OCH3 analogues. Likewise, in the solid state infrared spectra of the ligands, the hydroxyl stretching band of the ortho-hydroxyl Schiff base ligands was observed as a very broad band and at much lower frequency, 3100-2100 cm⁻¹, indicating the existence of strong intramolecular hydrogen bonding. In the same vein, ¹H- and ¹³C-NMR spectral data for the Schiff base ligands indicated that the prepared compounds exist in the enol form in aprotic solvent, chloroform. The methine proton appeared as singlet and there was no carbonyl signal in the ¹³C-NMR spectra of the Schiff base ligands. This was supported by the infrared data having no vibrational band attributable to the carbonyl stretching of the keto-form of the Schiff base ligands in solid state. However, the UV/Visible study of the Schiff base ligands in protic solvent, methanol, suggested the existence of some of the Schiff base ligands in keto-enol form. A band at greater than 400 nm was observed in the UV/Visible spectra of the ligands and this has been attributed to the presence of the keto form of orthohydroxyl Schiff base ligands in solution. A plot of the molar absorptivity (ε) of the band at greater than 400 nm against Hammett substituent parameters revealed that the intensity of the bands increased with the electronegativity of the substituents. The Cu(II) complexes of salicylaldehyde, o-vanillin and a few p-vanillin based Schiff base ligands are reported in this work. It was observed that introduction of Cu(II) ions into the ligand system resulted in the hydrolysis of the imine band in few cases. All the isolated complexes have been characterized by elemental analysis, conductivity measurement, infrared and UV/Visible spectral data. The structures of three of the Cu(II) complexes were further confirmed by X-ray single crystal diffraction. The Schiff base ligands either coordinated as neutral base through the imine nitrogen or via the imine nitrogen and the phenolic oxygen atoms. In addition, the benzimidazole-based and ovan-2-pico analogues equally coordinated through the imidazole N-3 nitrogen and the azine nitrogen respectively; thus acted as tridentate. In general, the synthesized Cu(II) complexes fell into seven categories viz: [Cu(LH)Cl(H₂O)]Cl; [Cu(LH)₂Cl₂].xH₂O; [CuL₂]; [Cu₂L₂]; [Cu(LH)Cl(H₂O)]Cl; and [MLCl]. The Cu(II) complexes of the form, M(LH)₂Cl₂.xH₂O were either 1:1 or non-electrolyte in methanol and DMF. The third category, CuL₂, was however, non-electrolyte existing as neutral four coordinate Cu(II) complexes. X-ray single crystal structure of Cu(II) complexes derived from the ammonia-based Schiff bases revealed a square planar geometry for the complexes and this agreed with the planar geometry that has been reported for Cu(II) complexes of N-arylsalicylaldimines of the type studied in this work. The complexes, [Cu₂L₂], resulted from the ortho-hydroxyaniline analogues and were polymeric with the Schiff base ligands coordinating to the Cu(II) ions as tridentate dibasic via the imine nitrogen, phenolic oxygen and the aminophenolic oxygen atoms. Cu(II) complexes prepared from ovan-2-ampy and ovan-2-pico Schiff bases were of the forms [Cu(LH)Cl(H₂O)]Cl and [CuLCl] respectively. The X-ray crystal structure of [Cu(ovan-2- pico)Cl] revealed a four-coordinate square planar geometry for the complex. In the same vein, the o-phenylenediamine complexes were of the form [Cu(L)(H₂O)], with the X-ray crystal structure of [Cu(bis-ovanphen)(H₂O)] revealing a square pyramidal geometry. The Schiff base ligands and the isolated Cu(II) complexes have been evaluated for their antimicrobial activity against three bacterial strains (Escherichia coli ATCC® 8739™*, Staphylococcus aureus subsp. aureus ATCC® 6538™* and Bacillus subtilis subsp. spizizeni ATCC® 6633™*) and one fungal strain, Candida albicans ATCC® 2091™*, using agar disc diffusion and broth dilution techniques. It was observed that the presence of the methoxyl group at the ortho-position of the aldehyde moiety of the Schiff base ligands enhanced the activity of the ligand tremendously and thus the o-vanillin analogues showed the highest potency against the tested organisms. In addition, the hydroxyaniline analogues were equally the most promising of all the substituted aniline based Schiff bases. The o-vanillin analogues of the aminopyridines and aminomethylpyridines also exhibited significant activity against the tested organisms. All the 2-aminobenzimidazole series were active against the tested organisms. It should be noted that E. coli was the least susceptible of all the microorganisms while the highest potency was exhibited against the fungus of choice, Candida albicans. Lastly, chelation of the Schiff base ligands with Cu(II) ions did not have significant influence on the activity of the free ligands.
