Management and the dynamics of labour process: study of workplace relations in an oil refinery, Nigeria
- Oladeinde, Olusegun Olurotimi
- Authors: Oladeinde, Olusegun Olurotimi
- Date: 2011
- Subjects: Nigerian National Petroleum Corporation Personnel management -- Nigeria Petroleum industry and trade -- Personnel management -- Nigeria Performance -- Management -- Nigeria Industrial relations -- Nigeria Organizational behavior -- Nigeria Total quality management -- Nigeria Labor unions -- Nigeria Petroleum workers -- Nigeria -- Attitudes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3299 , http://hdl.handle.net/10962/d1003087
- Description: The focus of this thesis is on labour-management relations in the Nigerian National Petroleum Corporation (NNPC), Nigeria. The study explores current managerial practices in the corporation and their effects on the intensification of work, and how the management sought to control workers and the labour process. The study explores the experiences of workers and their perception of managerial practices. Evidence suggests that managerial practices and their impacts on workplace relations in NNPC have become more subtle, with wider implications for workers’ experience and the labour process. Using primary data obtained through interviews, participant observation, and documentary sources, the thesis assesses how managerial practices are varieties of controls of labour in which workers’ consent is also embedded. This embeddedness of the labour process generates new types of worker subjectivity and identity, with significant implications for labour relations. The study suggests that multiple dimensions of workers’ sense-making reflect the structural and subjective dimensions of the labour process. In NNPC, the consequence of managerial practices has been an emergence of a new type of subjectivity; one that has closely identified with the corporate values and is not overtly disposed towards resistance or dissent. While workers consent at NNPC continues to be an outcome of managerial practices, the thesis examined its implications. The thesis seeks to explain the effects of managerial control mechanisms in shaping workers’ experience and identity. However, the thesis shows that while workers remain susceptible to these forms of managerial influence, an erasure or closure of oppositions or recalcitrance will not adequately account for workers’ identity-formation. The thesis shows that while managerial control remains significant, workers inhabit domains that are ‘unmanaged’ and ‘unmanageable’ where ‘resistance’ and ‘misbehaviour’ reside. Without a conceptual and empirical interrogation, evidence of normative and mutual benefits of managerial practices or a submissive image of workers will produce images of workers that obscure their covert opposition and resistance. Workers ‘collude’ with the ‘hubris’ of management in order to invert and subvert managerial practices and intentions. Through theoretical reconceptualization, the thesis demonstrates the specific dimensions of these inversions and subversions. The thesis therefore seeks to re-insert “worker-agency” back into the analysis of power-relations in the workplace; agency that is not overtly under the absolute grip of managerial control, but with a multiplicity of identities and multilevel manifestations.
- Full Text:
- Authors: Oladeinde, Olusegun Olurotimi
- Date: 2011
- Subjects: Nigerian National Petroleum Corporation Personnel management -- Nigeria Petroleum industry and trade -- Personnel management -- Nigeria Performance -- Management -- Nigeria Industrial relations -- Nigeria Organizational behavior -- Nigeria Total quality management -- Nigeria Labor unions -- Nigeria Petroleum workers -- Nigeria -- Attitudes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3299 , http://hdl.handle.net/10962/d1003087
- Description: The focus of this thesis is on labour-management relations in the Nigerian National Petroleum Corporation (NNPC), Nigeria. The study explores current managerial practices in the corporation and their effects on the intensification of work, and how the management sought to control workers and the labour process. The study explores the experiences of workers and their perception of managerial practices. Evidence suggests that managerial practices and their impacts on workplace relations in NNPC have become more subtle, with wider implications for workers’ experience and the labour process. Using primary data obtained through interviews, participant observation, and documentary sources, the thesis assesses how managerial practices are varieties of controls of labour in which workers’ consent is also embedded. This embeddedness of the labour process generates new types of worker subjectivity and identity, with significant implications for labour relations. The study suggests that multiple dimensions of workers’ sense-making reflect the structural and subjective dimensions of the labour process. In NNPC, the consequence of managerial practices has been an emergence of a new type of subjectivity; one that has closely identified with the corporate values and is not overtly disposed towards resistance or dissent. While workers consent at NNPC continues to be an outcome of managerial practices, the thesis examined its implications. The thesis seeks to explain the effects of managerial control mechanisms in shaping workers’ experience and identity. However, the thesis shows that while workers remain susceptible to these forms of managerial influence, an erasure or closure of oppositions or recalcitrance will not adequately account for workers’ identity-formation. The thesis shows that while managerial control remains significant, workers inhabit domains that are ‘unmanaged’ and ‘unmanageable’ where ‘resistance’ and ‘misbehaviour’ reside. Without a conceptual and empirical interrogation, evidence of normative and mutual benefits of managerial practices or a submissive image of workers will produce images of workers that obscure their covert opposition and resistance. Workers ‘collude’ with the ‘hubris’ of management in order to invert and subvert managerial practices and intentions. Through theoretical reconceptualization, the thesis demonstrates the specific dimensions of these inversions and subversions. The thesis therefore seeks to re-insert “worker-agency” back into the analysis of power-relations in the workplace; agency that is not overtly under the absolute grip of managerial control, but with a multiplicity of identities and multilevel manifestations.
- Full Text:
Modelling the relationship between flow and water quality in South African rivers
- Authors: Slaughter, Andrew Robert
- Date: 2011
- Subjects: Water quality -- Measurement -- South Africa Water quality -- Mathematical models -- South Africa Streamflow -- South Africa Stream measurements -- Mathematical models -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6039 , http://hdl.handle.net/10962/d1006196
- Description: The National Water Act (Act 36 of 1998) provides for an ecological Reserve as the quantity (flow) and quality of water needed to protect aquatic ecosystems. While there are methods available to quantify the ecological Reserve in terms of flow, methods of linking flow to water quality are lacking. Therefore, the research presented in this thesis investigated various modelling techniques to estimate the effect of flow on water quality. The aims of the research presented in this thesis were: Aim 1: Can the relationship between flow and water quality be accurately represented by simple statistical models? Aim 2: Can relatively simple models accurately represent the relationship between flow and water quality? Aim 3: Can the effect of diffuse sources be omitted from a water quality model and still obtain realistic simulations, and if so under what conditions? Aim 4: Can models that solely use historical monitoring data, accurately represent the relationships between flow and water quality? In Chapter 3, simple Q-C regressions of flow and water quality were investigated using Department of Water Affairs (DWA) historical monitoring data. It was found that while flow versus salinity regressions gave good regression fits in many cases, the Q-C regression approach is limited. A mechanistic/statistical model that attempted to estimate the point and diffuse signatures of nutrients in response to flow was developed in Chapter 4 using DWA historical monitoring data. The model was verified as accurate in certain case studies using observed point loading information. In Chapter 5, statistical models that link land cover information to diffuse nutrient signatures in response to flow using DWA historical data were developed. While the model estimations are uncertain due to a lack of data, they do provide an estimation of the diffuse signature within catchments where there is flow and land cover information available. Chapter 6 investigates the extension of an existing mass-balance salinity model to estimate the effect of saline irrigation return flow on in-stream salinity. The model gave accurate salinity estimates for a low order stream with little or no irrigation within its catchment, and for a permanently flowing river within a catchment used extensively for irrigation. Chapter 7 investigated a modelling method to estimate the reaction coefficients involved in nitrification using only DWA historical monitoring data. Here, the model used flow information to estimate the residence time of nutrients within the studied river reaches. While the model obtained good estimations of nitrification for the data it was applied to, very few DWA data sets were suitable for the model. Chapter 8 investigated the ability of the in-stream model QUAL2K to estimate nutrient concentrations downstream of point and diffuse inputs of nutrients. It was found that the QUAL2K model can give accurate results in cases where point sources dominate the total nutrient inputs into a river. However, the QUAL2K simulations are too uncertain in cases where there are large diffuse source inputs of nutrients as the load of the diffuse inputs is difficult to measure in the field. This research highlights the problem of data scarcity in terms of temporal resolution as well as the range of constituents measured within DWA historical monitoring data for water quality. This thesis in addition argues that the approach of applying a number of models is preferable to applying one model to investigate the research aims, as particular models would be suited to particular circumstances, and the development of new models allowed the research aims of this thesis to be explored more thoroughly. It is also argued that simpler models that simulate a few key processes that explain the variation in observed data, are more suitable for implementing Integrated Water Resource Management (IWRM) than large comprehensive water quality models. From this research, it is clear that simple statistical models are not adequate for modelling the relationship between flow and water quality, however, relatively simple mechanistic models that simulate a limited number of processes and water quality variables, can provide accurate representations of this relationship. Under conditions where diffuse sources are not a major factor within a catchment, models that omit diffuse sources can obtain realistic simulations of the relationship between flow and water quality. Most of the models investigated in this thesis demonstrate that accurate simulations of the relationships between flow and water quality can be obtained using solely historical monitoring data.
- Full Text:
- Authors: Slaughter, Andrew Robert
- Date: 2011
- Subjects: Water quality -- Measurement -- South Africa Water quality -- Mathematical models -- South Africa Streamflow -- South Africa Stream measurements -- Mathematical models -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6039 , http://hdl.handle.net/10962/d1006196
- Description: The National Water Act (Act 36 of 1998) provides for an ecological Reserve as the quantity (flow) and quality of water needed to protect aquatic ecosystems. While there are methods available to quantify the ecological Reserve in terms of flow, methods of linking flow to water quality are lacking. Therefore, the research presented in this thesis investigated various modelling techniques to estimate the effect of flow on water quality. The aims of the research presented in this thesis were: Aim 1: Can the relationship between flow and water quality be accurately represented by simple statistical models? Aim 2: Can relatively simple models accurately represent the relationship between flow and water quality? Aim 3: Can the effect of diffuse sources be omitted from a water quality model and still obtain realistic simulations, and if so under what conditions? Aim 4: Can models that solely use historical monitoring data, accurately represent the relationships between flow and water quality? In Chapter 3, simple Q-C regressions of flow and water quality were investigated using Department of Water Affairs (DWA) historical monitoring data. It was found that while flow versus salinity regressions gave good regression fits in many cases, the Q-C regression approach is limited. A mechanistic/statistical model that attempted to estimate the point and diffuse signatures of nutrients in response to flow was developed in Chapter 4 using DWA historical monitoring data. The model was verified as accurate in certain case studies using observed point loading information. In Chapter 5, statistical models that link land cover information to diffuse nutrient signatures in response to flow using DWA historical data were developed. While the model estimations are uncertain due to a lack of data, they do provide an estimation of the diffuse signature within catchments where there is flow and land cover information available. Chapter 6 investigates the extension of an existing mass-balance salinity model to estimate the effect of saline irrigation return flow on in-stream salinity. The model gave accurate salinity estimates for a low order stream with little or no irrigation within its catchment, and for a permanently flowing river within a catchment used extensively for irrigation. Chapter 7 investigated a modelling method to estimate the reaction coefficients involved in nitrification using only DWA historical monitoring data. Here, the model used flow information to estimate the residence time of nutrients within the studied river reaches. While the model obtained good estimations of nitrification for the data it was applied to, very few DWA data sets were suitable for the model. Chapter 8 investigated the ability of the in-stream model QUAL2K to estimate nutrient concentrations downstream of point and diffuse inputs of nutrients. It was found that the QUAL2K model can give accurate results in cases where point sources dominate the total nutrient inputs into a river. However, the QUAL2K simulations are too uncertain in cases where there are large diffuse source inputs of nutrients as the load of the diffuse inputs is difficult to measure in the field. This research highlights the problem of data scarcity in terms of temporal resolution as well as the range of constituents measured within DWA historical monitoring data for water quality. This thesis in addition argues that the approach of applying a number of models is preferable to applying one model to investigate the research aims, as particular models would be suited to particular circumstances, and the development of new models allowed the research aims of this thesis to be explored more thoroughly. It is also argued that simpler models that simulate a few key processes that explain the variation in observed data, are more suitable for implementing Integrated Water Resource Management (IWRM) than large comprehensive water quality models. From this research, it is clear that simple statistical models are not adequate for modelling the relationship between flow and water quality, however, relatively simple mechanistic models that simulate a limited number of processes and water quality variables, can provide accurate representations of this relationship. Under conditions where diffuse sources are not a major factor within a catchment, models that omit diffuse sources can obtain realistic simulations of the relationship between flow and water quality. Most of the models investigated in this thesis demonstrate that accurate simulations of the relationships between flow and water quality can be obtained using solely historical monitoring data.
