An investigation of the learning processes that take place during practical work activities when using electrical circuit boards in grade: a case study
- Authors: Accom, Gerald Charles
- Date: 2012
- Subjects: Competency-based education -- South Africa -- Eastern Cape -- Case studies Educational tests and measurements -- South Africa -- Eastern Cape -- Case studies Education -- Evaluation -- South Africa -- Eastern Cape -- Case studies
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1961 , http://hdl.handle.net/10962/d1009687
- Description: Since the introduction of Outcomes Based Education (OBE) as a preferred method of teaching and learning with Curriculum 2005 in 1997, its existence has come under continuous threat for the past thirteen years. Its teething experiences included a revision in 2004 which saw the introduction of the Revised National Curriculum Statements (RNCS) and most recently, we are now standing on the threshold of the implementation of the Curriculum Assessment Policy Statements (CAPS) in 2012. Throughout the turbulent educational milieu, social constructivism has always been upheld as the preferred teaching and learning methodology and millions of rands have been invested in this regard. This study is thus premised on the concern that now after all the years of actively promoting social constructivist methodologies, the implementation of the CAPS could seriously negate reasonable strides made in this regard. Triggered by these curricular issues, a qualitative case study was conducted at a school in Grahamstown in the Eastern Cape, South Africa, investigating the learning processes occurring in group work sessions during lessons involving practical work in electricity using circuit boards in grade 8. Underpinned by an interpretivist paradigm, the study took place in two phases. The data was mainly generated through audio and video recording of two focus groups. An open coding system was employed to derive analytical categories and frequency tables were used to establish trends. In order to validate the data, two observer teachers were involved throughout the research process and this was followed up with semistructured interviews after the second phase. The two case studies, involving learners fitting a similar profile in respect of mother-tongue and age group, were engaged in a similar activity for almost a year apart. This study anticipated the revelation of the extent to which group practical activities in electricity promoted learning, how knowledge is constructed in group-settings and whether practical activities involving electrical circuit boards in grade 8 enhance learning? The main findings of my study revealed that these practical activities can promote learning and therefore should remain a preferred method of teaching.
- Full Text:
- Date Issued: 2012
- Authors: Accom, Gerald Charles
- Date: 2012
- Subjects: Competency-based education -- South Africa -- Eastern Cape -- Case studies Educational tests and measurements -- South Africa -- Eastern Cape -- Case studies Education -- Evaluation -- South Africa -- Eastern Cape -- Case studies
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1961 , http://hdl.handle.net/10962/d1009687
- Description: Since the introduction of Outcomes Based Education (OBE) as a preferred method of teaching and learning with Curriculum 2005 in 1997, its existence has come under continuous threat for the past thirteen years. Its teething experiences included a revision in 2004 which saw the introduction of the Revised National Curriculum Statements (RNCS) and most recently, we are now standing on the threshold of the implementation of the Curriculum Assessment Policy Statements (CAPS) in 2012. Throughout the turbulent educational milieu, social constructivism has always been upheld as the preferred teaching and learning methodology and millions of rands have been invested in this regard. This study is thus premised on the concern that now after all the years of actively promoting social constructivist methodologies, the implementation of the CAPS could seriously negate reasonable strides made in this regard. Triggered by these curricular issues, a qualitative case study was conducted at a school in Grahamstown in the Eastern Cape, South Africa, investigating the learning processes occurring in group work sessions during lessons involving practical work in electricity using circuit boards in grade 8. Underpinned by an interpretivist paradigm, the study took place in two phases. The data was mainly generated through audio and video recording of two focus groups. An open coding system was employed to derive analytical categories and frequency tables were used to establish trends. In order to validate the data, two observer teachers were involved throughout the research process and this was followed up with semistructured interviews after the second phase. The two case studies, involving learners fitting a similar profile in respect of mother-tongue and age group, were engaged in a similar activity for almost a year apart. This study anticipated the revelation of the extent to which group practical activities in electricity promoted learning, how knowledge is constructed in group-settings and whether practical activities involving electrical circuit boards in grade 8 enhance learning? The main findings of my study revealed that these practical activities can promote learning and therefore should remain a preferred method of teaching.
- Full Text:
- Date Issued: 2012
Movements of sub-adult sicklefin lemon sharks Negaprion acutidens in a remote Indian Ocean atoll
- Authors: Filmalter, John David
- Date: 2012
- Subjects: Silky shark , Silky shark -- Habitat , Sharks -- Amirante Islands (Seychelles)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5383 , http://hdl.handle.net/10962/d1018229
- Description: The sicklefin lemon shark Negaprion acutidens is a large-bodied (> 3m) coastal shark species, widely distributed in tropical and sub-tropical Indo-Pacific waters. Despite its large size and wide distribution, very little is known about its movement behaviour throughout ontogeny. The primary aim of this thesis was to gain an understanding of the movements of sub-adult N. acutidens, in and around the St. Joseph Atoll, Republic of Seychelles, to facilitate the effective conservation of this vulnerable species. A total of 22 sharks (139 – 202 cm TL) were equipped with coded acoustic transmitters and passively monitored using moored acoustic receivers for a period of 20 month from March 2009 to October 2010. The use of passive acoustic telemetry arrays to study behavioural ecology has increased in popularity in recent years and been successfully applied to study a host of teleost and elasmobranch species in a diversity of habitats, ranging from sheltered estuaries to the offshore pelagic environment. However, the practicalities of designing an effective network of receivers to optimally monitor animal movements can be challenging. In this study the receiver array was optimised through a series of incremental steps to achieve an efficient design that allowed for the specific objectives to be addressed. The specific objectives of this study were to i) gain an understanding of the long term space use patterns and site fidelity of sub-adult N. acutidens within degree of use of the St. Joseph Atoll lagoon and surrounding habitats, and ii) investigate their short term behavioural patterns in response to natural rhythmic cycles. The important role the atoll plays in the sub-adult stage of this species was demonstrated by the very low numbers of detections outside the atoll compared to the very large numbers of detections inside the atoll. Over the course of a year the tagged sharks showed a high degree of site fidelity to the atoll, with 79 – 100% of the individuals detected during each month and 50% being detected on a near daily basis. This result provides testimony of the nursery role of the atoll and importance of these habitats in the early life history for this species. Individual area use was generally found to be restricted to the eastern part of the atoll incorporating a portion of the central deep lagoon and a nearby adjacent area of the sand flats. The movements of sub-adult N. acutidens on and off of the shallow flats surrounding the central lagoon (likely for foraging) were found to be strongly influenced by the tidal height and the diel cycle. Tagged sharks were found to utilise the flats more regularly when the tidal height was greater than 90 cm and particularly more so during the night and early morning than during daylight times. The combined results of this study expose the vulnerability of this species to rapid local depletion. Similarly, the effectiveness of spatial management measures, such as no-take marine protected areas is highlighted as an efficient tool for the future conservation of this species. In the St. Joseph Atoll in particular, the use of a multi-levelled protection approach, where the eastern portion on the atoll is completely restricted while the remaining area is utilized for non-consumptive tourism activities, could be highly effective. Future research should investigate changes in area use throughout the ontogeny of this species as well improve the understanding of the breeding site fidelity and population size of reproductive females using the St. Joseph Atoll.
- Full Text:
- Date Issued: 2012
- Authors: Filmalter, John David
- Date: 2012
- Subjects: Silky shark , Silky shark -- Habitat , Sharks -- Amirante Islands (Seychelles)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5383 , http://hdl.handle.net/10962/d1018229
- Description: The sicklefin lemon shark Negaprion acutidens is a large-bodied (> 3m) coastal shark species, widely distributed in tropical and sub-tropical Indo-Pacific waters. Despite its large size and wide distribution, very little is known about its movement behaviour throughout ontogeny. The primary aim of this thesis was to gain an understanding of the movements of sub-adult N. acutidens, in and around the St. Joseph Atoll, Republic of Seychelles, to facilitate the effective conservation of this vulnerable species. A total of 22 sharks (139 – 202 cm TL) were equipped with coded acoustic transmitters and passively monitored using moored acoustic receivers for a period of 20 month from March 2009 to October 2010. The use of passive acoustic telemetry arrays to study behavioural ecology has increased in popularity in recent years and been successfully applied to study a host of teleost and elasmobranch species in a diversity of habitats, ranging from sheltered estuaries to the offshore pelagic environment. However, the practicalities of designing an effective network of receivers to optimally monitor animal movements can be challenging. In this study the receiver array was optimised through a series of incremental steps to achieve an efficient design that allowed for the specific objectives to be addressed. The specific objectives of this study were to i) gain an understanding of the long term space use patterns and site fidelity of sub-adult N. acutidens within degree of use of the St. Joseph Atoll lagoon and surrounding habitats, and ii) investigate their short term behavioural patterns in response to natural rhythmic cycles. The important role the atoll plays in the sub-adult stage of this species was demonstrated by the very low numbers of detections outside the atoll compared to the very large numbers of detections inside the atoll. Over the course of a year the tagged sharks showed a high degree of site fidelity to the atoll, with 79 – 100% of the individuals detected during each month and 50% being detected on a near daily basis. This result provides testimony of the nursery role of the atoll and importance of these habitats in the early life history for this species. Individual area use was generally found to be restricted to the eastern part of the atoll incorporating a portion of the central deep lagoon and a nearby adjacent area of the sand flats. The movements of sub-adult N. acutidens on and off of the shallow flats surrounding the central lagoon (likely for foraging) were found to be strongly influenced by the tidal height and the diel cycle. Tagged sharks were found to utilise the flats more regularly when the tidal height was greater than 90 cm and particularly more so during the night and early morning than during daylight times. The combined results of this study expose the vulnerability of this species to rapid local depletion. Similarly, the effectiveness of spatial management measures, such as no-take marine protected areas is highlighted as an efficient tool for the future conservation of this species. In the St. Joseph Atoll in particular, the use of a multi-levelled protection approach, where the eastern portion on the atoll is completely restricted while the remaining area is utilized for non-consumptive tourism activities, could be highly effective. Future research should investigate changes in area use throughout the ontogeny of this species as well improve the understanding of the breeding site fidelity and population size of reproductive females using the St. Joseph Atoll.