- Full Text:
- Date Issued: 2012
- Authors: Sobola, Abdullahi Owolabi
- Date: 2012
- Subjects: Copper , Schiff bases , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4534 , http://hdl.handle.net/10962/d1016258
- Description: This study focuses on the antimicrobial activity of Cu(II) complexes of some orthohydroxybenzaldimines and its derivatives. Four different categories of Schiff base ligands were prepared by condensing salicylaldehyde, o-vanillin, p-vanillin and vanillin with p- and osubstituted anilines; 1-aminonaphthalene; 2- and 3-aminopyridine; 2- and 3- aminomethylpyridine as well as 2-aminobenzimidazole. The last category was prepared from ophenylenediamine and o-vanillin. The Schiff base ligands have been characterized by a combination of elemental analysis and spectral (¹H- and ¹³C-NMR, UV/Visible, infrared and Raman) data. The existence of strong intramolecular hydrogen bonding in the orthohydoxybenzaldimines was evident from the chemical shift values of the hydroxyl proton in the ¹H-NMR spectra of the Schiff base ligands. The hydroxyl proton resonates at high frequency and thus absorbed far downfield at 13.46-11.83 ppm, reflecting the presence of hydrogen bonding between the hydroxyl proton and the imine nitrogen. In the p-substituted aniline analogues of the Schiff base, a plot of the chemical shift values of the hydroxyl proton against the Hammett's substituent parameters gave a linear correlation between the electronegativities of the substituents and the chemical shift values. The nitro group with the highest electronegativity caused the least deshielding of the hydroxyl proton and thus absorbed upfield compared to the less electronegative substituents such as the CH3 and OCH3 analogues. Likewise, in the solid state infrared spectra of the ligands, the hydroxyl stretching band of the ortho-hydroxyl Schiff base ligands was observed as a very broad band and at much lower frequency, 3100-2100 cm⁻¹, indicating the existence of strong intramolecular hydrogen bonding. In the same vein, ¹H- and ¹³C-NMR spectral data for the Schiff base ligands indicated that the prepared compounds exist in the enol form in aprotic solvent, chloroform. The methine proton appeared as singlet and there was no carbonyl signal in the ¹³C-NMR spectra of the Schiff base ligands. This was supported by the infrared data having no vibrational band attributable to the carbonyl stretching of the keto-form of the Schiff base ligands in solid state. However, the UV/Visible study of the Schiff base ligands in protic solvent, methanol, suggested the existence of some of the Schiff base ligands in keto-enol form. A band at greater than 400 nm was observed in the UV/Visible spectra of the ligands and this has been attributed to the presence of the keto form of orthohydroxyl Schiff base ligands in solution. A plot of the molar absorptivity (ε) of the band at greater than 400 nm against Hammett substituent parameters revealed that the intensity of the bands increased with the electronegativity of the substituents. The Cu(II) complexes of salicylaldehyde, o-vanillin and a few p-vanillin based Schiff base ligands are reported in this work. It was observed that introduction of Cu(II) ions into the ligand system resulted in the hydrolysis of the imine band in few cases. All the isolated complexes have been characterized by elemental analysis, conductivity measurement, infrared and UV/Visible spectral data. The structures of three of the Cu(II) complexes were further confirmed by X-ray single crystal diffraction. The Schiff base ligands either coordinated as neutral base through the imine nitrogen or via the imine nitrogen and the phenolic oxygen atoms. In addition, the benzimidazole-based and ovan-2-pico analogues equally coordinated through the imidazole N-3 nitrogen and the azine nitrogen respectively; thus acted as tridentate. In general, the synthesized Cu(II) complexes fell into seven categories viz: [Cu(LH)Cl(H₂O)]Cl; [Cu(LH)₂Cl₂].xH₂O; [CuL₂]; [Cu₂L₂]; [Cu(LH)Cl(H₂O)]Cl; and [MLCl]. The Cu(II) complexes of the form, M(LH)₂Cl₂.xH₂O were either 1:1 or non-electrolyte in methanol and DMF. The third category, CuL₂, was however, non-electrolyte existing as neutral four coordinate Cu(II) complexes. X-ray single crystal structure of Cu(II) complexes derived from the ammonia-based Schiff bases revealed a square planar geometry for the complexes and this agreed with the planar geometry that has been reported for Cu(II) complexes of N-arylsalicylaldimines of the type studied in this work. The complexes, [Cu₂L₂], resulted from the ortho-hydroxyaniline analogues and were polymeric with the Schiff base ligands coordinating to the Cu(II) ions as tridentate dibasic via the imine nitrogen, phenolic oxygen and the aminophenolic oxygen atoms. Cu(II) complexes prepared from ovan-2-ampy and ovan-2-pico Schiff bases were of the forms [Cu(LH)Cl(H₂O)]Cl and [CuLCl] respectively. The X-ray crystal structure of [Cu(ovan-2- pico)Cl] revealed a four-coordinate square planar geometry for the complex. In the same vein, the o-phenylenediamine complexes were of the form [Cu(L)(H₂O)], with the X-ray crystal structure of [Cu(bis-ovanphen)(H₂O)] revealing a square pyramidal geometry. The Schiff base ligands and the isolated Cu(II) complexes have been evaluated for their antimicrobial activity against three bacterial strains (Escherichia coli ATCC® 8739™*, Staphylococcus aureus subsp. aureus ATCC® 6538™* and Bacillus subtilis subsp. spizizeni ATCC® 6633™*) and one fungal strain, Candida albicans ATCC® 2091™*, using agar disc diffusion and broth dilution techniques. It was observed that the presence of the methoxyl group at the ortho-position of the aldehyde moiety of the Schiff base ligands enhanced the activity of the ligand tremendously and thus the o-vanillin analogues showed the highest potency against the tested organisms. In addition, the hydroxyaniline analogues were equally the most promising of all the substituted aniline based Schiff bases. The o-vanillin analogues of the aminopyridines and aminomethylpyridines also exhibited significant activity against the tested organisms. All the 2-aminobenzimidazole series were active against the tested organisms. It should be noted that E. coli was the least susceptible of all the microorganisms while the highest potency was exhibited against the fungus of choice, Candida albicans. Lastly, chelation of the Schiff base ligands with Cu(II) ions did not have significant influence on the activity of the free ligands.