- Full Text:
Molecular analysis of genetic diversity in dometicated pigeonpea (Cajanus cajan (L.) Millsp.) and wild relatives
- Authors: Kassa, Mulualem Tamiru
- Date: 2011
- Subjects: Pigeon pea -- Variation Cajanus -- Variation Pigeon pea -- Genetics Cajanus -- Genetics Biodiversity Pigeon pea -- Phylogeny Cajanus -- Phylogeny Plant hybridization Plant diversity Transgenic plants
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4204 , http://hdl.handle.net/10962/d1003773
- Description: Cajanus cajan (L.) Millsp. (Pigeonpea) belongs to the Leguminosae genus Cajanus which is composed of 34 species. Pigeonpea is the only cultivated member of the genus, while the remaining species are wild relatives belonging mainly to the secondary gene pool. DNA sequence data from the nuclear ITS region and the chloroplast trnL-F spacer were utilized to investigate the phylogenetic relationships between Cajanus and five other allied genera in the subtribe Cajaninae. This study revealed the non-monophyly of Cajanus and Rhynchosia and supported the monophyly of Eriosema and Flemingia, but more sampling ,especially from the large genera of Rhynchosia and Eriosema, is recommend to adequately test the hypothesis of generic monophyly. The phylogenetic relationships within the genus Cajanus resolved Cajanus scarabaeoides (L.) Thouars as the most basal species in the Cajanus clade. The study also utilized Single Nucleotide Polymorphism (SNP) markers derived from low copy orthologous genes and genotyped using the high throughput SNP-OPA Illumina golden gate assay. The aim was to understand phylogenetic and domestication history, genetic structure, patterns of genetic diversity, gene flow and historical hybridization between Cajanus cajan (pigeonpea) and wild relatives. The neighbor-joining tree resolved well-supported clusters, which reflect the distinctiveness of species and congruence with their geographical origin. It supported the ITS based phylogeny and resolved C. scarabaeoides as basal to the Cajanus clade. The phylogenetic signal and genetic signatures revealed insights into the domestication history of pigeonpea. Our results supported Cajanus cajanifolius as the presumed progenitor of pigeonpea and we speculate that for pigeonpea there was a single major domestication event in India. Genetic admixture and historical hybridization were evident between pigeonpea and wild relatives. Abundant allelic variation and genetic diversity was found in the wild relatives, with the exception of wild species from Australia, as compared to the domesticated pigeonpea. There was a reduction of about 75% in genetic polymorphism in domesticated pigeonpea as compared to the wild relatives, indicating a severe “domestication bottleneck” during pigeonpea domestication. We discovered SNP markers associated with disease resistance (NBS-LRR) loci. The SNPs were mined in a comparison of BAC-end sequences (BES) of C. cajan and amplicons of the wild species, C. scarabaeoides. A total of ~3000 SNPs were identified from 304 BES. These SNPs could potentially be used in constructing a genetic map and for marker assisted breeding.
- Full Text:
- Authors: Kassa, Mulualem Tamiru
- Date: 2011
- Subjects: Pigeon pea -- Variation Cajanus -- Variation Pigeon pea -- Genetics Cajanus -- Genetics Biodiversity Pigeon pea -- Phylogeny Cajanus -- Phylogeny Plant hybridization Plant diversity Transgenic plants
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4204 , http://hdl.handle.net/10962/d1003773
- Description: Cajanus cajan (L.) Millsp. (Pigeonpea) belongs to the Leguminosae genus Cajanus which is composed of 34 species. Pigeonpea is the only cultivated member of the genus, while the remaining species are wild relatives belonging mainly to the secondary gene pool. DNA sequence data from the nuclear ITS region and the chloroplast trnL-F spacer were utilized to investigate the phylogenetic relationships between Cajanus and five other allied genera in the subtribe Cajaninae. This study revealed the non-monophyly of Cajanus and Rhynchosia and supported the monophyly of Eriosema and Flemingia, but more sampling ,especially from the large genera of Rhynchosia and Eriosema, is recommend to adequately test the hypothesis of generic monophyly. The phylogenetic relationships within the genus Cajanus resolved Cajanus scarabaeoides (L.) Thouars as the most basal species in the Cajanus clade. The study also utilized Single Nucleotide Polymorphism (SNP) markers derived from low copy orthologous genes and genotyped using the high throughput SNP-OPA Illumina golden gate assay. The aim was to understand phylogenetic and domestication history, genetic structure, patterns of genetic diversity, gene flow and historical hybridization between Cajanus cajan (pigeonpea) and wild relatives. The neighbor-joining tree resolved well-supported clusters, which reflect the distinctiveness of species and congruence with their geographical origin. It supported the ITS based phylogeny and resolved C. scarabaeoides as basal to the Cajanus clade. The phylogenetic signal and genetic signatures revealed insights into the domestication history of pigeonpea. Our results supported Cajanus cajanifolius as the presumed progenitor of pigeonpea and we speculate that for pigeonpea there was a single major domestication event in India. Genetic admixture and historical hybridization were evident between pigeonpea and wild relatives. Abundant allelic variation and genetic diversity was found in the wild relatives, with the exception of wild species from Australia, as compared to the domesticated pigeonpea. There was a reduction of about 75% in genetic polymorphism in domesticated pigeonpea as compared to the wild relatives, indicating a severe “domestication bottleneck” during pigeonpea domestication. We discovered SNP markers associated with disease resistance (NBS-LRR) loci. The SNPs were mined in a comparison of BAC-end sequences (BES) of C. cajan and amplicons of the wild species, C. scarabaeoides. A total of ~3000 SNPs were identified from 304 BES. These SNPs could potentially be used in constructing a genetic map and for marker assisted breeding.
- Full Text:
My other - my self: post-Cartesian ontological possibilities in the fiction of J M Coetzee
- Authors: Mfune, Damazio Laston
- Date: 2011
- Subjects: Coetzee, J. M., 1940- -- Criticism and interpretation Self in literature Identity (Psychology) in literature Consciousness in literature Intersubjectivity in literature Ontology in literature Metaphysics in literature South African fiction (English) -- 20th century -- History and criticism
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2246 , http://hdl.handle.net/10962/d1002289
- Description: The central argument of my study is that, among other matters, in his works, J.M. Coetzee could be said to demonstrate that the known Self is an embodied being and is not autonomous. With regard to the latter contention, Coetzee intimates that any two Subjects are implicated in each other’s subjectivities in a reciprocal process that involves what Derek Attridge has called “irruptions of otherness” (2005: xii) into the Subject’s subjectivity. These irruptions, which happen during the encounter, lead to a double loss of autonomy for each Subject and this phenomenon renders the relationship between Subjects non-dichotomus or non-binaric. In other words, the Subject does not produce the contents of his or her consciousness in a sui generis and ex nihilo fashion, and his or her ontological indebtedness to the Other constitutes his or her first loss of autonomy. As for those Others that do possess consciousness, the Subject is implicated in their consciousness and this constitutes the Subject’s second loss of autonomy. These losses counter the near solipsistic Nagelian neo-Cartesianism and paves the way for imagining both intra- and inter-species “intersubjectivity”. It is my view that this double loss of autonomy accounts for the sympathetic and empathetic imagination that we encounter in Coetzee’s fiction. Following Coetzee’s intimations of intersubjectivity through irruptions of otherness, what I see as my contribution to studies on this author’s work through this study is the link I have established between the physicalist strain within the philosophy of mind (whose central thesis is that consciousness is an embodied phenomenon) and a modified Kantian “metaphysics”, especially Immanuel Kant’s conception of concepts as comprising form and content. I have deployed this conception in demonstrating the Subject’s ontological indebtedness to external sources of the content part of consciousness. And, through the Husserlian concept of intentionality, and Kant’s (1929: 27) observation that we cannot have appearances without something that appears, I have linked the Subject to the sources of his or her content and thereby also demonstrated that the Subject is not eternally separated or alienated from those sources. Instead, the Subject is not simply contiguous but coterminous and co-extensive, albeit in a mediated way, with the external sources of the content part of his or her consciousness. Thus, while accepting the thesis of the Other’s radical otherness, I modify the thesis of the Other’s radical exteriority. Ultimately, then, ontologically speaking, the Coetzeean project could be described as one of embodying and grounding the supposedly autonomous, solipsistic and freefloating/disembodied Cartesian Subject. This he does by alerting this Subject, first and foremost, to its embodiedness and, further to that, pointing out its ontological indebtedness to its Others and its implication in the Others’s consciousnesses and so prevent it from continuing with its imperialistic and ecological barbarities. However, ethically speaking, beyond the reciprocal ethics that arises from mutual ontological indebtedness and implication, it is the selflessness that characterises a cruciform logic that comes across as the epitome of Coetzeean ethics.
- Full Text:
- Authors: Mfune, Damazio Laston
- Date: 2011
- Subjects: Coetzee, J. M., 1940- -- Criticism and interpretation Self in literature Identity (Psychology) in literature Consciousness in literature Intersubjectivity in literature Ontology in literature Metaphysics in literature South African fiction (English) -- 20th century -- History and criticism
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2246 , http://hdl.handle.net/10962/d1002289
- Description: The central argument of my study is that, among other matters, in his works, J.M. Coetzee could be said to demonstrate that the known Self is an embodied being and is not autonomous. With regard to the latter contention, Coetzee intimates that any two Subjects are implicated in each other’s subjectivities in a reciprocal process that involves what Derek Attridge has called “irruptions of otherness” (2005: xii) into the Subject’s subjectivity. These irruptions, which happen during the encounter, lead to a double loss of autonomy for each Subject and this phenomenon renders the relationship between Subjects non-dichotomus or non-binaric. In other words, the Subject does not produce the contents of his or her consciousness in a sui generis and ex nihilo fashion, and his or her ontological indebtedness to the Other constitutes his or her first loss of autonomy. As for those Others that do possess consciousness, the Subject is implicated in their consciousness and this constitutes the Subject’s second loss of autonomy. These losses counter the near solipsistic Nagelian neo-Cartesianism and paves the way for imagining both intra- and inter-species “intersubjectivity”. It is my view that this double loss of autonomy accounts for the sympathetic and empathetic imagination that we encounter in Coetzee’s fiction. Following Coetzee’s intimations of intersubjectivity through irruptions of otherness, what I see as my contribution to studies on this author’s work through this study is the link I have established between the physicalist strain within the philosophy of mind (whose central thesis is that consciousness is an embodied phenomenon) and a modified Kantian “metaphysics”, especially Immanuel Kant’s conception of concepts as comprising form and content. I have deployed this conception in demonstrating the Subject’s ontological indebtedness to external sources of the content part of consciousness. And, through the Husserlian concept of intentionality, and Kant’s (1929: 27) observation that we cannot have appearances without something that appears, I have linked the Subject to the sources of his or her content and thereby also demonstrated that the Subject is not eternally separated or alienated from those sources. Instead, the Subject is not simply contiguous but coterminous and co-extensive, albeit in a mediated way, with the external sources of the content part of his or her consciousness. Thus, while accepting the thesis of the Other’s radical otherness, I modify the thesis of the Other’s radical exteriority. Ultimately, then, ontologically speaking, the Coetzeean project could be described as one of embodying and grounding the supposedly autonomous, solipsistic and freefloating/disembodied Cartesian Subject. This he does by alerting this Subject, first and foremost, to its embodiedness and, further to that, pointing out its ontological indebtedness to its Others and its implication in the Others’s consciousnesses and so prevent it from continuing with its imperialistic and ecological barbarities. However, ethically speaking, beyond the reciprocal ethics that arises from mutual ontological indebtedness and implication, it is the selflessness that characterises a cruciform logic that comes across as the epitome of Coetzeean ethics.
- Full Text:
Nanomaterial modified electrodes : optimization of voltammetric sensors for pharmaceutical and industrial application
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
Oil enclave economy and sexual liaisons in Nigeria's Niger Delta region
- Authors: Gandu, Yohanna Kagoro
- Date: 2011
- Subjects: Women -- Violence against -- Nigeria Abused women -- Nigeria Sexual abuse victims -- Nigeria Prostitution -- Nigeria Oil industries -- Nigeria
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3318 , http://hdl.handle.net/10962/d1003106
- Description: This thesis examines the intersection of oil enclave economy and the phenomenon of sexual liaisons in Nigeria’s Niger Delta region. The particular focus of this thesis is on the extent to which oil enclavity contributes to the emergence of sexual liaisons between local women and expatriate oil workers. Despite the fact that the Nigerian oil industry has been subjected to considerable scholarly debate for over five decades, this aspect of the social dimension of oil has not received adequate scholarly attention. Gender-specific discourse has tended to focus more on women protest. Other aspects, such as gender-specific violence that women in the region have had to live with, are either ignored or poorly articulated. Picketing of oil platforms by protesting women is celebrated as signs that women are active in the struggle against oil Transnational Companies (TNCs). While women protest is a significant struggle against oil TNCs, it has the potential of blurring our intellectual focus on the specific challenges confronting women in the Niger Delta. This study shows that since the inauguration of the Willink Commission in 1957, national palliatives meant to alleviate poverty in the Niger Delta region have not been gender sensitive. A review of the 1957 Willink Commission and others that came after it shows that the Nigerian state is yet to address the peculiar problems that the oil industry has brought to the women folk in the region. The paradox is that while oil provides enormous wealth and means of patronage to the Nigerian state elite, the oil TNCs, and better paid expatriate oil workers, a large section of the local Oil Bearing Communities (OBCs), especially women and unemployed youth, are not only dispossessed but survive in an environment characterised by anxiety and misery. With limited survival alternatives, youths resort to violent protest including oil thefts and bunkering. Local women are also immersed in this debacle because some of them resort to sexual liaisons with economically empowered expatriate oil workers as an alternative means of survival. This study therefore shifts the focus to women by exploring the extent to which sexual liaison reflects the contradictions in the enclave oil economy. The study employed an enclave economy conceptual framework to demonstrate that oil extractive activities compromise and distort the local economies of OBCs. This situation compels local women to seek for alternative means of survival by entering into sexual liaisons with more financially privileged expatriate oil workers. The study reviewed relevant secondary documentary sources of data. Further, it employed primary data collection techniques which include in-depth interviews/life histories, ethnographic observations, focus group discussions, and visual sociology. Besides obtaining the social profile and challenges facing the women involved in sexual liaisons with expatriate oil workers, the study provides an outline of participants’ narratives on the different social and economic dimensions of the intersection of oil enclave economy and sexual liaisons. The study found that some of the women involved in sexual liaisons with expatriate oil workers have been abandoned with ‘fatherless’ children. Some of them have also been rejected by their immediate family members and, in some cases, by their community. The study also found that the phenomenon of sexual liaisons and the incidents of abandoned ‘fatherless’ children that result from the practice, has over the years been played out through local resentment against oil TNCs and their expatriate employees. This finding helps to fill the gap in narratives and to make sense of the civic revolt and deepening instability in the Niger Delta region.