- Full Text:
- Date Issued: 2012
High pressure liquid chromatographic quantification of nitrile biocatalysis
- Authors: Mathiba, Kgama
- Date: 2012
- Subjects: High performance liquid chromatography , Rhodococcus , Biocatalysis , Organic compounds -- Industrial applications
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4129 , http://hdl.handle.net/10962/d1015710
- Description: Nitrile biocatalysts are of use in the chemical and pharmaceutical industries for the synthesis of carboxyamides and carboxylic acids. In particular, the application of biocatalysts in the synthesis of single enantiomer compounds is of increasing interest, but requires novel substrate specific highly stereoselective biocatalysts. Addition to the limited toolbox of known nitrile biocatalysts requires definitive characterisation of the biocatalysts through accurate determination of the substrate profiles and quantification of activity. The accurate quantification of stereoisomers chiral mixtures to determine biocatalyst stereoselectivity remains a significant challenge due to the difficulty in separating stereoisomers by physical methods. The known nitrile metabolising organism, Rhodococcus rhodochrous ATCC BAA-870, was grown in a defined medium and harvested, providing whole cell biocatalyst. Additional biomass was disrupted to provide a cell free enzyme extract, which was put through an enzyme purification protocol to provide a solution with specific activity of 351 U.mg⁻¹. A portion of the enzyme was self immobilised using the SphereZyme™ technique. The nitrile hydratase SphereZymes™ (1.2 U.mg⁻¹ initial activity) that were prepared had pH and temperature optima of 6 and 30°C respectively, and could be recovered by repeated washing. The particles retained activity in the presence of the organic solvents isooctane and n-hexadecane saturated with 50 mM phosphate buffer (pH 7.5). An initial analytical system was devised for quantification of the nitrile hydratase activity using the non-chiral substrate benzonitrile. An improved reversed phase high performance liquid chromatography method was developed to separate and quantify benzamide, benzoic acid and benzonitrile. The mobile phase consisting of 0.1% trifluoroacetic acid in H₂O and acetonitrile (70:30, %v/v), at a flow rate of 0.5 ml.ml⁻¹, 25°C, resolved all three analytes in 3.5 minutes on a Waters X-Terra MS C18 3.5μm column. UV detection was carried out at 210 nm. Analytical methods to determine activity and enantioselectivity of the whole cell biocatalyst were subsequently developed for both β-amino nitriles and β-hydroxy nitrile substrates and hydrolysis products.
- Full Text:
- Date Issued: 2012
- Authors: Mathiba, Kgama
- Date: 2012
- Subjects: High performance liquid chromatography , Rhodococcus , Biocatalysis , Organic compounds -- Industrial applications
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4129 , http://hdl.handle.net/10962/d1015710
- Description: Nitrile biocatalysts are of use in the chemical and pharmaceutical industries for the synthesis of carboxyamides and carboxylic acids. In particular, the application of biocatalysts in the synthesis of single enantiomer compounds is of increasing interest, but requires novel substrate specific highly stereoselective biocatalysts. Addition to the limited toolbox of known nitrile biocatalysts requires definitive characterisation of the biocatalysts through accurate determination of the substrate profiles and quantification of activity. The accurate quantification of stereoisomers chiral mixtures to determine biocatalyst stereoselectivity remains a significant challenge due to the difficulty in separating stereoisomers by physical methods. The known nitrile metabolising organism, Rhodococcus rhodochrous ATCC BAA-870, was grown in a defined medium and harvested, providing whole cell biocatalyst. Additional biomass was disrupted to provide a cell free enzyme extract, which was put through an enzyme purification protocol to provide a solution with specific activity of 351 U.mg⁻¹. A portion of the enzyme was self immobilised using the SphereZyme™ technique. The nitrile hydratase SphereZymes™ (1.2 U.mg⁻¹ initial activity) that were prepared had pH and temperature optima of 6 and 30°C respectively, and could be recovered by repeated washing. The particles retained activity in the presence of the organic solvents isooctane and n-hexadecane saturated with 50 mM phosphate buffer (pH 7.5). An initial analytical system was devised for quantification of the nitrile hydratase activity using the non-chiral substrate benzonitrile. An improved reversed phase high performance liquid chromatography method was developed to separate and quantify benzamide, benzoic acid and benzonitrile. The mobile phase consisting of 0.1% trifluoroacetic acid in H₂O and acetonitrile (70:30, %v/v), at a flow rate of 0.5 ml.ml⁻¹, 25°C, resolved all three analytes in 3.5 minutes on a Waters X-Terra MS C18 3.5μm column. UV detection was carried out at 210 nm. Analytical methods to determine activity and enantioselectivity of the whole cell biocatalyst were subsequently developed for both β-amino nitriles and β-hydroxy nitrile substrates and hydrolysis products.
- Full Text:
- Date Issued: 2012
The isolation, quantification and synthetic modification of antiplasmodial natural products from sargassum heterophyllum
- Authors: Munedzimwe, Tatenda Carol
- Date: 2012
- Subjects: Malaria -- Developing countries -- Prevention , Antimalarials
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3871 , http://hdl.handle.net/10962/d1018252
- Description: Malaria is one of the most deadly parasitic diseases known to man. Although the number of malaria cases reported each year is decreasing, this disease continues to pose health and economic problems mainly in developing countries. Significant progress has been made in the fight against this disease. This includes the discovery and development of potent antimalarial agents. However, the development of resistance to most of these potent antimalarials has made the development of new antiplasmodial agents of paramount importance. Several promising antiplasmodial agents have been found from the marine environment. Amongst these are the tetraprenylated toluquinols from the brown alga: Sargassum heterophyllum. These metabolites have been reported to exhibit a range of antiplasmodial activity; however, the mechanisms by which these compounds bring about their antiplasmodial activity and the pharmacophoric groups responsible for such activity are unknown. Two species of Sargassum algae were encountered during the course of this project. From the investigation of the geographical and seasonal variation of metabolites of S. heterophyllum and S. elegans we established that there were no significant intra and inter site variations amongst metabolite profiles of both species both within and between the sampled seasons. These results enabled us to establish that the collection of both species from three different sites on the eastern coast of South Africa namely; Kenton on Sea, Port Alfred and Noordhoek in autumn, winter or spring would qualitatively yield the same metabolites. A comparison of metabolite profiles of both species also revealed no qualitative differences between metabolites of S. heterophyllum and S. elegans. The quantities of selected prenylated metabolites extracted from S. heterophyllum using four different extraction techniques was also assessed using qNMR as the method of quantification. This led to the identification of optimal extraction techniques and conditions for the extraction of sargahydroquinoic acid (1.38), sargaquinoic aid (1.39) and sargachromenol (2.10) from S. heterophyllum. From this study, the extraction of algae by soxhlet extraction using EtOH as the extraction solvent led to the extraction of the highest quantities of sargahydroquinoic acid. The potential of other extraction techniques such as microwave assisted extraction, to yield high quantities of the selected metabolites were also identified. With gram quantities of sargahydroquinoic acid (1.38) in hand, this compound was modified by oxidation, reduction, acetylation, methylation and cyclization reactions to yield nine derivatives. The derivatives and four naturally occurring prenylated toluquinols were assessed for antiplasmodial and cytotoxic activity against the FCR-3 Gambian Chloroquine resistant strain of P. falciparum and the MDA-MB-231 breast carcinoma cell line respectively. Comparison of antiplasmodial data for all twelve compounds showed that the hydroquinone moeity of sargahydroquinoic acid (1.38) is important for antiplasmodial activity while esterification of the carboxylic acid group in 1.38 resulted in more potent antiplasmodial compounds. Of all twelve compounds, compound 5.2, the hydroquinone methyl ester of 1.38 was found to be the most potent antiplasmodial compound with an IC₅₀ value of 1.94 μM and a selectivity index of 22.68.
- Full Text:
- Date Issued: 2012
- Authors: Munedzimwe, Tatenda Carol
- Date: 2012
- Subjects: Malaria -- Developing countries -- Prevention , Antimalarials
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3871 , http://hdl.handle.net/10962/d1018252
- Description: Malaria is one of the most deadly parasitic diseases known to man. Although the number of malaria cases reported each year is decreasing, this disease continues to pose health and economic problems mainly in developing countries. Significant progress has been made in the fight against this disease. This includes the discovery and development of potent antimalarial agents. However, the development of resistance to most of these potent antimalarials has made the development of new antiplasmodial agents of paramount importance. Several promising antiplasmodial agents have been found from the marine environment. Amongst these are the tetraprenylated toluquinols from the brown alga: Sargassum heterophyllum. These metabolites have been reported to exhibit a range of antiplasmodial activity; however, the mechanisms by which these compounds bring about their antiplasmodial activity and the pharmacophoric groups responsible for such activity are unknown. Two species of Sargassum algae were encountered during the course of this project. From the investigation of the geographical and seasonal variation of metabolites of S. heterophyllum and S. elegans we established that there were no significant intra and inter site variations amongst metabolite profiles of both species both within and between the sampled seasons. These results enabled us to establish that the collection of both species from three different sites on the eastern coast of South Africa namely; Kenton on Sea, Port Alfred and Noordhoek in autumn, winter or spring would qualitatively yield the same metabolites. A comparison of metabolite profiles of both species also revealed no qualitative differences between metabolites of S. heterophyllum and S. elegans. The quantities of selected prenylated metabolites extracted from S. heterophyllum using four different extraction techniques was also assessed using qNMR as the method of quantification. This led to the identification of optimal extraction techniques and conditions for the extraction of sargahydroquinoic acid (1.38), sargaquinoic aid (1.39) and sargachromenol (2.10) from S. heterophyllum. From this study, the extraction of algae by soxhlet extraction using EtOH as the extraction solvent led to the extraction of the highest quantities of sargahydroquinoic acid. The potential of other extraction techniques such as microwave assisted extraction, to yield high quantities of the selected metabolites were also identified. With gram quantities of sargahydroquinoic acid (1.38) in hand, this compound was modified by oxidation, reduction, acetylation, methylation and cyclization reactions to yield nine derivatives. The derivatives and four naturally occurring prenylated toluquinols were assessed for antiplasmodial and cytotoxic activity against the FCR-3 Gambian Chloroquine resistant strain of P. falciparum and the MDA-MB-231 breast carcinoma cell line respectively. Comparison of antiplasmodial data for all twelve compounds showed that the hydroquinone moeity of sargahydroquinoic acid (1.38) is important for antiplasmodial activity while esterification of the carboxylic acid group in 1.38 resulted in more potent antiplasmodial compounds. Of all twelve compounds, compound 5.2, the hydroquinone methyl ester of 1.38 was found to be the most potent antiplasmodial compound with an IC₅₀ value of 1.94 μM and a selectivity index of 22.68.