- Full Text:
- Date Issued: 2012
Transgressive Christian iconography in post-apartheid South African art
- Authors: Von Veh, Karen Elaine
- Date: 2012
- Subjects: Art -- South Africa -- 20th century Art -- South Africa -- 21st century Christian art and symbolism Apartheid in art Art and society -- South Africa -- History -- 20th century Art and society -- South Africa -- History -- 21st century Parody in art
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2424 , http://hdl.handle.net/10962/d1002220
- Description: In this study I propose that transgressive interpretations of Christian iconography provide a valuable strategy for contemporary artists to engage with perceived social inequalities in postapartheid South Africa. Working in light of Michel Foucault’s idea of an “ontology of the present”, I investigate the ways in which religious iconography has been implicated in the regulation of society. Parodic reworking of Christian imagery in the selected examples is investigated as a strategy to expose these controls and offer a critique of mechanisms which produce normative ‘truths’. I also consider how such imagery has been received and the factors accounting for that reception. The study is contextualized by a brief, literary based, historical overview of Christian religious imagery to explain the strength of feeling evinced by religious images. This includes a review of the conflation of religion and state control of the masses, an analysis of the sovereign controls and disciplinary powers that they wield, and an explication of their illustration in religious iconography. I also identify reasons why such imagery may have seemed compelling to artists working in a post-apartheid context. By locating recent works in terms of those made elsewhere or South African examples prior to the period that is my focus, the works discussed are explored in terms of broader orientations in post-apartheid South African art. Artworks that respond to specific Christian iconography are discussed, including Adam and Eve, The Virgin Mary, Christ, and various saints and sinners. The selected artists whose works form the focus of this study are Diane Victor, Christine Dixie, Majak Bredell, Tracey Rose, Wim Botha, Conrad Botes, Johannes Phokela and Lawrence Lemaoana. Through transgressive depictions of Christian icons these artists address current inequalities in society. The content of their works analysed here includes (among others): the construction of both female and male identities; sexual roles, social roles, and racial identity; the social expectations of contemporary motherhood; repressive role models; Afrikaner heritage; political and social change and its effects; colonial power; sacrifice; murder, rape, and violence in South Africa; abuses of power by role models and politicians; rugby; heroism; and patricide. Christian iconography is a useful communicative tool because it has permeated many cultures over centuries, and the meanings it carries are thus accessible to large numbers of people. Religious imagery is often held sacred or is regarded with a degree of reverence, thus ensuring an emotive response when iconoclasm or transgression of any sort is identified. This study argues that by parodying sacred imagery these artists are able to disturb complacent viewing and encourage viewers to engage critically with some of its underlying implications.
- Full Text:
- Date Issued: 2012
- Authors: Von Veh, Karen Elaine
- Date: 2012
- Subjects: Art -- South Africa -- 20th century Art -- South Africa -- 21st century Christian art and symbolism Apartheid in art Art and society -- South Africa -- History -- 20th century Art and society -- South Africa -- History -- 21st century Parody in art
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2424 , http://hdl.handle.net/10962/d1002220
- Description: In this study I propose that transgressive interpretations of Christian iconography provide a valuable strategy for contemporary artists to engage with perceived social inequalities in postapartheid South Africa. Working in light of Michel Foucault’s idea of an “ontology of the present”, I investigate the ways in which religious iconography has been implicated in the regulation of society. Parodic reworking of Christian imagery in the selected examples is investigated as a strategy to expose these controls and offer a critique of mechanisms which produce normative ‘truths’. I also consider how such imagery has been received and the factors accounting for that reception. The study is contextualized by a brief, literary based, historical overview of Christian religious imagery to explain the strength of feeling evinced by religious images. This includes a review of the conflation of religion and state control of the masses, an analysis of the sovereign controls and disciplinary powers that they wield, and an explication of their illustration in religious iconography. I also identify reasons why such imagery may have seemed compelling to artists working in a post-apartheid context. By locating recent works in terms of those made elsewhere or South African examples prior to the period that is my focus, the works discussed are explored in terms of broader orientations in post-apartheid South African art. Artworks that respond to specific Christian iconography are discussed, including Adam and Eve, The Virgin Mary, Christ, and various saints and sinners. The selected artists whose works form the focus of this study are Diane Victor, Christine Dixie, Majak Bredell, Tracey Rose, Wim Botha, Conrad Botes, Johannes Phokela and Lawrence Lemaoana. Through transgressive depictions of Christian icons these artists address current inequalities in society. The content of their works analysed here includes (among others): the construction of both female and male identities; sexual roles, social roles, and racial identity; the social expectations of contemporary motherhood; repressive role models; Afrikaner heritage; political and social change and its effects; colonial power; sacrifice; murder, rape, and violence in South Africa; abuses of power by role models and politicians; rugby; heroism; and patricide. Christian iconography is a useful communicative tool because it has permeated many cultures over centuries, and the meanings it carries are thus accessible to large numbers of people. Religious imagery is often held sacred or is regarded with a degree of reverence, thus ensuring an emotive response when iconoclasm or transgression of any sort is identified. This study argues that by parodying sacred imagery these artists are able to disturb complacent viewing and encourage viewers to engage critically with some of its underlying implications.
- Full Text:
- Date Issued: 2012
A systematic revision of selected genera of afrotropical curtonotidae (Diptera: schizophora: ephydroidea) : a phylogenetic approach
- Authors: Kirk-Spriggs, Ashley H
- Date: 2012
- Subjects: Curtonotidae -- Research Diptera -- Research Flies -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5627 , http://hdl.handle.net/10962/d1004747
- Description: The first comprehensive phylogeny of the family Curtonotidae is presented based on molecular markers and morphology. This enabled assessment of evolutionary relatedness, species radiation and zoogeography. A revised classification of the world fauna of the family, based on the results of this study is outlined. Nomenclatural acts flowing from these analyses include: the recognition three new Afrotropical species of Axinota van der Wulp; four new species of a new genus, Tigrisomyia Kirk-Spriggs; and nineteen new species of Curtonotum (six Madagascan and thirteen African). Ten informal species-groups of Curtonotum are recognised. Identification keys are provided for the Afrotropical species of these genera and errors in previous interpretations and designation of type specimens are resolved. Species distributions are mapped and interpreted and discussion is made of the historical biogeographical significance of these distributions.