- Full Text:
- Authors: Gandu, Yohanna Kagoro
- Date: 2011
- Subjects: Women -- Violence against -- Nigeria Abused women -- Nigeria Sexual abuse victims -- Nigeria Prostitution -- Nigeria Oil industries -- Nigeria
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3318 , http://hdl.handle.net/10962/d1003106
- Description: This thesis examines the intersection of oil enclave economy and the phenomenon of sexual liaisons in Nigeria’s Niger Delta region. The particular focus of this thesis is on the extent to which oil enclavity contributes to the emergence of sexual liaisons between local women and expatriate oil workers. Despite the fact that the Nigerian oil industry has been subjected to considerable scholarly debate for over five decades, this aspect of the social dimension of oil has not received adequate scholarly attention. Gender-specific discourse has tended to focus more on women protest. Other aspects, such as gender-specific violence that women in the region have had to live with, are either ignored or poorly articulated. Picketing of oil platforms by protesting women is celebrated as signs that women are active in the struggle against oil Transnational Companies (TNCs). While women protest is a significant struggle against oil TNCs, it has the potential of blurring our intellectual focus on the specific challenges confronting women in the Niger Delta. This study shows that since the inauguration of the Willink Commission in 1957, national palliatives meant to alleviate poverty in the Niger Delta region have not been gender sensitive. A review of the 1957 Willink Commission and others that came after it shows that the Nigerian state is yet to address the peculiar problems that the oil industry has brought to the women folk in the region. The paradox is that while oil provides enormous wealth and means of patronage to the Nigerian state elite, the oil TNCs, and better paid expatriate oil workers, a large section of the local Oil Bearing Communities (OBCs), especially women and unemployed youth, are not only dispossessed but survive in an environment characterised by anxiety and misery. With limited survival alternatives, youths resort to violent protest including oil thefts and bunkering. Local women are also immersed in this debacle because some of them resort to sexual liaisons with economically empowered expatriate oil workers as an alternative means of survival. This study therefore shifts the focus to women by exploring the extent to which sexual liaison reflects the contradictions in the enclave oil economy. The study employed an enclave economy conceptual framework to demonstrate that oil extractive activities compromise and distort the local economies of OBCs. This situation compels local women to seek for alternative means of survival by entering into sexual liaisons with more financially privileged expatriate oil workers. The study reviewed relevant secondary documentary sources of data. Further, it employed primary data collection techniques which include in-depth interviews/life histories, ethnographic observations, focus group discussions, and visual sociology. Besides obtaining the social profile and challenges facing the women involved in sexual liaisons with expatriate oil workers, the study provides an outline of participants’ narratives on the different social and economic dimensions of the intersection of oil enclave economy and sexual liaisons. The study found that some of the women involved in sexual liaisons with expatriate oil workers have been abandoned with ‘fatherless’ children. Some of them have also been rejected by their immediate family members and, in some cases, by their community. The study also found that the phenomenon of sexual liaisons and the incidents of abandoned ‘fatherless’ children that result from the practice, has over the years been played out through local resentment against oil TNCs and their expatriate employees. This finding helps to fill the gap in narratives and to make sense of the civic revolt and deepening instability in the Niger Delta region.
- Full Text:
Post-impoundment population dynamics of non-native common carp Cyprinus Carpio in relation to two large native cyprinids in Lake Gariep, South Africa
- Authors: Winker, Henning
- Date: 2011
- Subjects: Cyprinidae -- South Africa -- Gariep Dam Carp -- South Africa -- Gariep Dam Fish populations -- South Africa -- Gariep Dam Fishes -- Physiology -- South Africa -- Gariep Dam Barbus aeneus -- South Africa -- Gariep Dam Mudfishes -- South Africa -- Gariep Dam Freshwater fishes -- South Africa -- Gariep Dam
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5311 , http://hdl.handle.net/10962/d1005156
- Description: To contribute to the understanding of the invasion biology of common carp Cyprinus carpio in southern Africa, this thesis investigated the life history, relative abundance, long-term population demographics and trophic niche utilisations of non-native common carp C. carpio in relation to two endemic cyprinids, Orange River mudfish Labeo capensis and smallmouth yellowfish Labeobarbus aeneus in South Africa‟s largest impoundment, Lake Gariep. The growth zone deposition rates in astericus otoliths of the three species were validated as biannual for C. carpio and as annual for L. capensis and L. aeneus, which allowed for reliable estimation of lengths-at-age upon which growth, age-at-maturity and mortality rates could be estimated. Cyprinus carpio exhibited fast growth, matured relatively early at two years of age and attained a maximum age of seven years. Labeo capensis grew significantly slower, but attained older ages of up to 12 years. Females showed notably delayed maturation at approximately six years of age. The life history parameter estimates for L. aeneus were similar to those of L. capensis. These species-specific life history characteristics contributed to a substantially higher population growth potential of C. carpio compared to L. capensis and L. aeneus. Delta-lognormal and delta-gamma Generalized Linear Models (GLMs) were used to analyse patterns of relative abundance of L. capensis, L. aeneus and C. carpio. The application of these GLMs was necessary to account for large proportions of zeros and strong skewness in the catch-per-unit-effort (CPUE) from experimental gillnet and fisheries-dependent angler surveys. Confidence intervals around predicted abundance indices were obtained through the development of a generalised parametric bootstrap procedure. The resulting standardised abundance indices were coupled with results from analysis of stable isotope ratios of fish tissues and potential food resources and revealed that C. carpio was mainly confined to soft-bottom habitats, where it predominantly foraged on benthic invertebrates. Labeo capensis was abundant in a wide range of benthic habitats and was consumed basal food resources such as detritus. Labeobarbus aeneus was found to feed mostly on pelagic zooplankton. There were no significant interspecific differences in trophic niche space, suggesting limited resource competition among the three species. Standardised historical and contemporary gillnet CPUE data indicated slow population growth rates of L. capensis and L. aeneus during the first ten years postimpoundment, but showed high biomass levels some four decades after impoundment. These results could be corroborated by stochastic age-structured production model (ASPM) simulations. In contrast to the two endemic species, the gillnet CPUE of C. carpio showed a clear „boom and bust‟ pattern, which, based on ASPM simulations, could be best explained by increased food availability during the first five years postimpoundment, followed by suboptimal conditions thereafter. Together, these results provided evidence that the establishment of the C. carpio population did not prevent the slow but successful long-term establishment of the two large endemic cyprinids. Both endemic fishes revealed specialised feeding within the impoundment.
- Full Text:
- Authors: Winker, Henning
- Date: 2011
- Subjects: Cyprinidae -- South Africa -- Gariep Dam Carp -- South Africa -- Gariep Dam Fish populations -- South Africa -- Gariep Dam Fishes -- Physiology -- South Africa -- Gariep Dam Barbus aeneus -- South Africa -- Gariep Dam Mudfishes -- South Africa -- Gariep Dam Freshwater fishes -- South Africa -- Gariep Dam
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5311 , http://hdl.handle.net/10962/d1005156
- Description: To contribute to the understanding of the invasion biology of common carp Cyprinus carpio in southern Africa, this thesis investigated the life history, relative abundance, long-term population demographics and trophic niche utilisations of non-native common carp C. carpio in relation to two endemic cyprinids, Orange River mudfish Labeo capensis and smallmouth yellowfish Labeobarbus aeneus in South Africa‟s largest impoundment, Lake Gariep. The growth zone deposition rates in astericus otoliths of the three species were validated as biannual for C. carpio and as annual for L. capensis and L. aeneus, which allowed for reliable estimation of lengths-at-age upon which growth, age-at-maturity and mortality rates could be estimated. Cyprinus carpio exhibited fast growth, matured relatively early at two years of age and attained a maximum age of seven years. Labeo capensis grew significantly slower, but attained older ages of up to 12 years. Females showed notably delayed maturation at approximately six years of age. The life history parameter estimates for L. aeneus were similar to those of L. capensis. These species-specific life history characteristics contributed to a substantially higher population growth potential of C. carpio compared to L. capensis and L. aeneus. Delta-lognormal and delta-gamma Generalized Linear Models (GLMs) were used to analyse patterns of relative abundance of L. capensis, L. aeneus and C. carpio. The application of these GLMs was necessary to account for large proportions of zeros and strong skewness in the catch-per-unit-effort (CPUE) from experimental gillnet and fisheries-dependent angler surveys. Confidence intervals around predicted abundance indices were obtained through the development of a generalised parametric bootstrap procedure. The resulting standardised abundance indices were coupled with results from analysis of stable isotope ratios of fish tissues and potential food resources and revealed that C. carpio was mainly confined to soft-bottom habitats, where it predominantly foraged on benthic invertebrates. Labeo capensis was abundant in a wide range of benthic habitats and was consumed basal food resources such as detritus. Labeobarbus aeneus was found to feed mostly on pelagic zooplankton. There were no significant interspecific differences in trophic niche space, suggesting limited resource competition among the three species. Standardised historical and contemporary gillnet CPUE data indicated slow population growth rates of L. capensis and L. aeneus during the first ten years postimpoundment, but showed high biomass levels some four decades after impoundment. These results could be corroborated by stochastic age-structured production model (ASPM) simulations. In contrast to the two endemic species, the gillnet CPUE of C. carpio showed a clear „boom and bust‟ pattern, which, based on ASPM simulations, could be best explained by increased food availability during the first five years postimpoundment, followed by suboptimal conditions thereafter. Together, these results provided evidence that the establishment of the C. carpio population did not prevent the slow but successful long-term establishment of the two large endemic cyprinids. Both endemic fishes revealed specialised feeding within the impoundment.
- Full Text:
Pressurized hot water extraction of nutraceuticals and organic pollutants from medicinal plants
- Authors: Mokgadi, Janes
- Date: 2011
- Subjects: Functional foods Medicinal plants -- Biotechnology Extraction (Chemistry) Goldenseal Botanical pesticides Sorbents Organic solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4338 , http://hdl.handle.net/10962/d1004999
- Description: This thesis explores the robustness and the versatility of pressurized hot water extraction (PHWE) for a variety of analytes and matrices. Applications discussed include: selective extraction of alkaloids in goldenseal followed by their degradation studies; in-cell clean-up of pesticides in medicinal plants employing custom made molecularly imprinted polymers (MIPs) sorbents; in-cell pre-concentration followed by desorption of aflatoxins in plants with MIPs; desorption of pesticides from electrospun nanofiber sorbents; and removal of templates from MIPs sorbents. It was demonstrated that selective extractions could be achieved by just changing the temperature of water while adjusting the pressure. For instance, the alkaloids in goldenseal (hydrastine and berberine), were extracted at 140 °C, 50 bars, 1 mL min⁻¹ in 15 min; organochlorine pesticides from medicinal plants were extracted at 260 °C, 80 bars, 1 mL min-1 in 10 min; while aflatoxins AFG2, AFG1, AFB2 and AFB1 were extracted at 180 °C, 60 bars and a flow rate of 0.5 mL min⁻¹ in 10 min. The selectivity of PHWE was further enhanced by combining it with selective MIPs sorbents at higher temperatutes. In-cell clean-up of interfering chlorophyll was successfully removed from the medicinal plants during pesticides analysis while clean-up of aflatoxins AFG2, AFG1, AFB2 and AFB1 was achieved in two extraction cells connected in series. Ultrasound was also combined with PHWE for extraction of hydrastine and berberine at 80 °C and 40 bars in 30 min. PHWE was further evaluated for removal of templates from quercetin, phthalocynine and chlorophyll MIPs. The templates were thoroughly washed off their MIPs within 70 min with PHWE compared to over 8 h for Soxhlet and ultrasound assisted extraction. Pesticides were also desorbed from electrospun nanofibers at 260 °C, 80 bars in 10 min employing only water at 0.5 mL min⁻¹. In the light of green chemistry, the decrease in the usage of organic solvents was 100%, resulting in no organic solvent waste.