- Full Text:
- Date Issued: 2012
Language and social services in rural North West the status of Setswana
- Authors: Nkashe, Esther
- Date: 2012
- Subjects: Tswana language Linguistic rights -- South Africa -- North-West Linguistic rights Language policy -- South Africa -- North-West Linguistic minorities -- South Africa -- North-West Multiculturalism -- South Africa -- North-West Language and languages -- Political aspects -- South Africa -- North-West
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3590 , http://hdl.handle.net/10962/d1002165
- Description: This study seeks to support the thesis that African indigenous languages in South Africa should enjoy equal treatment in terms of the South African Constitution. Therefore, it will explore and find ways and means of how the South African government can reach out to rural communities with inadequate English proficiency, in an English-dominated South Africa, by breaking down the existing language barriers and curbing social inequalities. Language rights, like any other human rights, should be protected, as enshrined in the new democratic Constitution of South Africa.
- Full Text:
- Date Issued: 2012
- Authors: Nkashe, Esther
- Date: 2012
- Subjects: Tswana language Linguistic rights -- South Africa -- North-West Linguistic rights Language policy -- South Africa -- North-West Linguistic minorities -- South Africa -- North-West Multiculturalism -- South Africa -- North-West Language and languages -- Political aspects -- South Africa -- North-West
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3590 , http://hdl.handle.net/10962/d1002165
- Description: This study seeks to support the thesis that African indigenous languages in South Africa should enjoy equal treatment in terms of the South African Constitution. Therefore, it will explore and find ways and means of how the South African government can reach out to rural communities with inadequate English proficiency, in an English-dominated South Africa, by breaking down the existing language barriers and curbing social inequalities. Language rights, like any other human rights, should be protected, as enshrined in the new democratic Constitution of South Africa.
- Full Text:
- Date Issued: 2012
Mechanistic studies of unusual Miruta-Baylis-Hillman reactions
- Authors: Nyoni, Dubekile
- Date: 2012
- Subjects: Chemical reactions Benzaldehyde Acrylonitrile Methyl acrylate Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4400 , http://hdl.handle.net/10962/d1006692
- Description: This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.
- Full Text:
- Date Issued: 2012
- Authors: Nyoni, Dubekile
- Date: 2012
- Subjects: Chemical reactions Benzaldehyde Acrylonitrile Methyl acrylate Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4400 , http://hdl.handle.net/10962/d1006692
- Description: This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.
- Full Text:
- Date Issued: 2012
Electrochemical sensing and immunosensing using metallophthalocyanines and biomolecular modified surfaces
- Authors: Mashazi, Philani Nkosinathi
- Date: 2012
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Measles -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5580 , http://hdl.handle.net/10962/d1018248
- Description: The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease.
- Full Text:
- Date Issued: 2012
- Authors: Mashazi, Philani Nkosinathi
- Date: 2012
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Measles -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5580 , http://hdl.handle.net/10962/d1018248
- Description: The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease.
- Full Text:
- Date Issued: 2012
Rivers as borders, dividing or uniting? : the effect of topography and implications for catchment management in South Africa
- Authors: Smedley, David Alan
- Date: 2012
- Subjects: Rivers -- South Africa , Water-supply -- Management -- South Africa , Water-supply -- Management -- Orange River Watershed , Watershed management -- South Africa , Watershed management -- Orange River Watershed , South Africa -- Boundaries , Water-supply -- Management -- Citizen participation , Water-supply -- Government policy -- South Africa , Water-supply -- Political aspects -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4851 , http://hdl.handle.net/10962/d1005527 , Rivers -- South Africa , Water-supply -- Management -- South Africa , Water-supply -- Management -- Orange River Watershed , Watershed management -- South Africa , Watershed management -- Orange River Watershed , South Africa -- Boundaries , Water-supply -- Management -- Citizen participation , Water-supply -- Government policy -- South Africa , Water-supply -- Political aspects -- South Africa
- Description: South Africa's water resources are unequally distributed over space and time to a high degree and our already stressed water resources situation will only be exacerbated by climate change if current predictions are correct. The potential for conflict over increasingly strained water resources in South Africa is thus very real. In order to deal with these complex problems national legislation is demanding that water resource management be decentralized to the local level where active participation can take place in an integrated manner in accordance with the principles of IWRM. However, administrative and political boundaries rarely match those of catchments as, throughout South Africa, rivers have been employed extensively to delineate administrative and political boundaries at a number of spatial scales. The aim of this research is to determine if rivers act as dividing or uniting features in a socio-political landscape and whether topography will influence their role in this context. By considering sections of the Orange-Senqu River, some of which are employed as political or administrative boundaries, this project furthermore aims to consider the implications of this for catchment management in South Africa. South Africa's proposed form of decentralized water management will have to contend with the effects of different topographies on the way in which rivers are perceived and utilized. The ability of a river to act as a dividing or uniting feature is dependent on a number of interrelated factors, the effects of which are either reduced or enhanced by the topography surrounding the river. Factors such as the state of the resource, levels of utilization, local histories and the employment of the river as a political or administrative border are all factors that determine the extent to which a river unites or divides the communities along its banks, and are all influenced by topography. The implications of this for the management of catchments in South Africa are significant. Local water management institutions will have to contend with a mismatch in borders and in many cases bridge social divides that are deeply entrenched along the banks of rivers. Importantly, the need for a context specific approach to catchment management is highlighted.
- Full Text:
- Date Issued: 2012
- Authors: Smedley, David Alan
- Date: 2012
- Subjects: Rivers -- South Africa , Water-supply -- Management -- South Africa , Water-supply -- Management -- Orange River Watershed , Watershed management -- South Africa , Watershed management -- Orange River Watershed , South Africa -- Boundaries , Water-supply -- Management -- Citizen participation , Water-supply -- Government policy -- South Africa , Water-supply -- Political aspects -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4851 , http://hdl.handle.net/10962/d1005527 , Rivers -- South Africa , Water-supply -- Management -- South Africa , Water-supply -- Management -- Orange River Watershed , Watershed management -- South Africa , Watershed management -- Orange River Watershed , South Africa -- Boundaries , Water-supply -- Management -- Citizen participation , Water-supply -- Government policy -- South Africa , Water-supply -- Political aspects -- South Africa
- Description: South Africa's water resources are unequally distributed over space and time to a high degree and our already stressed water resources situation will only be exacerbated by climate change if current predictions are correct. The potential for conflict over increasingly strained water resources in South Africa is thus very real. In order to deal with these complex problems national legislation is demanding that water resource management be decentralized to the local level where active participation can take place in an integrated manner in accordance with the principles of IWRM. However, administrative and political boundaries rarely match those of catchments as, throughout South Africa, rivers have been employed extensively to delineate administrative and political boundaries at a number of spatial scales. The aim of this research is to determine if rivers act as dividing or uniting features in a socio-political landscape and whether topography will influence their role in this context. By considering sections of the Orange-Senqu River, some of which are employed as political or administrative boundaries, this project furthermore aims to consider the implications of this for catchment management in South Africa. South Africa's proposed form of decentralized water management will have to contend with the effects of different topographies on the way in which rivers are perceived and utilized. The ability of a river to act as a dividing or uniting feature is dependent on a number of interrelated factors, the effects of which are either reduced or enhanced by the topography surrounding the river. Factors such as the state of the resource, levels of utilization, local histories and the employment of the river as a political or administrative border are all factors that determine the extent to which a river unites or divides the communities along its banks, and are all influenced by topography. The implications of this for the management of catchments in South Africa are significant. Local water management institutions will have to contend with a mismatch in borders and in many cases bridge social divides that are deeply entrenched along the banks of rivers. Importantly, the need for a context specific approach to catchment management is highlighted.
- Full Text:
- Date Issued: 2012
Butterfly bones
- Authors: Gowans, Elisabeth
- Date: 2012
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5986 , http://hdl.handle.net/10962/d1015723
- Description: Butterfly Bones is a lyrical sequence of poetry and prose poems organised to trace a rhythmical, emotional pattern of experience. In its subject matter, the sequence presents an implied personal narrative recording the author's grief in the ten months following her mother's death in January 2011. It presents brief, vivid scenes from the poet's daily life in a rural village outside Grahamstown, and observations of creatures and her natural surroundings, which serve as a counterpoint to her grief. It can also be read as a meditation on writing, solitude and the possibilities of poetry.
- Full Text:
- Date Issued: 2012
- Authors: Gowans, Elisabeth
- Date: 2012
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5986 , http://hdl.handle.net/10962/d1015723
- Description: Butterfly Bones is a lyrical sequence of poetry and prose poems organised to trace a rhythmical, emotional pattern of experience. In its subject matter, the sequence presents an implied personal narrative recording the author's grief in the ten months following her mother's death in January 2011. It presents brief, vivid scenes from the poet's daily life in a rural village outside Grahamstown, and observations of creatures and her natural surroundings, which serve as a counterpoint to her grief. It can also be read as a meditation on writing, solitude and the possibilities of poetry.