- Full Text:
- Date Issued: 2012
- Authors: Kirk-Spriggs, Ashley H
- Date: 2012
- Subjects: Curtonotidae -- Research Diptera -- Research Flies -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5627 , http://hdl.handle.net/10962/d1004747
- Description: The first comprehensive phylogeny of the family Curtonotidae is presented based on molecular markers and morphology. This enabled assessment of evolutionary relatedness, species radiation and zoogeography. A revised classification of the world fauna of the family, based on the results of this study is outlined. Nomenclatural acts flowing from these analyses include: the recognition three new Afrotropical species of Axinota van der Wulp; four new species of a new genus, Tigrisomyia Kirk-Spriggs; and nineteen new species of Curtonotum (six Madagascan and thirteen African). Ten informal species-groups of Curtonotum are recognised. Identification keys are provided for the Afrotropical species of these genera and errors in previous interpretations and designation of type specimens are resolved. Species distributions are mapped and interpreted and discussion is made of the historical biogeographical significance of these distributions.
- Full Text:
- Date Issued: 2012
Mechanistic studies of unusual Miruta-Baylis-Hillman reactions
- Authors: Nyoni, Dubekile
- Date: 2012
- Subjects: Chemical reactions Benzaldehyde Acrylonitrile Methyl acrylate Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4400 , http://hdl.handle.net/10962/d1006692
- Description: This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.
- Full Text:
- Date Issued: 2012
- Authors: Nyoni, Dubekile
- Date: 2012
- Subjects: Chemical reactions Benzaldehyde Acrylonitrile Methyl acrylate Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4400 , http://hdl.handle.net/10962/d1006692
- Description: This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.
- Full Text:
- Date Issued: 2012
Electrochemical sensing and immunosensing using metallophthalocyanines and biomolecular modified surfaces
- Authors: Mashazi, Philani Nkosinathi
- Date: 2012
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Measles -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5580 , http://hdl.handle.net/10962/d1018248
- Description: The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease.
- Full Text:
- Date Issued: 2012
- Authors: Mashazi, Philani Nkosinathi
- Date: 2012
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Measles -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5580 , http://hdl.handle.net/10962/d1018248
- Description: The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease.
- Full Text:
- Date Issued: 2012
The design, synthesis and antiplasmodial activity of a series of halogenated fosmidomycin analogues and hybrid drugs
- Authors: Afolayan, Anthonia Folake
- Date: 2012
- Subjects: Uncatalogued
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64370 , vital:28538
- Description: Malaria continues to be a devastating disease and a major cause of death in sub-Saharan Africa. With resistance against most of the available antimalarial drugs, there is a need for ongoing research and development of antimalarial agents. Fosmidomycin and its acetyl analogue FR900098 have been identified as potent inhibitors of Plasmodium falciparum, the causative agent of the most deadly form of malaria. Clinical trials of these agents have revealed poor absorption due to their high hydrophilicity. In the present studies the effect of halogenation of the acyl chain as well as the biological effect of extending the acyl sidechain was explored. This provided the basis on which fosmidomycin hybrids were designed to investigate the feasibility of hybrid extending into NADPH binding pocket. Synthesis of a series of halogenated FR900098 analogues was carried out in three stages. This included i) The introduction of the phosphonate group by reaction with 1,3dibromopropane in an Arbuzov reaction, ii) The introduction of a hydroxamate group by reaction of the propyl phosphonate by means of a nucleophilic substitution reaction with BocNHOBn and iii) The introduction of a halogenated acyl side chain on a protected fosmidomycin backbone. The synthesis of fosmidomycin-hybrids for which chloroquinefosmidomycin hybrids were used as the prototype, involved convergence of the two separately constructed moieties i.e. fosmidomycin and the quinoline moieties in a covalent linkage. The quinoline moiety was easily synthesized from the reaction of 4,7dichloroquinoline with 1,2-diamino ethane. The aminoquinoline so formed resulted in chloroquine-fosmidomycin hybrids 3.8 and 3.9 when reacted with halogenated FR900098 analogues. Antiplasmodial assays were conducted on the chloroquine-fosmidomycin hybrids and the halogenated fosmidomycin derivatives against the chloroquine resistant Gambian FCR-3 strain of P. falciparum. The most potent iodoacetyl fosmidomycin analogues 2.21 gave an IC50 value of 5.54 µM which is eight times more potent than the known antiplasmodial FR900098 which gave an IC50 value of 41.67 µM. All the halogenated FR900098 analogues showed better antiplasmodial activity than their non-halogenated derivatives. This indicated that the presence of halogens in the FR900098 analogues contributes to their biological Chapter 1 Literature review activity. The acetyl and propyl linked hybrids 3.8 and 3.9 showed potent antiplasmodial activity with IC50 values of 0.18 and 0.82 µM respectively. These were by far the most potent hybrids synthesized and provided leads for a new class of promising antimalarial agents. Preliminary E. coli DXR enzyme inhibition assays were carried out on the halogenated fosmidomycin analogues. The results showed good inhibition of the enzyme by the phosphonic acids of the chloroacetyl and chloropropyl analogues 2.1 and 2.2 respectively. Molecular modelling of the compounds on E. coli (PDB code: 2EGH) and P. falciparum (PDB code: 3AUA) DXR showed strong binding of the halogenated fosmidomycin analogues while the hybrids in the absence of docked NADPH showed minimum binding to the enzymes.