- Full Text:
- Authors: Mokgadi, Janes
- Date: 2011
- Subjects: Functional foods Medicinal plants -- Biotechnology Extraction (Chemistry) Goldenseal Botanical pesticides Sorbents Organic solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4338 , http://hdl.handle.net/10962/d1004999
- Description: This thesis explores the robustness and the versatility of pressurized hot water extraction (PHWE) for a variety of analytes and matrices. Applications discussed include: selective extraction of alkaloids in goldenseal followed by their degradation studies; in-cell clean-up of pesticides in medicinal plants employing custom made molecularly imprinted polymers (MIPs) sorbents; in-cell pre-concentration followed by desorption of aflatoxins in plants with MIPs; desorption of pesticides from electrospun nanofiber sorbents; and removal of templates from MIPs sorbents. It was demonstrated that selective extractions could be achieved by just changing the temperature of water while adjusting the pressure. For instance, the alkaloids in goldenseal (hydrastine and berberine), were extracted at 140 °C, 50 bars, 1 mL min⁻¹ in 15 min; organochlorine pesticides from medicinal plants were extracted at 260 °C, 80 bars, 1 mL min-1 in 10 min; while aflatoxins AFG2, AFG1, AFB2 and AFB1 were extracted at 180 °C, 60 bars and a flow rate of 0.5 mL min⁻¹ in 10 min. The selectivity of PHWE was further enhanced by combining it with selective MIPs sorbents at higher temperatutes. In-cell clean-up of interfering chlorophyll was successfully removed from the medicinal plants during pesticides analysis while clean-up of aflatoxins AFG2, AFG1, AFB2 and AFB1 was achieved in two extraction cells connected in series. Ultrasound was also combined with PHWE for extraction of hydrastine and berberine at 80 °C and 40 bars in 30 min. PHWE was further evaluated for removal of templates from quercetin, phthalocynine and chlorophyll MIPs. The templates were thoroughly washed off their MIPs within 70 min with PHWE compared to over 8 h for Soxhlet and ultrasound assisted extraction. Pesticides were also desorbed from electrospun nanofibers at 260 °C, 80 bars in 10 min employing only water at 0.5 mL min⁻¹. In the light of green chemistry, the decrease in the usage of organic solvents was 100%, resulting in no organic solvent waste.
- Full Text:
Regional application of the Pitman monthly rainfall-runoff model in Southern Africa incorporating uncertainty
- Authors: Kapangaziwiri, Evison
- Date: 2011
- Subjects: Water supply -- Africa, Southern Water supply -- Measurement -- Africa, Southern Hydrology -- Mathematical models -- Africa, Southern Hydrologic models Rain and rainfall -- Mathematical models -- Africa, Southern Runoff -- Mathematical models
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6037 , http://hdl.handle.net/10962/d1006178
- Description: Climate change and a growing demand for freshwater resources due to population increases and socio-economic changes will make water a limiting factor (in terms of both quantity and quality) in development. The need for reliable quantitative estimates of water availability cannot be over-emphasised. However, there is frequently a paucity of the data required for this quantification as many basins, especially in the developing world, are inadequately equipped with monitoring networks. Existing networks are also shrinking due mainly to shortages in human and financial resources. Over the past few decades mathematical models have been used to bridge the data gap by generating datasets for use in management and policy making. In southern Africa, the Pitman monthly rainfall-runoff model has enjoyed relatively popular use as a water resources estimation tool. However, it is acknowledged that models are abstractions of reality and the data used to drive them is imperfect, making the model outputs uncertain. While there is acknowledgement of the limitations of modelled data in the southern African region among water practitioners, there has been little effort to explicitly quantify and account for this uncertainty in water resources estimation tools and explore how it affects the decision making process. Uncertainty manifests itself in three major areas of the modelling chain; the input data used to force the model, the parameter estimation process and the model structural errors. A previous study concluded that the parameter estimation process for the Pitman model contributed more to the global uncertainty of the model than other sources. While the literature abounds with uncertainty estimation techniques, many of these are dependent on observations and are therefore unlikely to be easily applicable to the southern African region where there is an acute shortage of such data. This study focuses on two aspects of making hydrologic predictions in ungauged basins. Firstly, the study advocates the development of an a priori parameter estimation process for the Pitman model and secondly, uses indices of hydrological functional behaviour to condition and reduce predictive uncertainty in both gauged and ungauged basins. In this approach all the basins are treated as ungauged, while the historical records in the gauged basins are used to develop regional indices of expected hydrological behaviour and assess the applicability of these methods. Incorporating uncertainty into the hydrologic estimation tools used in southern Africa entails rethinking the way the uncertain results can be used in further analysis and how they will be interpreted by stakeholders. An uncertainty framework is proposed. The framework is made up of a number of components related to the estimation of the prior distribution of the parameters, used to generate output ensembles which are then assessed and constrained using regionalised indices of basin behavioural responses. This is premised on such indices being based on the best available knowledge covering different regions. This framework is flexible enough to be used with any model structure to ensure consistent and comparable results. While the aim is to eventually apply the uncertainty framework in the southern African region, this study reports on the preliminary work on the development and testing of the framework components based on South African basins. This is necessitated by the variations in the availability and quality of the data across the region. Uncertainty in the parameter estimation process was incorporated by assuming uncertainty in the physical and hydro-meteorological data used to directly quantify the parameter. This uncertainty was represented by the range of variability of these basin characteristics and probability distribution functions were developed to account for this uncertainty and propagate it through the estimation process to generate posterior distributions for the parameters. The results show that the framework has a great deal of potential but can still be improved. In general, the estimated uncertain parameters managed to produce hydrologically realistic model outputs capturing the expected regimes across the different hydro-climatic and geo-physical gradients examined. The regional relationships for the three indices developed and tested in this study were in general agreement with existing knowledge and managed to successfully provide a multi-criteria conditioning of the model output ensembles. The feedback loop included in the framework enabled a systematic re-examination of the estimation procedures for both the parameters and the indices when inconsistencies in the results were identified. This improved results. However, there is need to carefully examine the issues and problems that may arise within other basins outside South Africa and develop guidelines for the use of the framework. , iText 1.4.6 (by lowagie.com)
- Full Text:
- Authors: Kapangaziwiri, Evison
- Date: 2011
- Subjects: Water supply -- Africa, Southern Water supply -- Measurement -- Africa, Southern Hydrology -- Mathematical models -- Africa, Southern Hydrologic models Rain and rainfall -- Mathematical models -- Africa, Southern Runoff -- Mathematical models
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6037 , http://hdl.handle.net/10962/d1006178
- Description: Climate change and a growing demand for freshwater resources due to population increases and socio-economic changes will make water a limiting factor (in terms of both quantity and quality) in development. The need for reliable quantitative estimates of water availability cannot be over-emphasised. However, there is frequently a paucity of the data required for this quantification as many basins, especially in the developing world, are inadequately equipped with monitoring networks. Existing networks are also shrinking due mainly to shortages in human and financial resources. Over the past few decades mathematical models have been used to bridge the data gap by generating datasets for use in management and policy making. In southern Africa, the Pitman monthly rainfall-runoff model has enjoyed relatively popular use as a water resources estimation tool. However, it is acknowledged that models are abstractions of reality and the data used to drive them is imperfect, making the model outputs uncertain. While there is acknowledgement of the limitations of modelled data in the southern African region among water practitioners, there has been little effort to explicitly quantify and account for this uncertainty in water resources estimation tools and explore how it affects the decision making process. Uncertainty manifests itself in three major areas of the modelling chain; the input data used to force the model, the parameter estimation process and the model structural errors. A previous study concluded that the parameter estimation process for the Pitman model contributed more to the global uncertainty of the model than other sources. While the literature abounds with uncertainty estimation techniques, many of these are dependent on observations and are therefore unlikely to be easily applicable to the southern African region where there is an acute shortage of such data. This study focuses on two aspects of making hydrologic predictions in ungauged basins. Firstly, the study advocates the development of an a priori parameter estimation process for the Pitman model and secondly, uses indices of hydrological functional behaviour to condition and reduce predictive uncertainty in both gauged and ungauged basins. In this approach all the basins are treated as ungauged, while the historical records in the gauged basins are used to develop regional indices of expected hydrological behaviour and assess the applicability of these methods. Incorporating uncertainty into the hydrologic estimation tools used in southern Africa entails rethinking the way the uncertain results can be used in further analysis and how they will be interpreted by stakeholders. An uncertainty framework is proposed. The framework is made up of a number of components related to the estimation of the prior distribution of the parameters, used to generate output ensembles which are then assessed and constrained using regionalised indices of basin behavioural responses. This is premised on such indices being based on the best available knowledge covering different regions. This framework is flexible enough to be used with any model structure to ensure consistent and comparable results. While the aim is to eventually apply the uncertainty framework in the southern African region, this study reports on the preliminary work on the development and testing of the framework components based on South African basins. This is necessitated by the variations in the availability and quality of the data across the region. Uncertainty in the parameter estimation process was incorporated by assuming uncertainty in the physical and hydro-meteorological data used to directly quantify the parameter. This uncertainty was represented by the range of variability of these basin characteristics and probability distribution functions were developed to account for this uncertainty and propagate it through the estimation process to generate posterior distributions for the parameters. The results show that the framework has a great deal of potential but can still be improved. In general, the estimated uncertain parameters managed to produce hydrologically realistic model outputs capturing the expected regimes across the different hydro-climatic and geo-physical gradients examined. The regional relationships for the three indices developed and tested in this study were in general agreement with existing knowledge and managed to successfully provide a multi-criteria conditioning of the model output ensembles. The feedback loop included in the framework enabled a systematic re-examination of the estimation procedures for both the parameters and the indices when inconsistencies in the results were identified. This improved results. However, there is need to carefully examine the issues and problems that may arise within other basins outside South Africa and develop guidelines for the use of the framework. , iText 1.4.6 (by lowagie.com)
- Full Text:
Risk-based assessment of environmental asbestos contamination in the Northern Cape and North West provinces of South Africa
- Authors: Jones, Robert Ryan
- Date: 2011
- Subjects: Asbestos industry -- Health aspects -- South Africa -- Northern Cape Asbestos industry -- Health aspects -- South Africa -- North West Environmental risk assessment -- South Africa-- Northern Cape Environmental risk assessment -- North West Asbestos -- Toxicology -- South Africa -- Northern Cape Asbestos -- Toxicology -- South Africa -- North West Tailings (Metallurgy) -- Waste disposal -- South Africa -- Northern Cape Tailings (Metallurgy) -- Waste disposal -- South Africa -- North West
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4780 , http://hdl.handle.net/10962/d1012612
- Description: The commercial mining of asbestos occurred in four Provinces of South Africa (Northern Cape, North West, Limpopo and Mpumalanga). It was initiated in the late 1800's and lasted for over a hundred years into the beginning of this century. As a producer of amphibole asbestos, South Africa far outpaced every other country being responsible for 97% of global production. The last crocidolite mine closed in 1996 and chrysotile in 2002. Anecdotal information concerning environmental contamination as a result of the former mining activities and the improper disposal of mine waste tailings has been reported by a variety of authors. Few comprehensive or systematic surveys have been conducted to date to document this issue and very little quantifiable research has been completed on the communities located in close proximity to the former mine sites to determine the extent of contamination. In 2004-2006 communities were surveyed within the Northern Cape and North West Provinces to determine the extent and severity of environmental contamination. This research developed and applied a methodology to select those communities suspected of environmental contamination, a targeted survey methodology, and a protocol for rapid sample laboratory analysis. A total of 41 communities were initially predicted by the model to be suspected for environmental asbestos contamination. Based on the inclusion of local knowledge, a final 36 communities were selected for a screening-level field assessment, 34 of which were found to contain environmental asbestos contamination at rates ranging from 20 to 100% of the surveyed locations. A total of 1 843 samples of soil and building material were collected in the screening level assessment. One community (Ga-Mopedi) was selected as being representative of the total cohort and a more detailed house to house survey was completed. A total of 1 486 samples were collected during the detailed survey. Results of the detailed survey revealed 26.2% of the homes were contaminated with asbestos containing soil and/or building material. A theoretical quantitative cumulative exposure assessment was developed to estimate the disease burden within the study area population of 126,130 individuals within the surveyed communities resulting in a predicted range of 25-52.4 excess deaths per year from lung cancer and mesothelioma due solely to environmental exposures to asbestos pollution.