- Full Text:
- Date Issued: 2012
The design, synthesis and antiplasmodial activity of a series of halogenated fosmidomycin analogues and hybrid drugs
- Authors: Afolayan, Anthonia Folake
- Date: 2012
- Subjects: Uncatalogued
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64370 , vital:28538
- Description: Malaria continues to be a devastating disease and a major cause of death in sub-Saharan Africa. With resistance against most of the available antimalarial drugs, there is a need for ongoing research and development of antimalarial agents. Fosmidomycin and its acetyl analogue FR900098 have been identified as potent inhibitors of Plasmodium falciparum, the causative agent of the most deadly form of malaria. Clinical trials of these agents have revealed poor absorption due to their high hydrophilicity. In the present studies the effect of halogenation of the acyl chain as well as the biological effect of extending the acyl sidechain was explored. This provided the basis on which fosmidomycin hybrids were designed to investigate the feasibility of hybrid extending into NADPH binding pocket. Synthesis of a series of halogenated FR900098 analogues was carried out in three stages. This included i) The introduction of the phosphonate group by reaction with 1,3dibromopropane in an Arbuzov reaction, ii) The introduction of a hydroxamate group by reaction of the propyl phosphonate by means of a nucleophilic substitution reaction with BocNHOBn and iii) The introduction of a halogenated acyl side chain on a protected fosmidomycin backbone. The synthesis of fosmidomycin-hybrids for which chloroquinefosmidomycin hybrids were used as the prototype, involved convergence of the two separately constructed moieties i.e. fosmidomycin and the quinoline moieties in a covalent linkage. The quinoline moiety was easily synthesized from the reaction of 4,7dichloroquinoline with 1,2-diamino ethane. The aminoquinoline so formed resulted in chloroquine-fosmidomycin hybrids 3.8 and 3.9 when reacted with halogenated FR900098 analogues. Antiplasmodial assays were conducted on the chloroquine-fosmidomycin hybrids and the halogenated fosmidomycin derivatives against the chloroquine resistant Gambian FCR-3 strain of P. falciparum. The most potent iodoacetyl fosmidomycin analogues 2.21 gave an IC50 value of 5.54 µM which is eight times more potent than the known antiplasmodial FR900098 which gave an IC50 value of 41.67 µM. All the halogenated FR900098 analogues showed better antiplasmodial activity than their non-halogenated derivatives. This indicated that the presence of halogens in the FR900098 analogues contributes to their biological Chapter 1 Literature review activity. The acetyl and propyl linked hybrids 3.8 and 3.9 showed potent antiplasmodial activity with IC50 values of 0.18 and 0.82 µM respectively. These were by far the most potent hybrids synthesized and provided leads for a new class of promising antimalarial agents. Preliminary E. coli DXR enzyme inhibition assays were carried out on the halogenated fosmidomycin analogues. The results showed good inhibition of the enzyme by the phosphonic acids of the chloroacetyl and chloropropyl analogues 2.1 and 2.2 respectively. Molecular modelling of the compounds on E. coli (PDB code: 2EGH) and P. falciparum (PDB code: 3AUA) DXR showed strong binding of the halogenated fosmidomycin analogues while the hybrids in the absence of docked NADPH showed minimum binding to the enzymes.
- Full Text:
- Date Issued: 2012
- Authors: Afolayan, Anthonia Folake
- Date: 2012
- Subjects: Uncatalogued
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64370 , vital:28538
- Description: Malaria continues to be a devastating disease and a major cause of death in sub-Saharan Africa. With resistance against most of the available antimalarial drugs, there is a need for ongoing research and development of antimalarial agents. Fosmidomycin and its acetyl analogue FR900098 have been identified as potent inhibitors of Plasmodium falciparum, the causative agent of the most deadly form of malaria. Clinical trials of these agents have revealed poor absorption due to their high hydrophilicity. In the present studies the effect of halogenation of the acyl chain as well as the biological effect of extending the acyl sidechain was explored. This provided the basis on which fosmidomycin hybrids were designed to investigate the feasibility of hybrid extending into NADPH binding pocket. Synthesis of a series of halogenated FR900098 analogues was carried out in three stages. This included i) The introduction of the phosphonate group by reaction with 1,3dibromopropane in an Arbuzov reaction, ii) The introduction of a hydroxamate group by reaction of the propyl phosphonate by means of a nucleophilic substitution reaction with BocNHOBn and iii) The introduction of a halogenated acyl side chain on a protected fosmidomycin backbone. The synthesis of fosmidomycin-hybrids for which chloroquinefosmidomycin hybrids were used as the prototype, involved convergence of the two separately constructed moieties i.e. fosmidomycin and the quinoline moieties in a covalent linkage. The quinoline moiety was easily synthesized from the reaction of 4,7dichloroquinoline with 1,2-diamino ethane. The aminoquinoline so formed resulted in chloroquine-fosmidomycin hybrids 3.8 and 3.9 when reacted with halogenated FR900098 analogues. Antiplasmodial assays were conducted on the chloroquine-fosmidomycin hybrids and the halogenated fosmidomycin derivatives against the chloroquine resistant Gambian FCR-3 strain of P. falciparum. The most potent iodoacetyl fosmidomycin analogues 2.21 gave an IC50 value of 5.54 µM which is eight times more potent than the known antiplasmodial FR900098 which gave an IC50 value of 41.67 µM. All the halogenated FR900098 analogues showed better antiplasmodial activity than their non-halogenated derivatives. This indicated that the presence of halogens in the FR900098 analogues contributes to their biological Chapter 1 Literature review activity. The acetyl and propyl linked hybrids 3.8 and 3.9 showed potent antiplasmodial activity with IC50 values of 0.18 and 0.82 µM respectively. These were by far the most potent hybrids synthesized and provided leads for a new class of promising antimalarial agents. Preliminary E. coli DXR enzyme inhibition assays were carried out on the halogenated fosmidomycin analogues. The results showed good inhibition of the enzyme by the phosphonic acids of the chloroacetyl and chloropropyl analogues 2.1 and 2.2 respectively. Molecular modelling of the compounds on E. coli (PDB code: 2EGH) and P. falciparum (PDB code: 3AUA) DXR showed strong binding of the halogenated fosmidomycin analogues while the hybrids in the absence of docked NADPH showed minimum binding to the enzymes.
- Full Text:
- Date Issued: 2012
The role of culture in enabling or constraining the use of technology in higher education teaching and learning: the Commerce Curriculum Project
- Mostert, Markus, Snowball, Jeanette D, Boughey, Chrissie
- Authors: Mostert, Markus , Snowball, Jeanette D , Boughey, Chrissie
- Date: 2012
- Language: English
- Type: conference paper , text
- Identifier: http://hdl.handle.net/10962/61073 , vital:27945
- Description: This paper draws on a project located in one faculty at a South African university which aimed to use Information and Communication Technologies (ICTs) to enhance teaching and learning. More specifically, the paper uses Archer’s (1995, 1996, 2000, 1998) ‘analytical dualism’ and ‘morphogenesis’ to explore the way individuals involved in the project were able to exercise agency in departments which were relatively hostile to the goals they were aiming to pursue despite the wider cultural domain encompassing many ideas which construct the use of ICTs as significant in promoting student learning. The paper thus contributes to the culture/agency subtheme of the HECU6 conference. The paper begins by providing some background to the project before moving on to an exploration of the way Archer’s theoretical work was used to analyse data collected by project leaders.
- Full Text:
- Date Issued: 2012
- Authors: Mostert, Markus , Snowball, Jeanette D , Boughey, Chrissie
- Date: 2012
- Language: English
- Type: conference paper , text
- Identifier: http://hdl.handle.net/10962/61073 , vital:27945
- Description: This paper draws on a project located in one faculty at a South African university which aimed to use Information and Communication Technologies (ICTs) to enhance teaching and learning. More specifically, the paper uses Archer’s (1995, 1996, 2000, 1998) ‘analytical dualism’ and ‘morphogenesis’ to explore the way individuals involved in the project were able to exercise agency in departments which were relatively hostile to the goals they were aiming to pursue despite the wider cultural domain encompassing many ideas which construct the use of ICTs as significant in promoting student learning. The paper thus contributes to the culture/agency subtheme of the HECU6 conference. The paper begins by providing some background to the project before moving on to an exploration of the way Archer’s theoretical work was used to analyse data collected by project leaders.
- Full Text:
- Date Issued: 2012
A case study describing factors perceived to be impacting staff satisfaction amongst health care professionals at the East London Hospital complex
- Authors: Galo, Luntu
- Date: 2012
- Subjects: Medical personnel -- Job satisfaction -- South Africa -- Case studies Medical personnel -- Job stress -- South Africa -- Case studies Medical personnel -- South Africa -- Attitudes -- Case studies Hospitals -- South Africa -- Administration Health services administration -- South Africa Health planning -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:784 , http://hdl.handle.net/10962/d1003905
- Description: This thesis was born from a concern the researcher had with regard to negative reports in the media emanating from 4 babies that died at Cecilia Makiwane Hospital Peadiatric ICU unit due to power supply failure. The most significant of these negative reports was in 2007 when the Daily Dispatch ran a series of articles regarding what they termed avoidable deaths over the last 14 years. The ease with which staff communicated with the media together with the high absenteeism rate and high turnover was a cause for concern. When the researcher analysed the history of the problem, it immerged from the respondents’ responses that the rationalistion process undertaken by the Eastern Cape Department of Health (ECDoH) was a significant root cause to the problem. The literature review focused on three areas viz.: Organisational Culture, Organisational Change, Foundations of Satisfaction. This focus was used to confine the problem to a manageable project but secondly each of the aspects are interwoven. Routledge (2010) notes that culture is the reflection of the values advocated by a founder or leader by way of his/her day to day actions. This is done by the leader creating a perception or viewpoint that assists the employees to achieve the organisation’s mission, vision and goals. In any organisation change is a constant and it needs to be effectively managed. With government institutions like the East London Hospital Complex (ELHC) directives come from the top and are implemented by an unprepared and untrained leadership and management cadre and clear communication of vision and objective of the desired outcomes never happens. The aim of the research was to: describe the existing Organisational Culture present at ELHC (Perform an organisational diagnosis); describe the impact of change (rationalisation) and to analyze why there was such a high staff turnover. It is clear from the results of the survey conducted that significant dissatisfaction prevailed relating to how the institution was managed. Dissatisfaction amongst the health professionals was general but also specific to the following: leadership and management issues, fairness, remuneration and lack of resources. The recommendations therefore focused on developing management and leadership within the proposal of Dubrin’s model (2001).