- Full Text:
- Date Issued: 2012
- Authors: Afolayan, Anthonia Folake
- Date: 2012
- Subjects: Uncatalogued
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64370 , vital:28538
- Description: Malaria continues to be a devastating disease and a major cause of death in sub-Saharan Africa. With resistance against most of the available antimalarial drugs, there is a need for ongoing research and development of antimalarial agents. Fosmidomycin and its acetyl analogue FR900098 have been identified as potent inhibitors of Plasmodium falciparum, the causative agent of the most deadly form of malaria. Clinical trials of these agents have revealed poor absorption due to their high hydrophilicity. In the present studies the effect of halogenation of the acyl chain as well as the biological effect of extending the acyl sidechain was explored. This provided the basis on which fosmidomycin hybrids were designed to investigate the feasibility of hybrid extending into NADPH binding pocket. Synthesis of a series of halogenated FR900098 analogues was carried out in three stages. This included i) The introduction of the phosphonate group by reaction with 1,3dibromopropane in an Arbuzov reaction, ii) The introduction of a hydroxamate group by reaction of the propyl phosphonate by means of a nucleophilic substitution reaction with BocNHOBn and iii) The introduction of a halogenated acyl side chain on a protected fosmidomycin backbone. The synthesis of fosmidomycin-hybrids for which chloroquinefosmidomycin hybrids were used as the prototype, involved convergence of the two separately constructed moieties i.e. fosmidomycin and the quinoline moieties in a covalent linkage. The quinoline moiety was easily synthesized from the reaction of 4,7dichloroquinoline with 1,2-diamino ethane. The aminoquinoline so formed resulted in chloroquine-fosmidomycin hybrids 3.8 and 3.9 when reacted with halogenated FR900098 analogues. Antiplasmodial assays were conducted on the chloroquine-fosmidomycin hybrids and the halogenated fosmidomycin derivatives against the chloroquine resistant Gambian FCR-3 strain of P. falciparum. The most potent iodoacetyl fosmidomycin analogues 2.21 gave an IC50 value of 5.54 µM which is eight times more potent than the known antiplasmodial FR900098 which gave an IC50 value of 41.67 µM. All the halogenated FR900098 analogues showed better antiplasmodial activity than their non-halogenated derivatives. This indicated that the presence of halogens in the FR900098 analogues contributes to their biological Chapter 1 Literature review activity. The acetyl and propyl linked hybrids 3.8 and 3.9 showed potent antiplasmodial activity with IC50 values of 0.18 and 0.82 µM respectively. These were by far the most potent hybrids synthesized and provided leads for a new class of promising antimalarial agents. Preliminary E. coli DXR enzyme inhibition assays were carried out on the halogenated fosmidomycin analogues. The results showed good inhibition of the enzyme by the phosphonic acids of the chloroacetyl and chloropropyl analogues 2.1 and 2.2 respectively. Molecular modelling of the compounds on E. coli (PDB code: 2EGH) and P. falciparum (PDB code: 3AUA) DXR showed strong binding of the halogenated fosmidomycin analogues while the hybrids in the absence of docked NADPH showed minimum binding to the enzymes.
- Full Text:
- Date Issued: 2012
A comparative polarimetric study of the 43 GHz and 86 GHz SiO masers toward the supergiant star VY CMa
- Authors: Richter, Laura
- Date: 2012
- Subjects: Masers Supergiant stars Polarization (Light) Very long baseline interferometry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5454 , http://hdl.handle.net/10962/d1005239
- Description: The aim of this thesis is to perform observational tests of SiO maser polarisation and excitation models, using component-level comparisons of multiple SiO maser transitions in the 43 GHz and 86 GHz bands at milliarcsecond resolution. These observations reqwre very long baseline interferometric imaging with very accurate polarimetric calibration. The supergiant star VY CMa was chosen as the object of this study due to its high SiO maser luminosity, many detected SiO maser lines, and intrinsic scientific interest. Two epochs of full-polarisation VLBA observations of VY CMa were performed. The Epoch 2 observations were reduced using several new data reduction methods developed as part of this work, and designed specifically to improve the accuracy of circular polarisation calibration of spectral-line VLBI observations at millimetre wavelengths. The accuracy is estimated to be better than 1% using these methods. The Epoch 2 images show a concentration of v= l and v=2 J= 1-0 SiO masers to the east and northeast of the assumed stellar position. The v=l J=2-1 masers were more evenly distributed around the star, with a notable lack of emission in the northeast. There is appreciable spatial overlap between these three lines. The nature of the overlap is generally consistent with the predictions of hydrodynamical circumstellar SiO maser simulations. Where the v=l J = 1-0 and J =2-1 features overlap, the v=l J = 2-1 emission is usually considerably weaker. This is not predicted by current hydrodynamical models, but can be explained in the context of collisional pumping in a low density environment. Six observational tests of weak-splitting maser polarisation models were performed, including intercomparisons of linear polarisation in the v=l J=1-0 and J=2-1lines, linear polarisation versus saturation level, linear polarisation versus distance from the star, circular polarisation in the v= l J = 1-0 and J=2-1 lines, circular versus linear polarisation and modeling of ~ 900 electric-vector position angle rotations. The polarisation model tests generally do not support non-Zeeman circular polarisation mechanisms. For the linear polarisation tests, the results are more consistent with models that predict similar linear polarisation across transitions. The scientific importance of these tests is described in detail and avenues for future work are described.