- Full Text:
- Authors: Jones, Robert Ryan
- Date: 2011
- Subjects: Asbestos industry -- Health aspects -- South Africa -- Northern Cape Asbestos industry -- Health aspects -- South Africa -- North West Environmental risk assessment -- South Africa-- Northern Cape Environmental risk assessment -- North West Asbestos -- Toxicology -- South Africa -- Northern Cape Asbestos -- Toxicology -- South Africa -- North West Tailings (Metallurgy) -- Waste disposal -- South Africa -- Northern Cape Tailings (Metallurgy) -- Waste disposal -- South Africa -- North West
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4780 , http://hdl.handle.net/10962/d1012612
- Description: The commercial mining of asbestos occurred in four Provinces of South Africa (Northern Cape, North West, Limpopo and Mpumalanga). It was initiated in the late 1800's and lasted for over a hundred years into the beginning of this century. As a producer of amphibole asbestos, South Africa far outpaced every other country being responsible for 97% of global production. The last crocidolite mine closed in 1996 and chrysotile in 2002. Anecdotal information concerning environmental contamination as a result of the former mining activities and the improper disposal of mine waste tailings has been reported by a variety of authors. Few comprehensive or systematic surveys have been conducted to date to document this issue and very little quantifiable research has been completed on the communities located in close proximity to the former mine sites to determine the extent of contamination. In 2004-2006 communities were surveyed within the Northern Cape and North West Provinces to determine the extent and severity of environmental contamination. This research developed and applied a methodology to select those communities suspected of environmental contamination, a targeted survey methodology, and a protocol for rapid sample laboratory analysis. A total of 41 communities were initially predicted by the model to be suspected for environmental asbestos contamination. Based on the inclusion of local knowledge, a final 36 communities were selected for a screening-level field assessment, 34 of which were found to contain environmental asbestos contamination at rates ranging from 20 to 100% of the surveyed locations. A total of 1 843 samples of soil and building material were collected in the screening level assessment. One community (Ga-Mopedi) was selected as being representative of the total cohort and a more detailed house to house survey was completed. A total of 1 486 samples were collected during the detailed survey. Results of the detailed survey revealed 26.2% of the homes were contaminated with asbestos containing soil and/or building material. A theoretical quantitative cumulative exposure assessment was developed to estimate the disease burden within the study area population of 126,130 individuals within the surveyed communities resulting in a predicted range of 25-52.4 excess deaths per year from lung cancer and mesothelioma due solely to environmental exposures to asbestos pollution.
- Full Text:
Sedimentology of plio-pleistocene gravel barrier deposits in the palaeo-Orange River mouth, Namibia : depositional history and diamond mineralisation
- Authors: Spaggiari, Renato Igino
- Date: 2011 , 2013-08-19
- Subjects: Diamond mines and mining -- Namibia Sediments (Geology) -- South Africa and Namibia -- Orange River Estuary Diamond deposits -- Namibia Orange River Estuary (Namibia and South Africa)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4927 , http://hdl.handle.net/10962/d1004636
- Description: The largest known marine diamond placer, the Namibian mega-placer, lies along the Atlantic coast of south-western Africa from the Orange River mouth 1,000 km northwards to the Namibian-Angolan border. The most economically viable portion of the Namibian mega-placer (>75 million carats recovered at >95% gem quality) comprises onshore and offshore marine deposits that are developed within ∼100km of the Orange River outfall. For much of the Cainozoic, this long-lived fluvial system has been the main conduit transporting diamonds from kimberlitic and secondary sources in the cratonic hinterland of southern Africa to the Atlantic shelf that has been neutrally buoyant over this period. Highly energetic marine processes, driven in part, by southerly winds with an attendant northward-directed longshore drift, have generated terminal placers that are preserved both onshore and offshore. This study, through detailed field sedimentological and diamond analyses, investigates the development and mineralisation of gravel barrier deposits within the ancestral Orange River mouth area during a major ∼30 m regional transgression ('30 m Package') in the Late Pliocene. At that time, diamond supply from this fluvial conduit was minimal, yet the corresponding onshore marine deposits to the north of the Orange River mouth were significantly diamond enriched, enabling large-scale alluvial diamond mining to take place for over 75 years. Of the entire coastline of south-western Africa, the most complete accumulation of the '30 m Package' is preserved within the palaeo-Orange River mouth as barrier spit and barrier beach deposits. Arranged vertically and laterally in a 16m thick succession, these are deposits of: (1) intertidal beach, (2) lagoon and washover, (3) tidal inlet and spit recurve and (4) storm-dominated subtidal settings. These were parts of larger barrier features, the bulk of which are preserved as highstand deposits that are diamond-bearing with varying, but generally low grades (<13 stones (diamonds) per hundred tons, spht). Intertidal beach and spit recurve deposits have higher economic grades (12-13 spht) due to the energetic sieving and mobile trapping mechanisms associated with their emplacement. In contrast, the less reworked and more sandy subtidal, tidal inlet and washover deposits have un-economic grades (<2 spht). Despite these low grades, the barrier deposits have the largest average stone (diamond) size (1-2 carats/stone, cts/stn) of the entire Namibian mega-placer, given their proximity to the ancestral Orange River outfall. This study demonstrates that barrier shoreline evolution at the fluvial/marine interface was controlled by: (1) a strong and coarse fluvial sediment supply that sustained shoreline growth on a highly energetic coast, (2) accommodation space facilitating sediment preservation and (3) short-duration, high-frequency sea-level cycles superimposed on the∼30 m regional transgression, promoting hierarchal stacking of progradational deposits. During these sea-level fluctuations, diamonds were 'farmed' from older, shelf sequences in the offshore and driven landward to accumulate in '30 m Package' highstand barrier deposits. In spite of the large supply of diamonds, their retention in these deposits was poor due to an incompetent footwall of ancestral Orange River mouth sediment and the inherent cobble-boulder size of the barrier gravels. Thus the principal process controlling diamond entrapment in these barrier deposits was kinetic sieving in a coarse-grained framework. Consequently, at the marine/fluvial interface and down-drift for ∼5 km, larger diamonds (1-2 cts/stn) were retained in low-grade (<2 spht), coarse-gravel barrier shorelines. Smaller diamonds (mostly < I cts/stn) were rejected into the northward-driven littoral sediments and further size-sorted along ∼95 km of Namibian coast to accumulate in finer, high-grade beach placers (> 100 spht) where bedrock footwall promoted such high concentrations. The gravel-dominated palaeo-Orange River mouth is considered to be the ' heart' of the Namibian mega-placer, controlling sediment and diamond supply to the littoral zone further north. Although coarse gravel is retained at the river mouth, the incompetence of this highly energetic setting to trap diamonds renders it sub-economic. This ineffectiveness at the fluvial/marine interface is thus fundamental in enriching the coastal tract farther down-drift and developing highly economic coastal placers along the Atlantic coast of south-western Africa. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Authors: Spaggiari, Renato Igino
- Date: 2011 , 2013-08-19
- Subjects: Diamond mines and mining -- Namibia Sediments (Geology) -- South Africa and Namibia -- Orange River Estuary Diamond deposits -- Namibia Orange River Estuary (Namibia and South Africa)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4927 , http://hdl.handle.net/10962/d1004636
- Description: The largest known marine diamond placer, the Namibian mega-placer, lies along the Atlantic coast of south-western Africa from the Orange River mouth 1,000 km northwards to the Namibian-Angolan border. The most economically viable portion of the Namibian mega-placer (>75 million carats recovered at >95% gem quality) comprises onshore and offshore marine deposits that are developed within ∼100km of the Orange River outfall. For much of the Cainozoic, this long-lived fluvial system has been the main conduit transporting diamonds from kimberlitic and secondary sources in the cratonic hinterland of southern Africa to the Atlantic shelf that has been neutrally buoyant over this period. Highly energetic marine processes, driven in part, by southerly winds with an attendant northward-directed longshore drift, have generated terminal placers that are preserved both onshore and offshore. This study, through detailed field sedimentological and diamond analyses, investigates the development and mineralisation of gravel barrier deposits within the ancestral Orange River mouth area during a major ∼30 m regional transgression ('30 m Package') in the Late Pliocene. At that time, diamond supply from this fluvial conduit was minimal, yet the corresponding onshore marine deposits to the north of the Orange River mouth were significantly diamond enriched, enabling large-scale alluvial diamond mining to take place for over 75 years. Of the entire coastline of south-western Africa, the most complete accumulation of the '30 m Package' is preserved within the palaeo-Orange River mouth as barrier spit and barrier beach deposits. Arranged vertically and laterally in a 16m thick succession, these are deposits of: (1) intertidal beach, (2) lagoon and washover, (3) tidal inlet and spit recurve and (4) storm-dominated subtidal settings. These were parts of larger barrier features, the bulk of which are preserved as highstand deposits that are diamond-bearing with varying, but generally low grades (<13 stones (diamonds) per hundred tons, spht). Intertidal beach and spit recurve deposits have higher economic grades (12-13 spht) due to the energetic sieving and mobile trapping mechanisms associated with their emplacement. In contrast, the less reworked and more sandy subtidal, tidal inlet and washover deposits have un-economic grades (<2 spht). Despite these low grades, the barrier deposits have the largest average stone (diamond) size (1-2 carats/stone, cts/stn) of the entire Namibian mega-placer, given their proximity to the ancestral Orange River outfall. This study demonstrates that barrier shoreline evolution at the fluvial/marine interface was controlled by: (1) a strong and coarse fluvial sediment supply that sustained shoreline growth on a highly energetic coast, (2) accommodation space facilitating sediment preservation and (3) short-duration, high-frequency sea-level cycles superimposed on the∼30 m regional transgression, promoting hierarchal stacking of progradational deposits. During these sea-level fluctuations, diamonds were 'farmed' from older, shelf sequences in the offshore and driven landward to accumulate in '30 m Package' highstand barrier deposits. In spite of the large supply of diamonds, their retention in these deposits was poor due to an incompetent footwall of ancestral Orange River mouth sediment and the inherent cobble-boulder size of the barrier gravels. Thus the principal process controlling diamond entrapment in these barrier deposits was kinetic sieving in a coarse-grained framework. Consequently, at the marine/fluvial interface and down-drift for ∼5 km, larger diamonds (1-2 cts/stn) were retained in low-grade (<2 spht), coarse-gravel barrier shorelines. Smaller diamonds (mostly < I cts/stn) were rejected into the northward-driven littoral sediments and further size-sorted along ∼95 km of Namibian coast to accumulate in finer, high-grade beach placers (> 100 spht) where bedrock footwall promoted such high concentrations. The gravel-dominated palaeo-Orange River mouth is considered to be the ' heart' of the Namibian mega-placer, controlling sediment and diamond supply to the littoral zone further north. Although coarse gravel is retained at the river mouth, the incompetence of this highly energetic setting to trap diamonds renders it sub-economic. This ineffectiveness at the fluvial/marine interface is thus fundamental in enriching the coastal tract farther down-drift and developing highly economic coastal placers along the Atlantic coast of south-western Africa. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
Structural and functional characterisation of the protein inhibitor of activated STAT3 (PIAS3)
- Authors: Mautsa, Nicodemus
- Date: 2011
- Subjects: Cytokines Immune response Proteins Cancer cells -- Growth -- Regulation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3991 , http://hdl.handle.net/10962/d1004050
- Description: The signal transducer and activator of transcription (STAT) and protein inhibitor of STAT(PIAS) system represent an elegant regulatory mechanism of transcriptional control IN mammalian cytokine signalling. Abnormal activation of the system is associated with immune disorders and a large group of diverse tumours. PIAS3 is a multiple domain protein with distinct functions involved in regulation of cytokine-mediated gene activation pathways.Its over-expression significantly inhibits cell growth and renders cancer cells more sensitive to drugs. The objective of this study was to structurally and biochemically characterise the function of the PIAS3 protein using in silico, in vivo and in vitro analysis approaches.The conservation pattern of the PIAS protein family and critical conserved residues in the PINIT (Proline, Isoleucine, Asparagine, Isoleucine, Tyrosine) domain were identified. The PINIT domain model was generated based on the PINIT domain structure of yeast PIAS3 homologue Siz1 and structural determinants in the PIAS3-STAT3 interaction were evaluated.Guided by the in silico findings, in vivo analysis of the localisation of the PIAS3, mutantderivatives of PIAS3 (PIAS3-L97A, PIAS3-R99N, PIAS3-R99Q), PINIT and acidic domain was conducted. PIAS3 was completely localised in the nucleus while PIAS3 mutants appeared to exhibit diffuse cytoplasmic distribution. The PINIT domain was predominantly localised in the nucleus with some apparent perinuclear staining while the acidic domain exhibited a predominantly perinuclear staining pattern. Further analysis of the PINIT domain and the effect of the mutants on PIAS3-STAT3 interaction were assessed by in vitro analysis. Guided by in silico analysis, the PINIT domain and mutant derivatives of PINIT domain (PINIT-L97A, PINIT-R99N, and PINIT-R99Q) were heterologously expressed in Escherichia coli and subsequently purified using a combination of immobilized metal affinity and size exclusion based chromatography. The size and structural elements of the PINIT domain and its mutants were characterised. The 23 kDa PINIT domain was found to exist as a monomer in solution and its secondary structure was shown to consist of 66 % β-sheets by fourier transformed infrared spectroscopy consistent with the generated homology model.Using surface plasmonresonance spectroscopy (SPR) the PINIT domain was shown to bind to STAT3 in a specific concentration dependent manner. Recombinant PINIT-L97A,PINITR99N and PINIT-R99Q mutants, which exhibited similar structural integrity to the wildtype, were found to abrogate binding to STAT3. These findings suggest that these residues form part of a potential binding surface for stat3. In conclusion, this study has provided evidence that the PINIT domain is an important determinant of PIAS3 interaction with STAT3 and that the interaction is mediated by defined conserved residues directly involved in the PINITSTAT3 interaction.