- Full Text:
- Date Issued: 2012
- Authors: Galo, Luntu
- Date: 2012
- Subjects: Medical personnel -- Job satisfaction -- South Africa -- Case studies Medical personnel -- Job stress -- South Africa -- Case studies Medical personnel -- South Africa -- Attitudes -- Case studies Hospitals -- South Africa -- Administration Health services administration -- South Africa Health planning -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:784 , http://hdl.handle.net/10962/d1003905
- Description: This thesis was born from a concern the researcher had with regard to negative reports in the media emanating from 4 babies that died at Cecilia Makiwane Hospital Peadiatric ICU unit due to power supply failure. The most significant of these negative reports was in 2007 when the Daily Dispatch ran a series of articles regarding what they termed avoidable deaths over the last 14 years. The ease with which staff communicated with the media together with the high absenteeism rate and high turnover was a cause for concern. When the researcher analysed the history of the problem, it immerged from the respondents’ responses that the rationalistion process undertaken by the Eastern Cape Department of Health (ECDoH) was a significant root cause to the problem. The literature review focused on three areas viz.: Organisational Culture, Organisational Change, Foundations of Satisfaction. This focus was used to confine the problem to a manageable project but secondly each of the aspects are interwoven. Routledge (2010) notes that culture is the reflection of the values advocated by a founder or leader by way of his/her day to day actions. This is done by the leader creating a perception or viewpoint that assists the employees to achieve the organisation’s mission, vision and goals. In any organisation change is a constant and it needs to be effectively managed. With government institutions like the East London Hospital Complex (ELHC) directives come from the top and are implemented by an unprepared and untrained leadership and management cadre and clear communication of vision and objective of the desired outcomes never happens. The aim of the research was to: describe the existing Organisational Culture present at ELHC (Perform an organisational diagnosis); describe the impact of change (rationalisation) and to analyze why there was such a high staff turnover. It is clear from the results of the survey conducted that significant dissatisfaction prevailed relating to how the institution was managed. Dissatisfaction amongst the health professionals was general but also specific to the following: leadership and management issues, fairness, remuneration and lack of resources. The recommendations therefore focused on developing management and leadership within the proposal of Dubrin’s model (2001).
- Full Text:
- Date Issued: 2012
The implications of rural-urban migration on employment and household income with particular reference to Lesotho
- Authors: Damane, Moeti
- Date: 2012
- Subjects: Rural-urban migration -- Employment -- Lesotho Informal sector (Economics) -- Lesotho Lesotho -- Economic conditions
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:1002 , http://hdl.handle.net/10962/d1002737
- Description: The research investigates the impact of internal rural - urban migration III Lesotho on household income and employment. Using data gathered from the 2002/03 household survey, the 2006 nationwide census and a questionnaire on rural - urban migration in Lesotho administered to 500 respondents in Maseru and Leribe, we estimate a logit model of the probability of employment in Lesotho in 2008 given a set of independent variables. The independent variables are respondent's work experience; years of education completed; employment status in 2004; employment status in 2008; gender; job skill level; place of residence in 2004 and a categorical variable that measures whether or not the respondent is a rural - urban migrant. The results suggest that migration and work experience have no significant impact on an individual's likelihood of being employed in the country's formal sector. Also, it was found that the higher the level of education an individual has, the less likely are their chances of employment in the country's formal sector because of the lack of formal jobs in the urban areas. Over 50% of Lesotho's workforce employed in the urban areas was discovered to work in the informal sector. The study concludes that there is a lack of jobs in Lesotho's urban formal sector that results in a thriving informal sector. The advantages of informal sector jobs to the rural - urban migrant include an increase in their standard of living as well as that of their family members left behind in the rural areas but the disadvantages include low levels of investor confidence that lead to a decrease in overall economic development and growth in the country.
- Full Text:
- Date Issued: 2012
- Authors: Damane, Moeti
- Date: 2012
- Subjects: Rural-urban migration -- Employment -- Lesotho Informal sector (Economics) -- Lesotho Lesotho -- Economic conditions
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:1002 , http://hdl.handle.net/10962/d1002737
- Description: The research investigates the impact of internal rural - urban migration III Lesotho on household income and employment. Using data gathered from the 2002/03 household survey, the 2006 nationwide census and a questionnaire on rural - urban migration in Lesotho administered to 500 respondents in Maseru and Leribe, we estimate a logit model of the probability of employment in Lesotho in 2008 given a set of independent variables. The independent variables are respondent's work experience; years of education completed; employment status in 2004; employment status in 2008; gender; job skill level; place of residence in 2004 and a categorical variable that measures whether or not the respondent is a rural - urban migrant. The results suggest that migration and work experience have no significant impact on an individual's likelihood of being employed in the country's formal sector. Also, it was found that the higher the level of education an individual has, the less likely are their chances of employment in the country's formal sector because of the lack of formal jobs in the urban areas. Over 50% of Lesotho's workforce employed in the urban areas was discovered to work in the informal sector. The study concludes that there is a lack of jobs in Lesotho's urban formal sector that results in a thriving informal sector. The advantages of informal sector jobs to the rural - urban migrant include an increase in their standard of living as well as that of their family members left behind in the rural areas but the disadvantages include low levels of investor confidence that lead to a decrease in overall economic development and growth in the country.
- Full Text:
- Date Issued: 2012
Using co-located radars and instruments to analyse ionespheric events over South Africa
- Authors: Athieno, Racheal
- Date: 2012
- Subjects: Ionosphere -- Research -- South Africa , Space environment -- Research -- South Africa , Meteorology -- Research -- South Africa , Ionosondes -- Research -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5493 , http://hdl.handle.net/10962/d1005279 , Ionosphere -- Research -- South Africa , Space environment -- Research -- South Africa , Meteorology -- Research -- South Africa , Ionosondes -- Research -- South Africa
- Description: Space weather and its effect on technological systems are important for scientific research. Developing an understanding of the behaviour, sources and effects of ionospheric events form a basis for improving space weather prediction. This thesis attempts to use co-located radars and instruments for the analysis of ionospheric events over South Africa. The HF Doppler radar, ionosonde, Global Positioning System (GPS) and GPS ionospheric scintillation monitor (GISTM) receivers are co-located in Hermanus (34.4°S, 19.2°E), one of the observatories for the space science directorate of the South African National Space Agency (SANSA). Data was obtained from these radars and instruments and analysed for ionospheric events. Only the Hermanus station was selected for this analysis, because it is currently the only South African station that hosts all the mentioned radars and instruments. Ionospheric events identified include wave-like structures, Doppler spread, sudden frequency deviations and ionospheric oscillations associated with geomagnetic pulsations. For the purpose of this work, ionospheric events are defined as any unusual structures observed on the received signal and inferred from observations made by the HF Doppler radar. They were identified by visual inspection of the Doppler shift spectrograms. The magnitude and nature of the events vary, depending on their source and were observed by all, some or one instrument. This study suggests that the inclusion of a wider data coverage and more stations in South Africa merit consideration, especially since plans are underway to host a co-located radar network similar to that in Hermanus at at least three additional observatory sites in South Africa. This study lays a foundation for multi-station co-located radar and instrument observation and analysis of ionospheric events which should enhance the accuracy of space weather and HF communication prediction.
- Full Text:
- Date Issued: 2012
- Authors: Athieno, Racheal
- Date: 2012
- Subjects: Ionosphere -- Research -- South Africa , Space environment -- Research -- South Africa , Meteorology -- Research -- South Africa , Ionosondes -- Research -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5493 , http://hdl.handle.net/10962/d1005279 , Ionosphere -- Research -- South Africa , Space environment -- Research -- South Africa , Meteorology -- Research -- South Africa , Ionosondes -- Research -- South Africa
- Description: Space weather and its effect on technological systems are important for scientific research. Developing an understanding of the behaviour, sources and effects of ionospheric events form a basis for improving space weather prediction. This thesis attempts to use co-located radars and instruments for the analysis of ionospheric events over South Africa. The HF Doppler radar, ionosonde, Global Positioning System (GPS) and GPS ionospheric scintillation monitor (GISTM) receivers are co-located in Hermanus (34.4°S, 19.2°E), one of the observatories for the space science directorate of the South African National Space Agency (SANSA). Data was obtained from these radars and instruments and analysed for ionospheric events. Only the Hermanus station was selected for this analysis, because it is currently the only South African station that hosts all the mentioned radars and instruments. Ionospheric events identified include wave-like structures, Doppler spread, sudden frequency deviations and ionospheric oscillations associated with geomagnetic pulsations. For the purpose of this work, ionospheric events are defined as any unusual structures observed on the received signal and inferred from observations made by the HF Doppler radar. They were identified by visual inspection of the Doppler shift spectrograms. The magnitude and nature of the events vary, depending on their source and were observed by all, some or one instrument. This study suggests that the inclusion of a wider data coverage and more stations in South Africa merit consideration, especially since plans are underway to host a co-located radar network similar to that in Hermanus at at least three additional observatory sites in South Africa. This study lays a foundation for multi-station co-located radar and instrument observation and analysis of ionospheric events which should enhance the accuracy of space weather and HF communication prediction.