- Full Text:
- Date Issued: 2012
- Authors: Richter, Laura
- Date: 2012
- Subjects: Masers Supergiant stars Polarization (Light) Very long baseline interferometry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5454 , http://hdl.handle.net/10962/d1005239
- Description: The aim of this thesis is to perform observational tests of SiO maser polarisation and excitation models, using component-level comparisons of multiple SiO maser transitions in the 43 GHz and 86 GHz bands at milliarcsecond resolution. These observations reqwre very long baseline interferometric imaging with very accurate polarimetric calibration. The supergiant star VY CMa was chosen as the object of this study due to its high SiO maser luminosity, many detected SiO maser lines, and intrinsic scientific interest. Two epochs of full-polarisation VLBA observations of VY CMa were performed. The Epoch 2 observations were reduced using several new data reduction methods developed as part of this work, and designed specifically to improve the accuracy of circular polarisation calibration of spectral-line VLBI observations at millimetre wavelengths. The accuracy is estimated to be better than 1% using these methods. The Epoch 2 images show a concentration of v= l and v=2 J= 1-0 SiO masers to the east and northeast of the assumed stellar position. The v=l J=2-1 masers were more evenly distributed around the star, with a notable lack of emission in the northeast. There is appreciable spatial overlap between these three lines. The nature of the overlap is generally consistent with the predictions of hydrodynamical circumstellar SiO maser simulations. Where the v=l J = 1-0 and J =2-1 features overlap, the v=l J = 2-1 emission is usually considerably weaker. This is not predicted by current hydrodynamical models, but can be explained in the context of collisional pumping in a low density environment. Six observational tests of weak-splitting maser polarisation models were performed, including intercomparisons of linear polarisation in the v=l J=1-0 and J=2-1lines, linear polarisation versus saturation level, linear polarisation versus distance from the star, circular polarisation in the v= l J = 1-0 and J=2-1 lines, circular versus linear polarisation and modeling of ~ 900 electric-vector position angle rotations. The polarisation model tests generally do not support non-Zeeman circular polarisation mechanisms. For the linear polarisation tests, the results are more consistent with models that predict similar linear polarisation across transitions. The scientific importance of these tests is described in detail and avenues for future work are described.
- Full Text:
- Date Issued: 2012
Nanocomposites of nickel phthalocyanines as electrocatalysts for the oxidation of chlorophenols an experimental and theoretical approach
- Authors: Khene, Mielie Samson
- Date: 2012
- Subjects: Nanocomposites (Materials) -- Research Phthalocyanines -- Research Chlorophenols -- Research Electrocatalysis -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4326 , http://hdl.handle.net/10962/d1004986
- Description: In this work the interaction between peripherally (b) substituted nickel tetrahydroxyphthalocyanines (b-NiPc(OH)4 and poly-b-Ni(O)Pc(OH)4) with 4-chlorophenol is theoretically rationalized by performing calculations at the B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and 4-chlorophenol, in order to determine the reactive sites involved when 4-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: OPGE-α-NiPc(OH)8 (OPGE = ordinary pyrolytic graphite electrode, α = nonperipheral substitution), OPGE-a-NiPc(OH)4 and OPGE-β- NiPc(OH)4 are compared with those of the polymerized counterparts: OPGE-poly-α-Ni(O)Pc(OH)8, OPGE poly-a-NiPc(OH)4 and OPGE-poly-β-NiPc(OH)4, respectively. β-NiPc(NH2)4, β-NiPc(OH)4, α-NiPc(OH)4, α-NiPc(OH)8, α-NiPc(C10H21)8 are adsorbed on singled walled carbon nanotube (SWCNT) and β-NiPc(NH2)4-SWCNT (linked to SWCNT), are used to modify glassy carbon electrode (GCE) and employed for the electro oxidation of chlorophenols. The β-NiPc(NH2)4-SWCNT gave the best current response for the oxidation of 4-chlorophenol. α-NiPc(OH)8-SWCNT and α-NiPc(C10H21)8 gave the best resistance to electrode fouling due to oxidation by product of 4-chlorophenol. The synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) capped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (β-NiPc(NH2)4) complex were also employed for the oxidation of chlorophenols. Separation of one of the diastereomers of 1, 2-subnaphthalocyanine (SubNPc) was achieved as well as separation of the enantiomers. The absorption and magnetic circular dichroism spectra, together with theoretical calculations, reveal rather small variations in the frontier molecular orbitals of the SubNPc compared to conventional subphthalocyanine (SubPc), except for the destabilization of the highest occupied molecular orbital (HOMO), which results in a characteristic absorption in the Soret band region. The chirality of SubNPc, including the cyclic dichroism (CD) signs and intensities, are discussed in detail.