- Full Text:
- Authors: Mautsa, Nicodemus
- Date: 2011
- Subjects: Cytokines Immune response Proteins Cancer cells -- Growth -- Regulation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3991 , http://hdl.handle.net/10962/d1004050
- Description: The signal transducer and activator of transcription (STAT) and protein inhibitor of STAT(PIAS) system represent an elegant regulatory mechanism of transcriptional control IN mammalian cytokine signalling. Abnormal activation of the system is associated with immune disorders and a large group of diverse tumours. PIAS3 is a multiple domain protein with distinct functions involved in regulation of cytokine-mediated gene activation pathways.Its over-expression significantly inhibits cell growth and renders cancer cells more sensitive to drugs. The objective of this study was to structurally and biochemically characterise the function of the PIAS3 protein using in silico, in vivo and in vitro analysis approaches.The conservation pattern of the PIAS protein family and critical conserved residues in the PINIT (Proline, Isoleucine, Asparagine, Isoleucine, Tyrosine) domain were identified. The PINIT domain model was generated based on the PINIT domain structure of yeast PIAS3 homologue Siz1 and structural determinants in the PIAS3-STAT3 interaction were evaluated.Guided by the in silico findings, in vivo analysis of the localisation of the PIAS3, mutantderivatives of PIAS3 (PIAS3-L97A, PIAS3-R99N, PIAS3-R99Q), PINIT and acidic domain was conducted. PIAS3 was completely localised in the nucleus while PIAS3 mutants appeared to exhibit diffuse cytoplasmic distribution. The PINIT domain was predominantly localised in the nucleus with some apparent perinuclear staining while the acidic domain exhibited a predominantly perinuclear staining pattern. Further analysis of the PINIT domain and the effect of the mutants on PIAS3-STAT3 interaction were assessed by in vitro analysis. Guided by in silico analysis, the PINIT domain and mutant derivatives of PINIT domain (PINIT-L97A, PINIT-R99N, and PINIT-R99Q) were heterologously expressed in Escherichia coli and subsequently purified using a combination of immobilized metal affinity and size exclusion based chromatography. The size and structural elements of the PINIT domain and its mutants were characterised. The 23 kDa PINIT domain was found to exist as a monomer in solution and its secondary structure was shown to consist of 66 % β-sheets by fourier transformed infrared spectroscopy consistent with the generated homology model.Using surface plasmonresonance spectroscopy (SPR) the PINIT domain was shown to bind to STAT3 in a specific concentration dependent manner. Recombinant PINIT-L97A,PINITR99N and PINIT-R99Q mutants, which exhibited similar structural integrity to the wildtype, were found to abrogate binding to STAT3. These findings suggest that these residues form part of a potential binding surface for stat3. In conclusion, this study has provided evidence that the PINIT domain is an important determinant of PIAS3 interaction with STAT3 and that the interaction is mediated by defined conserved residues directly involved in the PINITSTAT3 interaction.
- Full Text:
Studies in marine quinone chemistry
- Authors: Sunassee, Suthananda Naidu
- Date: 2011
- Subjects: Quinone Marine natural products Marine invertebrates Marine pharmacology Cancer -- Treatment
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4355 , http://hdl.handle.net/10962/d1005020
- Description: This thesis is divided into two parts and the rationale of the research conducted is based on the cytotoxicity of the prenylated quinones 1.24-1.29, isolated from the South African nudibranch Leminda millecra, against oesophageal cancer cells. The first part (Chapters 2 and 3) of the thesis initially documents the distribution of cytotoxic and antioxidant prenylated quinones and hydroquinones in the marine environment. We have been able to show, for the first time, that these compounds can be divided into eight structural classes closely related to their phyletic distribution. Secondly, we attempted to synthesize the two marine natural products 1.24 and 1.26 in an effort to contribute to an ongoing collaborative search with the Division of Medical Biochemistry at the University of Cape Town for new compounds with anti-oesophageal cancer activity. Accordingly, we followed the published synthetic procedure for 1.26 and, although we were unable to reproduce the reported results, we have generated five new prenylated quinone analogues 3.53-3.55, 3.63 and 3.71, which are a potentially viable addition to our ongoing structure-activity relationship (SAR) studies. Moreover, we embarked on a 7Li NMR mechanistic study for the synthesis of 3.2 from 3.1 which rewarded us with an improved and reproducible methodology for this crucial reaction that is detailed in Chapter 3. The second part of this thesis (Chapters 4 and 5) is concerned with a synthetic, structural, electrochemical and biological exploration of the 1,4-naphthoquinone nucleus as a primary pharmacophore in our search for new chemical entities which can induce apoptosis in oesophageal cancer cells, thus contributing to our overall ongoing SAR study in this class of compounds. Seven new naphthoquinone derivatves (4.19, 4.30, 4.31, 4.33 and 4.46-4.48) of the natural products 2-deoxylapachol (2.44), lapachol (4.1) and β-lapachone (5.2) were synthesized and 2-(1`-hydroxy-`-phenylmethyl)-1,4-naphthoquinone (4.29) was found to be the most cytotoxic (IC50 1.5 μM) against the oesophageal cancer cell line WHCO1, while 5.2, which is currently in phase II clinical trials as an anticancer drug, was found to be similarly active (IC50 1.6 μM). Electrochemical investigations of the redox properties of the benzylic alcohol derivatives 4.29-4.31 indicated a higher reduction potential compared to their oxidized counterparts 4.45-4.48, and this finding has been correlated to the increased activity of 4.29-4.31 against the WHCO1 cell line. Additionally, 4.29 is synthetically more accessible than either 1.26 or 5.2 and potentially a lead compound in our search for new and more effective chemotherapeutic agents against oesophageal cancer
- Full Text:
- Authors: Sunassee, Suthananda Naidu
- Date: 2011
- Subjects: Quinone Marine natural products Marine invertebrates Marine pharmacology Cancer -- Treatment
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4355 , http://hdl.handle.net/10962/d1005020
- Description: This thesis is divided into two parts and the rationale of the research conducted is based on the cytotoxicity of the prenylated quinones 1.24-1.29, isolated from the South African nudibranch Leminda millecra, against oesophageal cancer cells. The first part (Chapters 2 and 3) of the thesis initially documents the distribution of cytotoxic and antioxidant prenylated quinones and hydroquinones in the marine environment. We have been able to show, for the first time, that these compounds can be divided into eight structural classes closely related to their phyletic distribution. Secondly, we attempted to synthesize the two marine natural products 1.24 and 1.26 in an effort to contribute to an ongoing collaborative search with the Division of Medical Biochemistry at the University of Cape Town for new compounds with anti-oesophageal cancer activity. Accordingly, we followed the published synthetic procedure for 1.26 and, although we were unable to reproduce the reported results, we have generated five new prenylated quinone analogues 3.53-3.55, 3.63 and 3.71, which are a potentially viable addition to our ongoing structure-activity relationship (SAR) studies. Moreover, we embarked on a 7Li NMR mechanistic study for the synthesis of 3.2 from 3.1 which rewarded us with an improved and reproducible methodology for this crucial reaction that is detailed in Chapter 3. The second part of this thesis (Chapters 4 and 5) is concerned with a synthetic, structural, electrochemical and biological exploration of the 1,4-naphthoquinone nucleus as a primary pharmacophore in our search for new chemical entities which can induce apoptosis in oesophageal cancer cells, thus contributing to our overall ongoing SAR study in this class of compounds. Seven new naphthoquinone derivatves (4.19, 4.30, 4.31, 4.33 and 4.46-4.48) of the natural products 2-deoxylapachol (2.44), lapachol (4.1) and β-lapachone (5.2) were synthesized and 2-(1`-hydroxy-`-phenylmethyl)-1,4-naphthoquinone (4.29) was found to be the most cytotoxic (IC50 1.5 μM) against the oesophageal cancer cell line WHCO1, while 5.2, which is currently in phase II clinical trials as an anticancer drug, was found to be similarly active (IC50 1.6 μM). Electrochemical investigations of the redox properties of the benzylic alcohol derivatives 4.29-4.31 indicated a higher reduction potential compared to their oxidized counterparts 4.45-4.48, and this finding has been correlated to the increased activity of 4.29-4.31 against the WHCO1 cell line. Additionally, 4.29 is synthetically more accessible than either 1.26 or 5.2 and potentially a lead compound in our search for new and more effective chemotherapeutic agents against oesophageal cancer
- Full Text:
Surface properties and electrocatalytic applications of metallophthalocyanines confined on electrode surfaces
- Authors: Akinbulu, Isaac Adebayo
- Date: 2011
- Subjects: Phthalocyanines Electrochemistry Electrocatalysis Pesticides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4365 , http://hdl.handle.net/10962/d1005030
- Description: New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.
- Full Text:
- Authors: Akinbulu, Isaac Adebayo
- Date: 2011
- Subjects: Phthalocyanines Electrochemistry Electrocatalysis Pesticides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4365 , http://hdl.handle.net/10962/d1005030
- Description: New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.
- Full Text:
Synthesis and evaluation of novel HIV-1 enzyme inhibitors
- Olomola, Temitope Oloruntoba
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
- Full Text:
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
- Full Text:
Synthesis of novel inhibitors of 1-Deoxy-D-xylulose-5-phosphate reductoisomerase as potential anti-malarial lead compounds
- Authors: Mutorwa, Marius Kudumo
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Malaria -- Chemotherapy Drug development Lead compounds Phosphonates Phosphonic acids Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4372 , http://hdl.handle.net/10962/d1005037
- Description: This research has focused on the development of novel substrate mimics as potential DXR inhibitors of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), an essential enzyme in the mevalonate-independent pathway for the biosynthesis of isoprenoids in Plasmodium falciparum. DXR mediates the isomerisation and reduction of 1-deoxy-D-xylulose-5-phosphate (DOXP) into 2C-methyl-D-erithrytol 4-phosphate (MEP) and has been validated as an attractive target for the development of novel anti-malarial chemotherapeutic agents. Reaction of various amines with specially prepared 4-phosphonated crotonic acid in the presence of the peptide coupling reagent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), has afforded a series of amido-phosphonate esters in moderate to good yields (48% - 73%) which, using a RuCl₃/CeCl₃/NaIO₄ catalyst system, have been dihydroxylated to furnish the dihydroxy-amido phosphonate ester pro-drugs; subsequent hydrolysis under microwave irradiation has afforded the corresponding phosphonic acids. A second series of potential inhibitors viz., 3-substituted aniline-derived phosphonate esters, their corresponding phosphonic acids and mono-sodium salts, have also been successfully synthesised. In these compounds, the essential functional groups are separated by one, two, three or four methylene groups, Deprotonation of the 3-substituted aniline substrates, followed by reaction with the appropriate ω-chloroalkanoyl chloride produced the ω-chloroamide intermediates, which were subjected to the Michaelis-Arbuzov reaction to afford the diethyl phosphonate esters in moderate to good yields (48% - 74%). Microwave-assisted TMSBrmediated cleavage of the phosphonate esters furnished the phosphonic acids, neutralisation of which afforded the mono-sodium salts. Furan-derived phosphate esters and phosphonic acids have been prepared as conformationally-restricted DOXP analogues. Functionalization at C-5 of the trityl-protected furan was achieved using the Vilsmeier-Haack formylation and Friedel-Crafts acylation reactions and, following de-tritylation, phosphorylation and oximation, using hydroxylamine hydrochloride, the novel oxime derivatives have been isolated as a third series of potential DXR inhibitors in very good yields (87% - 96%). Finally, in order to exploit an additional binding pocket in the PƒDXR active site, a series of N-benzylated phosphoramidic derivatives were obtained in seven steps from the starting material, diethyl phosphoramidate. The known inhibitors, fosmidomycin and its acetyl derivative FR900098, were also successfully synthesised as standards for STD-NMR binding and inhibition assays. In all, over 200 compounds (136 novel) have been prepared and appropriately characterised using 1-and 2-D NMR and IR spectroscopic analysis and, where necessary, HRMS or combustion analysis. Saturation Transfer Difference (STD) protein-NMR experiments, undertaken using selected compounds, have revealed binding of most of the ligands examined to EcDXR. Computersimulated docking studies have also been used to explore the preferred ligand-binding conformations and interactions between the ligands and essential DXR active-site residues, while DXR-enzyme inhibition assays of selected synthesised ligands have revealed certain patterns of inhibitory activity.