- Full Text:
- Date Issued: 2012
An assessment of inland fisheries in South Africa using fisheries-dependent and fisheries-independent data sources
- Authors: McCafferty, James Ross
- Date: 2012
- Subjects: Fisheries -- South Africa , Fishery management -- South Africa , Fisheries -- Economic aspects -- South Africa , Food security -- South Africa , Poverty -- South Africa , Economic development -- South Africa , Fishing -- South Africa , Fisheries -- Catch effort -- South Africa , Fish stock assessment -- South Africa , Fish populations -- South Africa , Linear models (Statistics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5229 , http://hdl.handle.net/10962/d1005072 , Fisheries -- South Africa , Fishery management -- South Africa , Fisheries -- Economic aspects -- South Africa , Food security -- South Africa , Poverty -- South Africa , Economic development -- South Africa , Fishing -- South Africa , Fisheries -- Catch effort -- South Africa , Fish stock assessment -- South Africa , Fish populations -- South Africa , Linear models (Statistics)
- Description: The role of inland fisheries as contributors to local and national economies in developing African countries is well documented. In South Africa, there is increasing interest in inland fisheries as vehicles for achieving national policy objectives including food security, livelihoods provision, poverty alleviation and economic development but there is surprisingly little literature on the history, current status, and potential of inland fishery resources. This lack of knowledge constrains the development of management strategies for ensuring the biological sustainability of these resources and the economic and social sustainability of the people that are dependent on them. In order to contribute to the knowledge base of inland fisheries in South Africa this thesis: (1) presents an exhaustive review of the available literature on inland fisheries in South Africa; (2) describes the organisation of recreational anglers (the primary users of the resource); (3) compiles recreational angling catch records and scientific gill net survey data, and assesses the applicability of these data for providing estimates of fish abundance (catch-per-unit effort [CPUE]); and finally, (4) determines the potential for models of fish abundance using morphometric, edaphic, and climatic factors. The literature review highlighted the data-poor nature of South African inland fisheries. In particular information on harvest rates was lacking. A lack of knowledge regarding different inland fishery sectors, governance systems, and potential user conflicts was also found. Recreational anglers were identified as the dominant user group and catch data from this sector were identified as potential sources of fish abundance and harvest information. Formal freshwater recreational angling in South Africa is a highly organised, multi-faceted activity which is based primarily on angling for non-native species, particularly common carp Cyprinus carpio and largemouth bass Micropterus salmoides. Bank anglers constituted the largest number of formal participants (5 309 anglers affiliated to formal angling organisations) followed by bass anglers (1 184 anglers affiliated to formal angling organisations). The highly structured nature of organised recreational angling and dominant utilisation of inland fisheries resources by this sector illustrated not only the vested interest of anglers in the management and development of inland fisheries but also the role that anglers may play in future decision-making and monitoring through the dissemination of catch data from organised angling events. Generalised linear models (GLMs) and generalised additive models (GAMs) were used to standardise CPUE estimates from bass- and bank angling catch records, which provided the most suitable data, and to determine environmental variables which most influenced capture probabilities and CPUE. Capture probabilities and CPUE for bass were influenced primarily by altitude and conductivity and multiple regression analysis revealed that predictive models incorporating altitude, conductivity, surface area and capacity explained significant (p<0.05) amounts of variability in CPUE (53%), probability of capture (49%) and probability of limit bag (74%). Bank angling CPUE was influenced by conductivity, surface area and rainfall although an insignificant (p>0.05) amount of variability (63%) was explained by a predictive model incorporating these variables as investigations were constrained by small sample sizes and aggregated catch information. Scientific survey data provided multi-species information and highlighted the high proportion of non-native fish species in Eastern Cape impoundments. Gillnet catches were influenced primarily by species composition and were less subject to fluctuations induced by environmental factors. Overall standardised gillnet CPUE was influenced by surface area, conductivity and age of impoundment. Although the model fit was not significant at the p<0.05 level, 23% of the variability in the data was explained by a predictive model incorporating these variables. The presence of species which could be effectively targeted by gillnets was hypothesised to represent the most important factor influencing catch rates. Investigation of factors influencing CPUE in impoundments dominated by Clarias gariepinus and native cyprinids indicated that warmer, younger impoundments and smaller, colder impoundments produced higher catches of C. gariepinus and native cyprinids respectively. A predictive model for C. gariepinus abundance explained a significant amount of variability (77%) in CPUE although the small sample size of impoundments suggests that predictions from this model may not be robust. CPUE of native cyprinids was influenced primarily by the presence of Labeo umbratus and constrained by small sample size of impoundments and the model did not adequately explain the variability in the data (r² = 0.31, p>0.05). These results indicate that angling catch- and scientific survey data can be useful in providing predictions of fish abundance that are biologically realistic. However, more data over a greater spatial scale would allow for more robust predictions of catch rates. This could be achieved through increased monitoring of existing resource users, the creation of a centralised database for catch records from angling competitions, and increased scientific surveys of South African impoundments conducted by a dedicated governmental function.
- Full Text:
- Date Issued: 2012
- Authors: McCafferty, James Ross
- Date: 2012
- Subjects: Fisheries -- South Africa , Fishery management -- South Africa , Fisheries -- Economic aspects -- South Africa , Food security -- South Africa , Poverty -- South Africa , Economic development -- South Africa , Fishing -- South Africa , Fisheries -- Catch effort -- South Africa , Fish stock assessment -- South Africa , Fish populations -- South Africa , Linear models (Statistics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5229 , http://hdl.handle.net/10962/d1005072 , Fisheries -- South Africa , Fishery management -- South Africa , Fisheries -- Economic aspects -- South Africa , Food security -- South Africa , Poverty -- South Africa , Economic development -- South Africa , Fishing -- South Africa , Fisheries -- Catch effort -- South Africa , Fish stock assessment -- South Africa , Fish populations -- South Africa , Linear models (Statistics)
- Description: The role of inland fisheries as contributors to local and national economies in developing African countries is well documented. In South Africa, there is increasing interest in inland fisheries as vehicles for achieving national policy objectives including food security, livelihoods provision, poverty alleviation and economic development but there is surprisingly little literature on the history, current status, and potential of inland fishery resources. This lack of knowledge constrains the development of management strategies for ensuring the biological sustainability of these resources and the economic and social sustainability of the people that are dependent on them. In order to contribute to the knowledge base of inland fisheries in South Africa this thesis: (1) presents an exhaustive review of the available literature on inland fisheries in South Africa; (2) describes the organisation of recreational anglers (the primary users of the resource); (3) compiles recreational angling catch records and scientific gill net survey data, and assesses the applicability of these data for providing estimates of fish abundance (catch-per-unit effort [CPUE]); and finally, (4) determines the potential for models of fish abundance using morphometric, edaphic, and climatic factors. The literature review highlighted the data-poor nature of South African inland fisheries. In particular information on harvest rates was lacking. A lack of knowledge regarding different inland fishery sectors, governance systems, and potential user conflicts was also found. Recreational anglers were identified as the dominant user group and catch data from this sector were identified as potential sources of fish abundance and harvest information. Formal freshwater recreational angling in South Africa is a highly organised, multi-faceted activity which is based primarily on angling for non-native species, particularly common carp Cyprinus carpio and largemouth bass Micropterus salmoides. Bank anglers constituted the largest number of formal participants (5 309 anglers affiliated to formal angling organisations) followed by bass anglers (1 184 anglers affiliated to formal angling organisations). The highly structured nature of organised recreational angling and dominant utilisation of inland fisheries resources by this sector illustrated not only the vested interest of anglers in the management and development of inland fisheries but also the role that anglers may play in future decision-making and monitoring through the dissemination of catch data from organised angling events. Generalised linear models (GLMs) and generalised additive models (GAMs) were used to standardise CPUE estimates from bass- and bank angling catch records, which provided the most suitable data, and to determine environmental variables which most influenced capture probabilities and CPUE. Capture probabilities and CPUE for bass were influenced primarily by altitude and conductivity and multiple regression analysis revealed that predictive models incorporating altitude, conductivity, surface area and capacity explained significant (p<0.05) amounts of variability in CPUE (53%), probability of capture (49%) and probability of limit bag (74%). Bank angling CPUE was influenced by conductivity, surface area and rainfall although an insignificant (p>0.05) amount of variability (63%) was explained by a predictive model incorporating these variables as investigations were constrained by small sample sizes and aggregated catch information. Scientific survey data provided multi-species information and highlighted the high proportion of non-native fish species in Eastern Cape impoundments. Gillnet catches were influenced primarily by species composition and were less subject to fluctuations induced by environmental factors. Overall standardised gillnet CPUE was influenced by surface area, conductivity and age of impoundment. Although the model fit was not significant at the p<0.05 level, 23% of the variability in the data was explained by a predictive model incorporating these variables. The presence of species which could be effectively targeted by gillnets was hypothesised to represent the most important factor influencing catch rates. Investigation of factors influencing CPUE in impoundments dominated by Clarias gariepinus and native cyprinids indicated that warmer, younger impoundments and smaller, colder impoundments produced higher catches of C. gariepinus and native cyprinids respectively. A predictive model for C. gariepinus abundance explained a significant amount of variability (77%) in CPUE although the small sample size of impoundments suggests that predictions from this model may not be robust. CPUE of native cyprinids was influenced primarily by the presence of Labeo umbratus and constrained by small sample size of impoundments and the model did not adequately explain the variability in the data (r² = 0.31, p>0.05). These results indicate that angling catch- and scientific survey data can be useful in providing predictions of fish abundance that are biologically realistic. However, more data over a greater spatial scale would allow for more robust predictions of catch rates. This could be achieved through increased monitoring of existing resource users, the creation of a centralised database for catch records from angling competitions, and increased scientific surveys of South African impoundments conducted by a dedicated governmental function.
- Full Text:
- Date Issued: 2012
A comparative polarimetric study of the 43 GHz and 86 GHz SiO masers toward the supergiant star VY CMa
- Authors: Richter, Laura
- Date: 2012
- Subjects: Masers Supergiant stars Polarization (Light) Very long baseline interferometry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5454 , http://hdl.handle.net/10962/d1005239
- Description: The aim of this thesis is to perform observational tests of SiO maser polarisation and excitation models, using component-level comparisons of multiple SiO maser transitions in the 43 GHz and 86 GHz bands at milliarcsecond resolution. These observations reqwre very long baseline interferometric imaging with very accurate polarimetric calibration. The supergiant star VY CMa was chosen as the object of this study due to its high SiO maser luminosity, many detected SiO maser lines, and intrinsic scientific interest. Two epochs of full-polarisation VLBA observations of VY CMa were performed. The Epoch 2 observations were reduced using several new data reduction methods developed as part of this work, and designed specifically to improve the accuracy of circular polarisation calibration of spectral-line VLBI observations at millimetre wavelengths. The accuracy is estimated to be better than 1% using these methods. The Epoch 2 images show a concentration of v= l and v=2 J= 1-0 SiO masers to the east and northeast of the assumed stellar position. The v=l J=2-1 masers were more evenly distributed around the star, with a notable lack of emission in the northeast. There is appreciable spatial overlap between these three lines. The nature of the overlap is generally consistent with the predictions of hydrodynamical circumstellar SiO maser simulations. Where the v=l J = 1-0 and J =2-1 features overlap, the v=l J = 2-1 emission is usually considerably weaker. This is not predicted by current hydrodynamical models, but can be explained in the context of collisional pumping in a low density environment. Six observational tests of weak-splitting maser polarisation models were performed, including intercomparisons of linear polarisation in the v=l J=1-0 and J=2-1lines, linear polarisation versus saturation level, linear polarisation versus distance from the star, circular polarisation in the v= l J = 1-0 and J=2-1 lines, circular versus linear polarisation and modeling of ~ 900 electric-vector position angle rotations. The polarisation model tests generally do not support non-Zeeman circular polarisation mechanisms. For the linear polarisation tests, the results are more consistent with models that predict similar linear polarisation across transitions. The scientific importance of these tests is described in detail and avenues for future work are described.