- Full Text:
- Date Issued: 2012
- Authors: Khene, Mielie Samson
- Date: 2012
- Subjects: Nanocomposites (Materials) -- Research Phthalocyanines -- Research Chlorophenols -- Research Electrocatalysis -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4326 , http://hdl.handle.net/10962/d1004986
- Description: In this work the interaction between peripherally (b) substituted nickel tetrahydroxyphthalocyanines (b-NiPc(OH)4 and poly-b-Ni(O)Pc(OH)4) with 4-chlorophenol is theoretically rationalized by performing calculations at the B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and 4-chlorophenol, in order to determine the reactive sites involved when 4-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: OPGE-α-NiPc(OH)8 (OPGE = ordinary pyrolytic graphite electrode, α = nonperipheral substitution), OPGE-a-NiPc(OH)4 and OPGE-β- NiPc(OH)4 are compared with those of the polymerized counterparts: OPGE-poly-α-Ni(O)Pc(OH)8, OPGE poly-a-NiPc(OH)4 and OPGE-poly-β-NiPc(OH)4, respectively. β-NiPc(NH2)4, β-NiPc(OH)4, α-NiPc(OH)4, α-NiPc(OH)8, α-NiPc(C10H21)8 are adsorbed on singled walled carbon nanotube (SWCNT) and β-NiPc(NH2)4-SWCNT (linked to SWCNT), are used to modify glassy carbon electrode (GCE) and employed for the electro oxidation of chlorophenols. The β-NiPc(NH2)4-SWCNT gave the best current response for the oxidation of 4-chlorophenol. α-NiPc(OH)8-SWCNT and α-NiPc(C10H21)8 gave the best resistance to electrode fouling due to oxidation by product of 4-chlorophenol. The synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) capped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (β-NiPc(NH2)4) complex were also employed for the oxidation of chlorophenols. Separation of one of the diastereomers of 1, 2-subnaphthalocyanine (SubNPc) was achieved as well as separation of the enantiomers. The absorption and magnetic circular dichroism spectra, together with theoretical calculations, reveal rather small variations in the frontier molecular orbitals of the SubNPc compared to conventional subphthalocyanine (SubPc), except for the destabilization of the highest occupied molecular orbital (HOMO), which results in a characteristic absorption in the Soret band region. The chirality of SubNPc, including the cyclic dichroism (CD) signs and intensities, are discussed in detail.
- Full Text:
- Date Issued: 2012
Assessing the effect of a laundry detergent ingredient (LAS) on organisms of a rural South African river
- Authors: Gordon, Andrew K
- Date: 2012
- Subjects: Detergent pollution of rivers, lakes, etc. -- Research -- South Africa -- Eastern Cape Water -- Pollution -- Research -- South Africa -- Eastern Cape Stream health -- Research -- South Africa -- Eastern Cape Stream ecology -- Research -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6042 , http://hdl.handle.net/10962/d1006201
- Description: Powdered laundry detergents are consumed in high volumes worldwide. Post use, they are directed toward water resources via wastewater treatment works or, as is the situation in many rural areas of South Africa, they enter the environment directly as a result of laundry washing activity undertaken alongside surface waters. Within wastewater treatment works, the main ingredient in powdered laundry detergents, the narcotic toxin linear alkylbenzene sulfonate (LAS), is mostly removed, rendering the waste stream a negligible risk to the aquatic biota of receiving waters. In contrast, the biological and ecological impacts of direct LAS input to the aquatic environment, as a consequence of near-stream laundry washing, are yet to be fully realised. Consequently, this thesis posed two research questions: 1) 'What are the LAS concentrations in a small rural South African river'? and 2) 'Is the in-stream biological community negatively affected at these concentrations?' The chosen study area, the community of Balfour in the Eastern Cape Province, is like many rural areas of South Africa where inadequate provision of piped water to homesteads necessitates laundry washing alongside the nearby Balfour River. The first research question was addressed in two ways: by predicting LAS concentrations in Balfour River water by assessing detergent consumption and laundry washing behaviour of residents living alongside the river; and measuring actual in- stream LAS concentrations on different days of the week and during different seasons. Results indicated that LAS concentrations were highly variable temporally and spatially. High peak concentrations of LAS occurred infrequently and were limited to the immediate vicinity of near-stream laundry washing activity with the highest measured concentration being 342 μg.L ⁻¹ and the average 21 μg.L ⁻¹ over the sampling period. The second research question was addressed by integrating the chemical evidence, determined from the first research question, with the biological evidence of stress responses measured in macroinvertebrates collected downstream of near-stream laundry washing activity on the Balfour River. Predicted and measured LAS exposure concentrations from the Balfour River were compared to a water quality guideline for LAS (304 μg.L ⁻¹), specifically derived in this thesis. Biological stress responses were measured at different levels of organisation: two sub-cellular responses (lipid peroxidation and cholinesterase activity); three measures of macroinvertebrate tolerance to water quality impairment; five measures of community composition; three measures of community richness; and a surrogate measure of ecosystem function (functional feeding groups). Weight-of-evidence methodology was utilised to assess, integrate and interpret the chemical and biological evidence, and at its conclusion, determined no effect on the in-stream biological community of the Balfour River downstream of laundry washing activity.
- Full Text:
- Date Issued: 2012
- Authors: Gordon, Andrew K
- Date: 2012
- Subjects: Detergent pollution of rivers, lakes, etc. -- Research -- South Africa -- Eastern Cape Water -- Pollution -- Research -- South Africa -- Eastern Cape Stream health -- Research -- South Africa -- Eastern Cape Stream ecology -- Research -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6042 , http://hdl.handle.net/10962/d1006201
- Description: Powdered laundry detergents are consumed in high volumes worldwide. Post use, they are directed toward water resources via wastewater treatment works or, as is the situation in many rural areas of South Africa, they enter the environment directly as a result of laundry washing activity undertaken alongside surface waters. Within wastewater treatment works, the main ingredient in powdered laundry detergents, the narcotic toxin linear alkylbenzene sulfonate (LAS), is mostly removed, rendering the waste stream a negligible risk to the aquatic biota of receiving waters. In contrast, the biological and ecological impacts of direct LAS input to the aquatic environment, as a consequence of near-stream laundry washing, are yet to be fully realised. Consequently, this thesis posed two research questions: 1) 'What are the LAS concentrations in a small rural South African river'? and 2) 'Is the in-stream biological community negatively affected at these concentrations?' The chosen study area, the community of Balfour in the Eastern Cape Province, is like many rural areas of South Africa where inadequate provision of piped water to homesteads necessitates laundry washing alongside the nearby Balfour River. The first research question was addressed in two ways: by predicting LAS concentrations in Balfour River water by assessing detergent consumption and laundry washing behaviour of residents living alongside the river; and measuring actual in- stream LAS concentrations on different days of the week and during different seasons. Results indicated that LAS concentrations were highly variable temporally and spatially. High peak concentrations of LAS occurred infrequently and were limited to the immediate vicinity of near-stream laundry washing activity with the highest measured concentration being 342 μg.L ⁻¹ and the average 21 μg.L ⁻¹ over the sampling period. The second research question was addressed by integrating the chemical evidence, determined from the first research question, with the biological evidence of stress responses measured in macroinvertebrates collected downstream of near-stream laundry washing activity on the Balfour River. Predicted and measured LAS exposure concentrations from the Balfour River were compared to a water quality guideline for LAS (304 μg.L ⁻¹), specifically derived in this thesis. Biological stress responses were measured at different levels of organisation: two sub-cellular responses (lipid peroxidation and cholinesterase activity); three measures of macroinvertebrate tolerance to water quality impairment; five measures of community composition; three measures of community richness; and a surrogate measure of ecosystem function (functional feeding groups). Weight-of-evidence methodology was utilised to assess, integrate and interpret the chemical and biological evidence, and at its conclusion, determined no effect on the in-stream biological community of the Balfour River downstream of laundry washing activity.
- Full Text:
- Date Issued: 2012
An analysis of ionospheric response to geomagnetic disturbances over South Africa and Antarctica
- Authors: Ngwira, Chigomezyo Mudala
- Date: 2012
- Subjects: Geomagnetism -- South Africa , Geomagnetism -- Antarctica , Ionospheric storms -- South Africa , Ionospheric storms -- Antarctica
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5534 , http://hdl.handle.net/10962/d1012957
- Description: The ionosphere is of practical importance for satellite-based communication and navigation systems due to its variable refractive nature which affects the propagation of trans-ionospheric radio signals. This thesis reports on the first attempt to investigate the mechanisms responsible for the generation of positive ionospheric storm effects over mid-latitude South Africa. The storm response on 15 May 2005 was associated with equatorward neutral winds and the passage of travelling ionospheric disturbances (TIDs). The two TIDs reported in this thesis propagated with average velocities of ∼438 m/s and ∼515 m/s respectively. The velocity of the first TID (i.e. 438 m/s) is consistent with the velocities calculated in other studies for the same storm event. In a second case study, the positive storm enhancement on both 25 and 27 July 2004 lasted for more than 7 hours, and were classified as long-duration positive ionospheric storm effects. It has been suggested that the long-duration positive storm effects could have been caused by large-scale thermospheric wind circulation and enhanced equatorward neutral winds. These processes were in turn most likely to have been driven by enhanced and sustained energy input in the high-latitude ionosphere due to Joule heating and particle energy injection. This is evident by the prolonged high-level geomagnetic activity on both 25 and 27 July. This thesis also reports on the phase scintillation investigation at the South African Antarctic polar research station during solar minimum conditions. The multi-instrument approach that was used shows that the scintillation events were associated with auroral electron precipitation and that substorms play an essential role in the production of scintillation in the high latitudes. Furthermore, the investigation reveals that external energy injection into the ionosphere is necessary for the development of high-latitude irregularities which produce scintillation. Finally, this thesis highlights inadequate data resources as one of the major shortcomings to be addressed in order to fully understand and distinguish between the various ionospheric storm drivers over the Southern Africa mid-latitude region. The results presented in this thesis on the ionospheric response during geomagnetic storms provide essential information to direct further investigation aimed at developing this emerging field of study in South Africa.
- Full Text:
- Date Issued: 2012
- Authors: Ngwira, Chigomezyo Mudala
- Date: 2012
- Subjects: Geomagnetism -- South Africa , Geomagnetism -- Antarctica , Ionospheric storms -- South Africa , Ionospheric storms -- Antarctica
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5534 , http://hdl.handle.net/10962/d1012957
- Description: The ionosphere is of practical importance for satellite-based communication and navigation systems due to its variable refractive nature which affects the propagation of trans-ionospheric radio signals. This thesis reports on the first attempt to investigate the mechanisms responsible for the generation of positive ionospheric storm effects over mid-latitude South Africa. The storm response on 15 May 2005 was associated with equatorward neutral winds and the passage of travelling ionospheric disturbances (TIDs). The two TIDs reported in this thesis propagated with average velocities of ∼438 m/s and ∼515 m/s respectively. The velocity of the first TID (i.e. 438 m/s) is consistent with the velocities calculated in other studies for the same storm event. In a second case study, the positive storm enhancement on both 25 and 27 July 2004 lasted for more than 7 hours, and were classified as long-duration positive ionospheric storm effects. It has been suggested that the long-duration positive storm effects could have been caused by large-scale thermospheric wind circulation and enhanced equatorward neutral winds. These processes were in turn most likely to have been driven by enhanced and sustained energy input in the high-latitude ionosphere due to Joule heating and particle energy injection. This is evident by the prolonged high-level geomagnetic activity on both 25 and 27 July. This thesis also reports on the phase scintillation investigation at the South African Antarctic polar research station during solar minimum conditions. The multi-instrument approach that was used shows that the scintillation events were associated with auroral electron precipitation and that substorms play an essential role in the production of scintillation in the high latitudes. Furthermore, the investigation reveals that external energy injection into the ionosphere is necessary for the development of high-latitude irregularities which produce scintillation. Finally, this thesis highlights inadequate data resources as one of the major shortcomings to be addressed in order to fully understand and distinguish between the various ionospheric storm drivers over the Southern Africa mid-latitude region. The results presented in this thesis on the ionospheric response during geomagnetic storms provide essential information to direct further investigation aimed at developing this emerging field of study in South Africa.
- Full Text:
- Date Issued: 2012