- Full Text:
- Authors: Mutorwa, Marius Kudumo
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Malaria -- Chemotherapy Drug development Lead compounds Phosphonates Phosphonic acids Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4372 , http://hdl.handle.net/10962/d1005037
- Description: This research has focused on the development of novel substrate mimics as potential DXR inhibitors of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), an essential enzyme in the mevalonate-independent pathway for the biosynthesis of isoprenoids in Plasmodium falciparum. DXR mediates the isomerisation and reduction of 1-deoxy-D-xylulose-5-phosphate (DOXP) into 2C-methyl-D-erithrytol 4-phosphate (MEP) and has been validated as an attractive target for the development of novel anti-malarial chemotherapeutic agents. Reaction of various amines with specially prepared 4-phosphonated crotonic acid in the presence of the peptide coupling reagent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), has afforded a series of amido-phosphonate esters in moderate to good yields (48% - 73%) which, using a RuCl₃/CeCl₃/NaIO₄ catalyst system, have been dihydroxylated to furnish the dihydroxy-amido phosphonate ester pro-drugs; subsequent hydrolysis under microwave irradiation has afforded the corresponding phosphonic acids. A second series of potential inhibitors viz., 3-substituted aniline-derived phosphonate esters, their corresponding phosphonic acids and mono-sodium salts, have also been successfully synthesised. In these compounds, the essential functional groups are separated by one, two, three or four methylene groups, Deprotonation of the 3-substituted aniline substrates, followed by reaction with the appropriate ω-chloroalkanoyl chloride produced the ω-chloroamide intermediates, which were subjected to the Michaelis-Arbuzov reaction to afford the diethyl phosphonate esters in moderate to good yields (48% - 74%). Microwave-assisted TMSBrmediated cleavage of the phosphonate esters furnished the phosphonic acids, neutralisation of which afforded the mono-sodium salts. Furan-derived phosphate esters and phosphonic acids have been prepared as conformationally-restricted DOXP analogues. Functionalization at C-5 of the trityl-protected furan was achieved using the Vilsmeier-Haack formylation and Friedel-Crafts acylation reactions and, following de-tritylation, phosphorylation and oximation, using hydroxylamine hydrochloride, the novel oxime derivatives have been isolated as a third series of potential DXR inhibitors in very good yields (87% - 96%). Finally, in order to exploit an additional binding pocket in the PƒDXR active site, a series of N-benzylated phosphoramidic derivatives were obtained in seven steps from the starting material, diethyl phosphoramidate. The known inhibitors, fosmidomycin and its acetyl derivative FR900098, were also successfully synthesised as standards for STD-NMR binding and inhibition assays. In all, over 200 compounds (136 novel) have been prepared and appropriately characterised using 1-and 2-D NMR and IR spectroscopic analysis and, where necessary, HRMS or combustion analysis. Saturation Transfer Difference (STD) protein-NMR experiments, undertaken using selected compounds, have revealed binding of most of the ligands examined to EcDXR. Computersimulated docking studies have also been used to explore the preferred ligand-binding conformations and interactions between the ligands and essential DXR active-site residues, while DXR-enzyme inhibition assays of selected synthesised ligands have revealed certain patterns of inhibitory activity.
- Full Text:
Systematics, morphology, phylogeny and historical biogeography of the Mayfly family Prosopistomatidae (Ephemeroptera: Insecta) of the world
- Barber-James, Helen Margaret
- Authors: Barber-James, Helen Margaret
- Date: 2011
- Subjects: Mayflies Mayflies -- Classification Mayflies -- Morphology Mayflies -- Phylogeny Mayflies -- Geographical distribution Ephemeridae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5785 , http://hdl.handle.net/10962/d1005473
- Description: The diversity, classification and historical biogeography of the mayfly family Prosopistomatidae are explored. First, the higher classification of the Ephemeroptera is reviewed, focussing on the phylogenetic placement of the Prosopistomatidae relative to other mayfly families. All relevant literature from 1762 to 2010 is synthesized. Baetiscidae are established as the probable sister lineage of Prosopistomatidae, the two constituting the superfamily Baetiscoidea. Next, qualitative morphological variation within the Prosopistomatidae is reviewed and revised, emphasizing nymphs because imaginal specimens are few. The labium and associated structures and the hypopharynx of nymphs, and the highly-derived wing venation of the imaginal stages, are re-interpreted. The structure of the male tarsal claws changes considerably between subimago and imago, which, together with deeply scalloped ridges on male imaginal forelegs and unusual pits on the female thorax, are interpreted as providing an unusual mating mechanism. These structures provide morphological characters for species definition and phylogenetic analyses. Two approaches to species delimitation are explored. First, morphometric variation is analysed using Principal Component Analysis, revealing groupings that can be interpreted as species, although there is some overlap between them. Discriminant Function Analysis shows that head width and carapace shape have the most value in identifying nymphs of different species. The carapace of Prosopistoma nymphs is shown to grow allometrically and gradually, in contrast with that of Baetisca, indicating a difference in early ontogeny. Second, an Artificial Neural Network algorithm applied to nymphal morphological characters accurately identified species. This computer-driven artificial intelligence method has power to provide future easy-to-use electronic identification aids. Phylogenetic analysis of nymphal morphology using the parsimony method shows two clades of Prosopistomatidae, one sharing characters with the type species, Prosopistoma variegatum and the other predominating in Africa, although also occurring in Asia; these clades are named the “P. variegatum” and “African” clades, respectively. Parsimony analysis of adult morphology supports these two clades, but supertree analysis obscures the relationships, nesting the “P. variegatum” lineage within the other clade. Preliminary molecular phylogenetic analysis of the 16S rRNA, (mitochondrial) 18S rRNA and Histone-3 genes using Bayesian Inference methods does not support the two clades shown by morphology. Instead, there is a strong relationship between the European species and one African species, with the single Asian representative being most distantly related. These results are limited by lack of fresh material, patchy taxon sampling, and problems with finding suitable primers. A molecular clock program, BEAST, calibrated using fossils, suggests divergence times for the oldest crown-group Prosopistoma clade, represented by the Asian P. wouterae, of about 131 Ma, with the youngest species, the African P. crassi, of 1.21 Ma. Stem-group relationships are analysed using parsimony analysis, focussing on wing characters of the Baetiscoidea, other extant mayfly lineages, and extinct stem-group lineages. This suggests that the Baetiscoidea diverged from main-line Ephemeroptera earlier than any other extant mayfly lineage. This approach expands upon ideas hinted at by earlier scientists. Finally, historical biogeographical analysis of the distribution of known Baetiscoidea s.s. stem-group fossils implies a once Pangean distribution of the lineage. Changing palaeo-climate, catastrophic extinction events and plate tectonic movements in relation to the distribution of crown-group species are reviewed. Other approaches to historical biogeography that build on both morphological and molecular phylogenies are used to interpret disperalist and vacarianist arguments. Distribution patterns of eight unrelated freshwater organisms which share a similar distribution pattern are compared, assuming that shared patterns indicate similar historic biogeographic processes. The distribution of recent Prosopistoma species is seen to be the product of evolution resulting from both vicariance and dispersal. In conclusion, this thesis encompasses a variety of disciplines. It successfully recognises new characters and distinguishes previously unknown species. It uses new approaches to delimiting species and known methods to determine phylogeny from several angles. The analysis of stem-group relationships offers an insight into possible early lineage splitting within Ephemeroptera. Interpretation of historical biogeography allows for both a Gondwanan origin of Prosopistomatidae, with rafting of species on the Deccan plate to Asia, and for subsequent dispersal from Asia down to Australia and across to Europe, and possibly back to Africa.
- Full Text:
- Authors: Barber-James, Helen Margaret
- Date: 2011
- Subjects: Mayflies Mayflies -- Classification Mayflies -- Morphology Mayflies -- Phylogeny Mayflies -- Geographical distribution Ephemeridae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5785 , http://hdl.handle.net/10962/d1005473
- Description: The diversity, classification and historical biogeography of the mayfly family Prosopistomatidae are explored. First, the higher classification of the Ephemeroptera is reviewed, focussing on the phylogenetic placement of the Prosopistomatidae relative to other mayfly families. All relevant literature from 1762 to 2010 is synthesized. Baetiscidae are established as the probable sister lineage of Prosopistomatidae, the two constituting the superfamily Baetiscoidea. Next, qualitative morphological variation within the Prosopistomatidae is reviewed and revised, emphasizing nymphs because imaginal specimens are few. The labium and associated structures and the hypopharynx of nymphs, and the highly-derived wing venation of the imaginal stages, are re-interpreted. The structure of the male tarsal claws changes considerably between subimago and imago, which, together with deeply scalloped ridges on male imaginal forelegs and unusual pits on the female thorax, are interpreted as providing an unusual mating mechanism. These structures provide morphological characters for species definition and phylogenetic analyses. Two approaches to species delimitation are explored. First, morphometric variation is analysed using Principal Component Analysis, revealing groupings that can be interpreted as species, although there is some overlap between them. Discriminant Function Analysis shows that head width and carapace shape have the most value in identifying nymphs of different species. The carapace of Prosopistoma nymphs is shown to grow allometrically and gradually, in contrast with that of Baetisca, indicating a difference in early ontogeny. Second, an Artificial Neural Network algorithm applied to nymphal morphological characters accurately identified species. This computer-driven artificial intelligence method has power to provide future easy-to-use electronic identification aids. Phylogenetic analysis of nymphal morphology using the parsimony method shows two clades of Prosopistomatidae, one sharing characters with the type species, Prosopistoma variegatum and the other predominating in Africa, although also occurring in Asia; these clades are named the “P. variegatum” and “African” clades, respectively. Parsimony analysis of adult morphology supports these two clades, but supertree analysis obscures the relationships, nesting the “P. variegatum” lineage within the other clade. Preliminary molecular phylogenetic analysis of the 16S rRNA, (mitochondrial) 18S rRNA and Histone-3 genes using Bayesian Inference methods does not support the two clades shown by morphology. Instead, there is a strong relationship between the European species and one African species, with the single Asian representative being most distantly related. These results are limited by lack of fresh material, patchy taxon sampling, and problems with finding suitable primers. A molecular clock program, BEAST, calibrated using fossils, suggests divergence times for the oldest crown-group Prosopistoma clade, represented by the Asian P. wouterae, of about 131 Ma, with the youngest species, the African P. crassi, of 1.21 Ma. Stem-group relationships are analysed using parsimony analysis, focussing on wing characters of the Baetiscoidea, other extant mayfly lineages, and extinct stem-group lineages. This suggests that the Baetiscoidea diverged from main-line Ephemeroptera earlier than any other extant mayfly lineage. This approach expands upon ideas hinted at by earlier scientists. Finally, historical biogeographical analysis of the distribution of known Baetiscoidea s.s. stem-group fossils implies a once Pangean distribution of the lineage. Changing palaeo-climate, catastrophic extinction events and plate tectonic movements in relation to the distribution of crown-group species are reviewed. Other approaches to historical biogeography that build on both morphological and molecular phylogenies are used to interpret disperalist and vacarianist arguments. Distribution patterns of eight unrelated freshwater organisms which share a similar distribution pattern are compared, assuming that shared patterns indicate similar historic biogeographic processes. The distribution of recent Prosopistoma species is seen to be the product of evolution resulting from both vicariance and dispersal. In conclusion, this thesis encompasses a variety of disciplines. It successfully recognises new characters and distinguishes previously unknown species. It uses new approaches to delimiting species and known methods to determine phylogeny from several angles. The analysis of stem-group relationships offers an insight into possible early lineage splitting within Ephemeroptera. Interpretation of historical biogeography allows for both a Gondwanan origin of Prosopistomatidae, with rafting of species on the Deccan plate to Asia, and for subsequent dispersal from Asia down to Australia and across to Europe, and possibly back to Africa.