- Full Text:
- Date Issued: 2012
- Authors: Richter, Laura
- Date: 2012
- Subjects: Masers Supergiant stars Polarization (Light) Very long baseline interferometry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5454 , http://hdl.handle.net/10962/d1005239
- Description: The aim of this thesis is to perform observational tests of SiO maser polarisation and excitation models, using component-level comparisons of multiple SiO maser transitions in the 43 GHz and 86 GHz bands at milliarcsecond resolution. These observations reqwre very long baseline interferometric imaging with very accurate polarimetric calibration. The supergiant star VY CMa was chosen as the object of this study due to its high SiO maser luminosity, many detected SiO maser lines, and intrinsic scientific interest. Two epochs of full-polarisation VLBA observations of VY CMa were performed. The Epoch 2 observations were reduced using several new data reduction methods developed as part of this work, and designed specifically to improve the accuracy of circular polarisation calibration of spectral-line VLBI observations at millimetre wavelengths. The accuracy is estimated to be better than 1% using these methods. The Epoch 2 images show a concentration of v= l and v=2 J= 1-0 SiO masers to the east and northeast of the assumed stellar position. The v=l J=2-1 masers were more evenly distributed around the star, with a notable lack of emission in the northeast. There is appreciable spatial overlap between these three lines. The nature of the overlap is generally consistent with the predictions of hydrodynamical circumstellar SiO maser simulations. Where the v=l J = 1-0 and J =2-1 features overlap, the v=l J = 2-1 emission is usually considerably weaker. This is not predicted by current hydrodynamical models, but can be explained in the context of collisional pumping in a low density environment. Six observational tests of weak-splitting maser polarisation models were performed, including intercomparisons of linear polarisation in the v=l J=1-0 and J=2-1lines, linear polarisation versus saturation level, linear polarisation versus distance from the star, circular polarisation in the v= l J = 1-0 and J=2-1 lines, circular versus linear polarisation and modeling of ~ 900 electric-vector position angle rotations. The polarisation model tests generally do not support non-Zeeman circular polarisation mechanisms. For the linear polarisation tests, the results are more consistent with models that predict similar linear polarisation across transitions. The scientific importance of these tests is described in detail and avenues for future work are described.
- Full Text:
- Date Issued: 2012
Nanocomposites of nickel phthalocyanines as electrocatalysts for the oxidation of chlorophenols an experimental and theoretical approach
- Authors: Khene, Mielie Samson
- Date: 2012
- Subjects: Nanocomposites (Materials) -- Research Phthalocyanines -- Research Chlorophenols -- Research Electrocatalysis -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4326 , http://hdl.handle.net/10962/d1004986
- Description: In this work the interaction between peripherally (b) substituted nickel tetrahydroxyphthalocyanines (b-NiPc(OH)4 and poly-b-Ni(O)Pc(OH)4) with 4-chlorophenol is theoretically rationalized by performing calculations at the B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and 4-chlorophenol, in order to determine the reactive sites involved when 4-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: OPGE-α-NiPc(OH)8 (OPGE = ordinary pyrolytic graphite electrode, α = nonperipheral substitution), OPGE-a-NiPc(OH)4 and OPGE-β- NiPc(OH)4 are compared with those of the polymerized counterparts: OPGE-poly-α-Ni(O)Pc(OH)8, OPGE poly-a-NiPc(OH)4 and OPGE-poly-β-NiPc(OH)4, respectively. β-NiPc(NH2)4, β-NiPc(OH)4, α-NiPc(OH)4, α-NiPc(OH)8, α-NiPc(C10H21)8 are adsorbed on singled walled carbon nanotube (SWCNT) and β-NiPc(NH2)4-SWCNT (linked to SWCNT), are used to modify glassy carbon electrode (GCE) and employed for the electro oxidation of chlorophenols. The β-NiPc(NH2)4-SWCNT gave the best current response for the oxidation of 4-chlorophenol. α-NiPc(OH)8-SWCNT and α-NiPc(C10H21)8 gave the best resistance to electrode fouling due to oxidation by product of 4-chlorophenol. The synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) capped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (β-NiPc(NH2)4) complex were also employed for the oxidation of chlorophenols. Separation of one of the diastereomers of 1, 2-subnaphthalocyanine (SubNPc) was achieved as well as separation of the enantiomers. The absorption and magnetic circular dichroism spectra, together with theoretical calculations, reveal rather small variations in the frontier molecular orbitals of the SubNPc compared to conventional subphthalocyanine (SubPc), except for the destabilization of the highest occupied molecular orbital (HOMO), which results in a characteristic absorption in the Soret band region. The chirality of SubNPc, including the cyclic dichroism (CD) signs and intensities, are discussed in detail.
- Full Text:
- Date Issued: 2012
- Authors: Khene, Mielie Samson
- Date: 2012
- Subjects: Nanocomposites (Materials) -- Research Phthalocyanines -- Research Chlorophenols -- Research Electrocatalysis -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4326 , http://hdl.handle.net/10962/d1004986
- Description: In this work the interaction between peripherally (b) substituted nickel tetrahydroxyphthalocyanines (b-NiPc(OH)4 and poly-b-Ni(O)Pc(OH)4) with 4-chlorophenol is theoretically rationalized by performing calculations at the B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and 4-chlorophenol, in order to determine the reactive sites involved when 4-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: OPGE-α-NiPc(OH)8 (OPGE = ordinary pyrolytic graphite electrode, α = nonperipheral substitution), OPGE-a-NiPc(OH)4 and OPGE-β- NiPc(OH)4 are compared with those of the polymerized counterparts: OPGE-poly-α-Ni(O)Pc(OH)8, OPGE poly-a-NiPc(OH)4 and OPGE-poly-β-NiPc(OH)4, respectively. β-NiPc(NH2)4, β-NiPc(OH)4, α-NiPc(OH)4, α-NiPc(OH)8, α-NiPc(C10H21)8 are adsorbed on singled walled carbon nanotube (SWCNT) and β-NiPc(NH2)4-SWCNT (linked to SWCNT), are used to modify glassy carbon electrode (GCE) and employed for the electro oxidation of chlorophenols. The β-NiPc(NH2)4-SWCNT gave the best current response for the oxidation of 4-chlorophenol. α-NiPc(OH)8-SWCNT and α-NiPc(C10H21)8 gave the best resistance to electrode fouling due to oxidation by product of 4-chlorophenol. The synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) capped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (β-NiPc(NH2)4) complex were also employed for the oxidation of chlorophenols. Separation of one of the diastereomers of 1, 2-subnaphthalocyanine (SubNPc) was achieved as well as separation of the enantiomers. The absorption and magnetic circular dichroism spectra, together with theoretical calculations, reveal rather small variations in the frontier molecular orbitals of the SubNPc compared to conventional subphthalocyanine (SubPc), except for the destabilization of the highest occupied molecular orbital (HOMO), which results in a characteristic absorption in the Soret band region. The chirality of SubNPc, including the cyclic dichroism (CD) signs and intensities, are discussed in detail.
- Full Text:
- Date Issued: 2012
Assessing the effect of a laundry detergent ingredient (LAS) on organisms of a rural South African river
- Authors: Gordon, Andrew K
- Date: 2012
- Subjects: Detergent pollution of rivers, lakes, etc. -- Research -- South Africa -- Eastern Cape Water -- Pollution -- Research -- South Africa -- Eastern Cape Stream health -- Research -- South Africa -- Eastern Cape Stream ecology -- Research -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6042 , http://hdl.handle.net/10962/d1006201
- Description: Powdered laundry detergents are consumed in high volumes worldwide. Post use, they are directed toward water resources via wastewater treatment works or, as is the situation in many rural areas of South Africa, they enter the environment directly as a result of laundry washing activity undertaken alongside surface waters. Within wastewater treatment works, the main ingredient in powdered laundry detergents, the narcotic toxin linear alkylbenzene sulfonate (LAS), is mostly removed, rendering the waste stream a negligible risk to the aquatic biota of receiving waters. In contrast, the biological and ecological impacts of direct LAS input to the aquatic environment, as a consequence of near-stream laundry washing, are yet to be fully realised. Consequently, this thesis posed two research questions: 1) 'What are the LAS concentrations in a small rural South African river'? and 2) 'Is the in-stream biological community negatively affected at these concentrations?' The chosen study area, the community of Balfour in the Eastern Cape Province, is like many rural areas of South Africa where inadequate provision of piped water to homesteads necessitates laundry washing alongside the nearby Balfour River. The first research question was addressed in two ways: by predicting LAS concentrations in Balfour River water by assessing detergent consumption and laundry washing behaviour of residents living alongside the river; and measuring actual in- stream LAS concentrations on different days of the week and during different seasons. Results indicated that LAS concentrations were highly variable temporally and spatially. High peak concentrations of LAS occurred infrequently and were limited to the immediate vicinity of near-stream laundry washing activity with the highest measured concentration being 342 μg.L ⁻¹ and the average 21 μg.L ⁻¹ over the sampling period. The second research question was addressed by integrating the chemical evidence, determined from the first research question, with the biological evidence of stress responses measured in macroinvertebrates collected downstream of near-stream laundry washing activity on the Balfour River. Predicted and measured LAS exposure concentrations from the Balfour River were compared to a water quality guideline for LAS (304 μg.L ⁻¹), specifically derived in this thesis. Biological stress responses were measured at different levels of organisation: two sub-cellular responses (lipid peroxidation and cholinesterase activity); three measures of macroinvertebrate tolerance to water quality impairment; five measures of community composition; three measures of community richness; and a surrogate measure of ecosystem function (functional feeding groups). Weight-of-evidence methodology was utilised to assess, integrate and interpret the chemical and biological evidence, and at its conclusion, determined no effect on the in-stream biological community of the Balfour River downstream of laundry washing activity.
- Full Text:
- Date Issued: 2012
- Authors: Gordon, Andrew K
- Date: 2012
- Subjects: Detergent pollution of rivers, lakes, etc. -- Research -- South Africa -- Eastern Cape Water -- Pollution -- Research -- South Africa -- Eastern Cape Stream health -- Research -- South Africa -- Eastern Cape Stream ecology -- Research -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6042 , http://hdl.handle.net/10962/d1006201
- Description: Powdered laundry detergents are consumed in high volumes worldwide. Post use, they are directed toward water resources via wastewater treatment works or, as is the situation in many rural areas of South Africa, they enter the environment directly as a result of laundry washing activity undertaken alongside surface waters. Within wastewater treatment works, the main ingredient in powdered laundry detergents, the narcotic toxin linear alkylbenzene sulfonate (LAS), is mostly removed, rendering the waste stream a negligible risk to the aquatic biota of receiving waters. In contrast, the biological and ecological impacts of direct LAS input to the aquatic environment, as a consequence of near-stream laundry washing, are yet to be fully realised. Consequently, this thesis posed two research questions: 1) 'What are the LAS concentrations in a small rural South African river'? and 2) 'Is the in-stream biological community negatively affected at these concentrations?' The chosen study area, the community of Balfour in the Eastern Cape Province, is like many rural areas of South Africa where inadequate provision of piped water to homesteads necessitates laundry washing alongside the nearby Balfour River. The first research question was addressed in two ways: by predicting LAS concentrations in Balfour River water by assessing detergent consumption and laundry washing behaviour of residents living alongside the river; and measuring actual in- stream LAS concentrations on different days of the week and during different seasons. Results indicated that LAS concentrations were highly variable temporally and spatially. High peak concentrations of LAS occurred infrequently and were limited to the immediate vicinity of near-stream laundry washing activity with the highest measured concentration being 342 μg.L ⁻¹ and the average 21 μg.L ⁻¹ over the sampling period. The second research question was addressed by integrating the chemical evidence, determined from the first research question, with the biological evidence of stress responses measured in macroinvertebrates collected downstream of near-stream laundry washing activity on the Balfour River. Predicted and measured LAS exposure concentrations from the Balfour River were compared to a water quality guideline for LAS (304 μg.L ⁻¹), specifically derived in this thesis. Biological stress responses were measured at different levels of organisation: two sub-cellular responses (lipid peroxidation and cholinesterase activity); three measures of macroinvertebrate tolerance to water quality impairment; five measures of community composition; three measures of community richness; and a surrogate measure of ecosystem function (functional feeding groups). Weight-of-evidence methodology was utilised to assess, integrate and interpret the chemical and biological evidence, and at its conclusion, determined no effect on the in-stream biological community of the Balfour River downstream of laundry washing activity.
- Full Text:
- Date Issued: 2012
The synthesis of fructooligosaccharides by the fructofuranosidase FopAp from Aspergillus niger
- Pindura, Mitchell Kingsley Chido
- Authors: Pindura, Mitchell Kingsley Chido
- Date: 2012
- Subjects: Aspergillus niger , Oligosaccharides
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4158 , http://hdl.handle.net/10962/d1018267
- Description: Fructooligosaccharides (FOS) are short-chain fructans with a terminal glucose moiety and are found naturally in many plant species. Besides their wide use as an alternative sweetener in food and beverage industry, FOS have shown great potential as neutraceuticals against diabetes, colon cancer and bowel disease. The uses of FOS are dependent on the degree of polymerisation that they exhibit. β-fructofuranosidase (FFase) and fructosyltransferase (FTase) enzymes are capable of synthesing FOS from carbohydrate raw materials such as chicory and sugar beet. The aim of this study was to investigate the synthesis of FOS of a pre-defined chain length, from sucrose, by the enzyme FopAp; a β-fructofuranosidase from Aspergillus niger. ATCC 20611. The crude enzyme FopAp was successfully purified, with a yield of 78.20 %, by ammonium sulphate precipitation and anion exchange chromatography. Two protein fractions, named FA and FB were shown to exhibit FFase activity. SDS PAGE analysis revealed two proteins with molecular weights of 112 kDa and 78 kDa, which were identified as a FFase and a hydrolase. Temperature and pH optima of 20 ºC and 9, respectively, were observed for the transfructosylation activity in the FFase. The purified FFase exhibited a half life of 1.5 hrs under optimal conditions. Substrate kinetic studies indicated a high hydrolytic activity at low sucrose concentrations, with Vmax and Km of 1.25 μmol/ml/min and 3.28 mM, respectively. Analysis by response surface methodology identified temperature and pH to be significant factors for the production of kestose and nystose, at a 95 % level of confidence. These findings were confirmed by neural networks constructed to identify optimal conditions of FOS synthesis.FOS synthesis was found to be optimal between pH 6 and pH 9 at 25 ºC. The factor of reaction time was found to be insignificant within the selected experimental constraints, for both FOS species. The findings of this investigation are very important as the foundations of a commercially viable synthetic process for the production of FOS.
- Full Text:
- Date Issued: 2012
- Authors: Pindura, Mitchell Kingsley Chido
- Date: 2012
- Subjects: Aspergillus niger , Oligosaccharides
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4158 , http://hdl.handle.net/10962/d1018267
- Description: Fructooligosaccharides (FOS) are short-chain fructans with a terminal glucose moiety and are found naturally in many plant species. Besides their wide use as an alternative sweetener in food and beverage industry, FOS have shown great potential as neutraceuticals against diabetes, colon cancer and bowel disease. The uses of FOS are dependent on the degree of polymerisation that they exhibit. β-fructofuranosidase (FFase) and fructosyltransferase (FTase) enzymes are capable of synthesing FOS from carbohydrate raw materials such as chicory and sugar beet. The aim of this study was to investigate the synthesis of FOS of a pre-defined chain length, from sucrose, by the enzyme FopAp; a β-fructofuranosidase from Aspergillus niger. ATCC 20611. The crude enzyme FopAp was successfully purified, with a yield of 78.20 %, by ammonium sulphate precipitation and anion exchange chromatography. Two protein fractions, named FA and FB were shown to exhibit FFase activity. SDS PAGE analysis revealed two proteins with molecular weights of 112 kDa and 78 kDa, which were identified as a FFase and a hydrolase. Temperature and pH optima of 20 ºC and 9, respectively, were observed for the transfructosylation activity in the FFase. The purified FFase exhibited a half life of 1.5 hrs under optimal conditions. Substrate kinetic studies indicated a high hydrolytic activity at low sucrose concentrations, with Vmax and Km of 1.25 μmol/ml/min and 3.28 mM, respectively. Analysis by response surface methodology identified temperature and pH to be significant factors for the production of kestose and nystose, at a 95 % level of confidence. These findings were confirmed by neural networks constructed to identify optimal conditions of FOS synthesis.FOS synthesis was found to be optimal between pH 6 and pH 9 at 25 ºC. The factor of reaction time was found to be insignificant within the selected experimental constraints, for both FOS species. The findings of this investigation are very important as the foundations of a commercially viable synthetic process for the production of FOS.
- Full Text:
- Date Issued: 2012
An analysis of ionospheric response to geomagnetic disturbances over South Africa and Antarctica
- Authors: Ngwira, Chigomezyo Mudala
- Date: 2012
- Subjects: Geomagnetism -- South Africa , Geomagnetism -- Antarctica , Ionospheric storms -- South Africa , Ionospheric storms -- Antarctica
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5534 , http://hdl.handle.net/10962/d1012957
- Description: The ionosphere is of practical importance for satellite-based communication and navigation systems due to its variable refractive nature which affects the propagation of trans-ionospheric radio signals. This thesis reports on the first attempt to investigate the mechanisms responsible for the generation of positive ionospheric storm effects over mid-latitude South Africa. The storm response on 15 May 2005 was associated with equatorward neutral winds and the passage of travelling ionospheric disturbances (TIDs). The two TIDs reported in this thesis propagated with average velocities of ∼438 m/s and ∼515 m/s respectively. The velocity of the first TID (i.e. 438 m/s) is consistent with the velocities calculated in other studies for the same storm event. In a second case study, the positive storm enhancement on both 25 and 27 July 2004 lasted for more than 7 hours, and were classified as long-duration positive ionospheric storm effects. It has been suggested that the long-duration positive storm effects could have been caused by large-scale thermospheric wind circulation and enhanced equatorward neutral winds. These processes were in turn most likely to have been driven by enhanced and sustained energy input in the high-latitude ionosphere due to Joule heating and particle energy injection. This is evident by the prolonged high-level geomagnetic activity on both 25 and 27 July. This thesis also reports on the phase scintillation investigation at the South African Antarctic polar research station during solar minimum conditions. The multi-instrument approach that was used shows that the scintillation events were associated with auroral electron precipitation and that substorms play an essential role in the production of scintillation in the high latitudes. Furthermore, the investigation reveals that external energy injection into the ionosphere is necessary for the development of high-latitude irregularities which produce scintillation. Finally, this thesis highlights inadequate data resources as one of the major shortcomings to be addressed in order to fully understand and distinguish between the various ionospheric storm drivers over the Southern Africa mid-latitude region. The results presented in this thesis on the ionospheric response during geomagnetic storms provide essential information to direct further investigation aimed at developing this emerging field of study in South Africa.
- Full Text:
- Date Issued: 2012
- Authors: Ngwira, Chigomezyo Mudala
- Date: 2012
- Subjects: Geomagnetism -- South Africa , Geomagnetism -- Antarctica , Ionospheric storms -- South Africa , Ionospheric storms -- Antarctica
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5534 , http://hdl.handle.net/10962/d1012957
- Description: The ionosphere is of practical importance for satellite-based communication and navigation systems due to its variable refractive nature which affects the propagation of trans-ionospheric radio signals. This thesis reports on the first attempt to investigate the mechanisms responsible for the generation of positive ionospheric storm effects over mid-latitude South Africa. The storm response on 15 May 2005 was associated with equatorward neutral winds and the passage of travelling ionospheric disturbances (TIDs). The two TIDs reported in this thesis propagated with average velocities of ∼438 m/s and ∼515 m/s respectively. The velocity of the first TID (i.e. 438 m/s) is consistent with the velocities calculated in other studies for the same storm event. In a second case study, the positive storm enhancement on both 25 and 27 July 2004 lasted for more than 7 hours, and were classified as long-duration positive ionospheric storm effects. It has been suggested that the long-duration positive storm effects could have been caused by large-scale thermospheric wind circulation and enhanced equatorward neutral winds. These processes were in turn most likely to have been driven by enhanced and sustained energy input in the high-latitude ionosphere due to Joule heating and particle energy injection. This is evident by the prolonged high-level geomagnetic activity on both 25 and 27 July. This thesis also reports on the phase scintillation investigation at the South African Antarctic polar research station during solar minimum conditions. The multi-instrument approach that was used shows that the scintillation events were associated with auroral electron precipitation and that substorms play an essential role in the production of scintillation in the high latitudes. Furthermore, the investigation reveals that external energy injection into the ionosphere is necessary for the development of high-latitude irregularities which produce scintillation. Finally, this thesis highlights inadequate data resources as one of the major shortcomings to be addressed in order to fully understand and distinguish between the various ionospheric storm drivers over the Southern Africa mid-latitude region. The results presented in this thesis on the ionospheric response during geomagnetic storms provide essential information to direct further investigation aimed at developing this emerging field of study in South Africa.
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- Date Issued: 2012