- Full Text:
The discoursal construction of female physical identity in selected works in children's literature
- Authors: Hunt, Sally Ann
- Date: 2011 , 2013-09-20
- Subjects: Rowling, J K -- Criticism and interpretation Lewis, C S (Clive Staples), 1898-1963 -- Criticism and interpretation Girls in literature Girls -- Identity Human body in literature Gender identity in literature Sex role in literature Children's stories, English -- History and criticism Young women in literature Women in literature
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2377 , http://hdl.handle.net/10962/d1005965
- Description: This thesis reports on an analysis of the discursive construction of female and male physical identity in children’s literature and explicitly combines corpus linguistic methods with a critical discourse approach. Based on three novels from each of the Chronicles of Narnia and the Harry Potter series, it shows clear gendering of body parts, not only in terms of the purely quantitative preferences for certain body parts to be associated with one or other gender, but in terms of discourse prosody, or the uses to which the body parts are put. Human body parts in these series are mostly used in the following four ways, all of which show differences in realisation in terms of gender: · to describe individuals, physically, in order to distinguish one from the other; · to convey emotion, unintentionally as well as consciously; · for physical interaction between people and · for interaction with the world more broadly: responses to danger and agency, i.e. the ability to act on the world and the nature of what is achieved. The use of body parts by characters to express emotion and act agentively on the world is revealed to be strongly gendered in the two series. I characterise the most prominent patterns in terms of the bodily products blood, sweat and tears, of which the last is strongly connected to female characters, who are generally associated with emotion. The other two, referring to active participation in fighting and injury, as well as agency, are almost exclusively reserved for males, with female characters rendered unable to act on the physical world as a result of overwhelming feelings. The females’ response to danger suggests stereotyped discourses of inequality which see women and girls as requiring protection and being physically incapable. Thus gender is still a particularly salient aspect in these widely-read examples of children’s literature, despite plots which appear to be fairly positive towards women. The strength of the inclusion of a corpus approach in this study lies in its capacity to reveal objective, and often fairly covert, trends in language use. These in turn enrich the critical analysis of discourses in these influential texts, which facilitates social change through linguistic analysis.
- Full Text:
- Authors: Hunt, Sally Ann
- Date: 2011 , 2013-09-20
- Subjects: Rowling, J K -- Criticism and interpretation Lewis, C S (Clive Staples), 1898-1963 -- Criticism and interpretation Girls in literature Girls -- Identity Human body in literature Gender identity in literature Sex role in literature Children's stories, English -- History and criticism Young women in literature Women in literature
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2377 , http://hdl.handle.net/10962/d1005965
- Description: This thesis reports on an analysis of the discursive construction of female and male physical identity in children’s literature and explicitly combines corpus linguistic methods with a critical discourse approach. Based on three novels from each of the Chronicles of Narnia and the Harry Potter series, it shows clear gendering of body parts, not only in terms of the purely quantitative preferences for certain body parts to be associated with one or other gender, but in terms of discourse prosody, or the uses to which the body parts are put. Human body parts in these series are mostly used in the following four ways, all of which show differences in realisation in terms of gender: · to describe individuals, physically, in order to distinguish one from the other; · to convey emotion, unintentionally as well as consciously; · for physical interaction between people and · for interaction with the world more broadly: responses to danger and agency, i.e. the ability to act on the world and the nature of what is achieved. The use of body parts by characters to express emotion and act agentively on the world is revealed to be strongly gendered in the two series. I characterise the most prominent patterns in terms of the bodily products blood, sweat and tears, of which the last is strongly connected to female characters, who are generally associated with emotion. The other two, referring to active participation in fighting and injury, as well as agency, are almost exclusively reserved for males, with female characters rendered unable to act on the physical world as a result of overwhelming feelings. The females’ response to danger suggests stereotyped discourses of inequality which see women and girls as requiring protection and being physically incapable. Thus gender is still a particularly salient aspect in these widely-read examples of children’s literature, despite plots which appear to be fairly positive towards women. The strength of the inclusion of a corpus approach in this study lies in its capacity to reveal objective, and often fairly covert, trends in language use. These in turn enrich the critical analysis of discourses in these influential texts, which facilitates social change through linguistic analysis.
- Full Text:
The druggable antimalarial target 1-deoxy-D-xylulose-5-phosphate reductoisomerase: purfication, kinetic characterization and inhibition studies
- Authors: Goble, Jessica Leigh
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Drug development Plasmodium falciparum -- Purification Plasmodium falciparum -- Inhibitors Enzyme kinetics Malaria -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3949 , http://hdl.handle.net/10962/d1004008
- Description: Plasmodium falciparum 1–deoxy–D–xylulose–5 phosphatereductoisomerase (PfDXR) plays a role in isoprenoid biosynthesis in the malaria parasite and is absent in the human host, making this parasite enzyme an attractive target for antimalarial drug design. To characterize PfDXR, it is necessary to produce large quantities of the enzyme in a soluble and functional form. However, the over–production of malarial proteins in prokaryotic host systems often results in the formation of truncated proteins or insoluble protein aggregates. A heterologous expression system was developed for the production of active PfDXR using codon harmonization and tight control of expression in the presence of lac repressor. Yields of up to 2 mg/l of enzyme were reported using the optimised expression system, which is 8 to 10– fold greater than previously reported yields. The kinetic parameters Km, Vmax and kcat were determined for PfDXR; values reported in this study were consistent with those reported in the literature for other DXR enzymes. A three–dimensional model of the malarial drug target protein PfDXR was generated, and validated using structure–checking programs and protein docking studies. Structural and functional features unique to PfDXR were identified using the model and comparative sequence analyses with apicomplexan and non–apicomplexan DXR proteins. Residues Val44 and Asn45, essential for NADPH binding; and catalytic hatch residues Lys224 and Lys226, which are unique to the species of Plasmodium, were mutated to resemble those of E. coli DXR. Interestingly,these mutations resulted in significant reductions in substrate affinity, when compared to the unmutated PfDXR. Mutant enzymes PfDXR(VN43,44AG) and PfDXR(KK224,226NS) also demonstrated a decreased ability to turnover substrate by 4–fold and 2–fold respectively. This study indicates a difference in the role of the catalytic hatch of PfDXR with regards to the way in which it captures substrates. The study also highlights subtle differences in cofactor binding to PfDXR, compared with the well characterized EcDXR enzyme. The validated PfDXR model was also used to develop a novel efficient in silico screening method for potential tool compounds for use in the rational design of novel DXR inhibitors. Following in silico screening of 46 potential DXR inhibitors, a two–tiered in vitro screening approach was undertaken. DXR inhibition was assessed for the 46 novel compounds using an NADPH– ependant DXP enzyme inhibition assay and antimalarial potential was assessed using P.falciparum–infected erythrocyte growth assays. Select compounds were tested in human cells in order to determine whether they were toxic to the host. From the parallel in silico and in vitro drug screening, it was evident that only a single compound demonstrated reasonable potential binding to DXR (determined using in silico docking), inhibited DXR in vitro and inhibited P. falciparum growth, without being toxic to human cells. Its potential as a lead compound in antimalarial drug development is therefore feasible. Two outcomes were evident from this work. Firstly, analogues of known antimalarial natural products can be screened against malaria, which may then lead towards the rational design of novel compounds that are effective against a specific antimalarial drug target enzyme, such as PfDXR. Secondly, the rational design of novel compounds against a specific antimalarial drug target enzyme can be untaken by adopting a coupled in silico and in vitro approach to drug discovery.
- Full Text:
- Authors: Goble, Jessica Leigh
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Drug development Plasmodium falciparum -- Purification Plasmodium falciparum -- Inhibitors Enzyme kinetics Malaria -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3949 , http://hdl.handle.net/10962/d1004008
- Description: Plasmodium falciparum 1–deoxy–D–xylulose–5 phosphatereductoisomerase (PfDXR) plays a role in isoprenoid biosynthesis in the malaria parasite and is absent in the human host, making this parasite enzyme an attractive target for antimalarial drug design. To characterize PfDXR, it is necessary to produce large quantities of the enzyme in a soluble and functional form. However, the over–production of malarial proteins in prokaryotic host systems often results in the formation of truncated proteins or insoluble protein aggregates. A heterologous expression system was developed for the production of active PfDXR using codon harmonization and tight control of expression in the presence of lac repressor. Yields of up to 2 mg/l of enzyme were reported using the optimised expression system, which is 8 to 10– fold greater than previously reported yields. The kinetic parameters Km, Vmax and kcat were determined for PfDXR; values reported in this study were consistent with those reported in the literature for other DXR enzymes. A three–dimensional model of the malarial drug target protein PfDXR was generated, and validated using structure–checking programs and protein docking studies. Structural and functional features unique to PfDXR were identified using the model and comparative sequence analyses with apicomplexan and non–apicomplexan DXR proteins. Residues Val44 and Asn45, essential for NADPH binding; and catalytic hatch residues Lys224 and Lys226, which are unique to the species of Plasmodium, were mutated to resemble those of E. coli DXR. Interestingly,these mutations resulted in significant reductions in substrate affinity, when compared to the unmutated PfDXR. Mutant enzymes PfDXR(VN43,44AG) and PfDXR(KK224,226NS) also demonstrated a decreased ability to turnover substrate by 4–fold and 2–fold respectively. This study indicates a difference in the role of the catalytic hatch of PfDXR with regards to the way in which it captures substrates. The study also highlights subtle differences in cofactor binding to PfDXR, compared with the well characterized EcDXR enzyme. The validated PfDXR model was also used to develop a novel efficient in silico screening method for potential tool compounds for use in the rational design of novel DXR inhibitors. Following in silico screening of 46 potential DXR inhibitors, a two–tiered in vitro screening approach was undertaken. DXR inhibition was assessed for the 46 novel compounds using an NADPH– ependant DXP enzyme inhibition assay and antimalarial potential was assessed using P.falciparum–infected erythrocyte growth assays. Select compounds were tested in human cells in order to determine whether they were toxic to the host. From the parallel in silico and in vitro drug screening, it was evident that only a single compound demonstrated reasonable potential binding to DXR (determined using in silico docking), inhibited DXR in vitro and inhibited P. falciparum growth, without being toxic to human cells. Its potential as a lead compound in antimalarial drug development is therefore feasible. Two outcomes were evident from this work. Firstly, analogues of known antimalarial natural products can be screened against malaria, which may then lead towards the rational design of novel compounds that are effective against a specific antimalarial drug target enzyme, such as PfDXR. Secondly, the rational design of novel compounds against a specific antimalarial drug target enzyme can be untaken by adopting a coupled in silico and in vitro approach to drug discovery.
- Full Text:
The existence of the value premium on the Johannesburg Stock Exchange from 1972 to 2001 and extrapolation as explanation
- Authors: Beukes, Anna
- Date: 2011
- Subjects: Johannesburg Stock Exchange Stocks -- Prices -- South Africa Rational expectations (Economic theory) Investments -- Psychological aspects
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:977 , http://hdl.handle.net/10962/d1002711
- Description: This study investigates the existence of the value premium in South Africa’s equity market, and tests extrapolation as a possible explanation for it. The value premium refers to the widely reported superior performance of share price returns of value companies compared to growth companies. The value premium represents an anomaly in mainstream rational finance theory, because it should not persist, unless it could be explained as the result of some composite form of risk. What is highly vexing is the fact that the value premium not only persists in most financial markets over a long period, but that the risk explanation cannot be upheld convincingly. This contributed to the rise of behavioral finance, an approach which introduces psychological factors to provide new explanations for financial phenomena. The behavioral finance explanation for the value premium observation is extrapolation (the tendency to project recent experience too far into the future). This study applies propositions and methods from behavioral finance to investigate the South African equity market. The existence of a value premium in South Africa was investigated by using twenty-nine years’ worth of accounting and share price data. The study employed one- and two-dimensional tests for portfolio formation, and tracked share price returns for up to five years after portfolio formation. The results indicated that a statistically and economically significant value premium existed in South Africa for the period between 1972 and 2001. Extrapolation as a potential explanation for the value premium observation was investigated by applying internationally used methods. Extrapolation was found to provide a robust explanation for the South African value premium.
- Full Text:
- Authors: Beukes, Anna
- Date: 2011
- Subjects: Johannesburg Stock Exchange Stocks -- Prices -- South Africa Rational expectations (Economic theory) Investments -- Psychological aspects
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:977 , http://hdl.handle.net/10962/d1002711
- Description: This study investigates the existence of the value premium in South Africa’s equity market, and tests extrapolation as a possible explanation for it. The value premium refers to the widely reported superior performance of share price returns of value companies compared to growth companies. The value premium represents an anomaly in mainstream rational finance theory, because it should not persist, unless it could be explained as the result of some composite form of risk. What is highly vexing is the fact that the value premium not only persists in most financial markets over a long period, but that the risk explanation cannot be upheld convincingly. This contributed to the rise of behavioral finance, an approach which introduces psychological factors to provide new explanations for financial phenomena. The behavioral finance explanation for the value premium observation is extrapolation (the tendency to project recent experience too far into the future). This study applies propositions and methods from behavioral finance to investigate the South African equity market. The existence of a value premium in South Africa was investigated by using twenty-nine years’ worth of accounting and share price data. The study employed one- and two-dimensional tests for portfolio formation, and tracked share price returns for up to five years after portfolio formation. The results indicated that a statistically and economically significant value premium existed in South Africa for the period between 1972 and 2001. Extrapolation as a potential explanation for the value premium observation was investigated by applying internationally used methods. Extrapolation was found to provide a robust explanation for the South African value premium.
- Full Text: