The solvent-free approach versus the use of ionic liquids in the synthesis of ferrocenes
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
Biosorption of precious metals from synthetic and refinery wastewaters by immobilized saccharomyces cerevisiae
- Authors: Mack, Cherie-Lynn
- Date: 2008
- Subjects: Metals -- Refining Metals -- Absorption and adsorption Saccharomyces cerevisiae Factory and trade waste Water reuse Platinum
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4071 , http://hdl.handle.net/10962/d1006977
- Description: The process of precious metal refining can be up to 99.99% efficient at best, and although it may seem small, the amount of valuable metal lost to waste streams is appreciable enough to warrant recovery. The method currently used to remove entrained metal ions from refinery wastewaters, chemical precipitation, is not an effective means for selective recovery of precious metals from a wastewater. Biosorption, the ability of certain types of biomass to bind and concentrate metals from even very dilute aqueous solutions, may be an effective point-source metal recovery strategy. The yeast, Saccharomyces cerevisiae, has been found capable of sorbing numerous precious and base metals, and is a cheap and abundant source of biomass. As such, it represents a possible precious metal sorbent for application to refining wastewaters. In this investigation, S. cerevisiae biomass was immobilized, using polyethyleneimine and glutaraldehyde, to produce a suitable sorbent, which was found to be capable of high platinum uptake (150 to 170 mg/g) at low pH (< 2). The sorption mechanism was elucidated and found to be a chemical reaction, which made effective desorption impossible. The sorption process was investigated in a packed bed column conformation, the results of which showed that the diameter and height of the column require further optimization in order to attain the metal uptake values achieved in the batch studies. When applied to a refinery wastewater, two key wastewater characteristics limited the success of the sorption process; the high inorganic ion content and the complex speciation of the platinum ions. The results proved the concept principle of platinum recovery by immobilized yeast biosorption and indicated that a more detailed understanding of the platinum speciation within the wastewater is required before the biosorption process can be applied. Overall, the sorption of platinum by the S. cerevisiae sorbent was demonstrated to be highly effective in principle, but the complexity of the wastewater requires that pretreatment steps be taken before the successful application of this process to an industrial wastewater.
- Full Text:
- Date Issued: 2008
- Authors: Mack, Cherie-Lynn
- Date: 2008
- Subjects: Metals -- Refining Metals -- Absorption and adsorption Saccharomyces cerevisiae Factory and trade waste Water reuse Platinum
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4071 , http://hdl.handle.net/10962/d1006977
- Description: The process of precious metal refining can be up to 99.99% efficient at best, and although it may seem small, the amount of valuable metal lost to waste streams is appreciable enough to warrant recovery. The method currently used to remove entrained metal ions from refinery wastewaters, chemical precipitation, is not an effective means for selective recovery of precious metals from a wastewater. Biosorption, the ability of certain types of biomass to bind and concentrate metals from even very dilute aqueous solutions, may be an effective point-source metal recovery strategy. The yeast, Saccharomyces cerevisiae, has been found capable of sorbing numerous precious and base metals, and is a cheap and abundant source of biomass. As such, it represents a possible precious metal sorbent for application to refining wastewaters. In this investigation, S. cerevisiae biomass was immobilized, using polyethyleneimine and glutaraldehyde, to produce a suitable sorbent, which was found to be capable of high platinum uptake (150 to 170 mg/g) at low pH (< 2). The sorption mechanism was elucidated and found to be a chemical reaction, which made effective desorption impossible. The sorption process was investigated in a packed bed column conformation, the results of which showed that the diameter and height of the column require further optimization in order to attain the metal uptake values achieved in the batch studies. When applied to a refinery wastewater, two key wastewater characteristics limited the success of the sorption process; the high inorganic ion content and the complex speciation of the platinum ions. The results proved the concept principle of platinum recovery by immobilized yeast biosorption and indicated that a more detailed understanding of the platinum speciation within the wastewater is required before the biosorption process can be applied. Overall, the sorption of platinum by the S. cerevisiae sorbent was demonstrated to be highly effective in principle, but the complexity of the wastewater requires that pretreatment steps be taken before the successful application of this process to an industrial wastewater.
- Full Text:
- Date Issued: 2008
A case for institutional investigations in economic research methods with reference to South Africa's agricultural sector
- Authors: Mbatha, Cyril
- Date: 2008
- Subjects: Economic development -- South Africa Economic development -- Research -- Methodology Agriculture -- South Africa Agriculture -- Economic aspects -- South Africa Agricultural productivity -- South Africa Agriculture -- Research -- South Africa South Africa -- Economic conditions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:972 , http://hdl.handle.net/10962/d1002706
- Description: Economic development remains elusive for many world economies, but especially those of African countries. The current global inequalities in terms of GNP per capita and human living standards between developed and developing nations have ensured that the challenges of food insecurities are only some of the many negative experiences of underdevelopment in the African continent. Hence, delivery pressures are increasing on policy makers and researchers to provide tangible and timely economic solutions to the resilient state of underdevelopment. In the policy fights against the challenges posed by a lack of development in South Africa, the agricultural sector has in the past and continues in the present to play a central role. Such is the case because the majority of citizens rely on agricultural production activities for their livelihoods. For instance, even though the sector only contributed four percent towards the national Gross Domestic Product in 2006, in the Eastern Cape Province, more than seventy percent of the total population resided in rural areas. Moreover, in 2004 more than sixty percent of the national formal and informal employment levels were found in the sector. These economic indicators do not only reinforce the assertions that high levels of geographical and sectoral inequalities exist in the country’s economy, but they also illustrate the importance of the agricultural sector in public policy attempts, which are aimed at achieving food security alongside long-term developmental objectives. Some economists, especially the proponents of institutionalism, have argued that most of the recommendations to public policy interventions from mainstream economic research endeavours are not adequately helpful. The recommendations generally lack well considered and socially effective ideas, mainly because there remains some level of ignorance about the impacts that institutions have on economic and social systems. Some argue that this ignorance is reflected in (flawed) hedonistic and rationalist assumptions made about economic actors and in the methodological thinking of many research designs and economic analyses. The misuse of formal tools and statistical methods, for example, are some of the important factors, which have led to failures of the discipline of economics to provide effective policy solutions to problems of underdevelopment and poverty, especially in poor country environments. The thesis, having taken account of the majority of criticisms levelled against the classical and new-classical economic schools of thought, argues that the discipline as a whole lacks a paradigmatic integration of institutional and new-classical economic perspectives to offer appropriate guidelines for a methodology aimed at achieving socially responsive research outputs. The lack of this integration has resulted in a skewed selection of methods by economists, which are employed in research without a supportive and in-depth understanding of institutional and social factors. To support the thesis, a more effective and integrated framework for economic research is developed and presented with case study illustrations in a cumulative manner. The 20th century history of agricultural policies in South Africa, the agricultural and institutional case studies from the Eastern Cape Province alongside reviews of other agricultural studies are all used in presenting a case for rigorous institutional investigations in general economic research. These are also used in developing the proposed integrated framework, which aims to give guidance in developing research methods, which are more socially responsive. Having shown the usefulness of the proposed research framework, the thesis recommends that public policy interventions (at national and local levels) should aim to eliminate all types of institutions which have high associated transactional costs. The interventions should also encourage the emergence and growth of the types of institutions, which present the lowest costs to initiatives of economic development. In the primary case studies from the Eastern Cape Province, the insecurity of land tenure and the various local initiatives of business ventures are highlighted as two examples of the types of institutions, which respectively present high and low transactional costs to local initiatives of agricultural and economic development.
- Full Text:
- Date Issued: 2008
- Authors: Mbatha, Cyril
- Date: 2008
- Subjects: Economic development -- South Africa Economic development -- Research -- Methodology Agriculture -- South Africa Agriculture -- Economic aspects -- South Africa Agricultural productivity -- South Africa Agriculture -- Research -- South Africa South Africa -- Economic conditions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:972 , http://hdl.handle.net/10962/d1002706
- Description: Economic development remains elusive for many world economies, but especially those of African countries. The current global inequalities in terms of GNP per capita and human living standards between developed and developing nations have ensured that the challenges of food insecurities are only some of the many negative experiences of underdevelopment in the African continent. Hence, delivery pressures are increasing on policy makers and researchers to provide tangible and timely economic solutions to the resilient state of underdevelopment. In the policy fights against the challenges posed by a lack of development in South Africa, the agricultural sector has in the past and continues in the present to play a central role. Such is the case because the majority of citizens rely on agricultural production activities for their livelihoods. For instance, even though the sector only contributed four percent towards the national Gross Domestic Product in 2006, in the Eastern Cape Province, more than seventy percent of the total population resided in rural areas. Moreover, in 2004 more than sixty percent of the national formal and informal employment levels were found in the sector. These economic indicators do not only reinforce the assertions that high levels of geographical and sectoral inequalities exist in the country’s economy, but they also illustrate the importance of the agricultural sector in public policy attempts, which are aimed at achieving food security alongside long-term developmental objectives. Some economists, especially the proponents of institutionalism, have argued that most of the recommendations to public policy interventions from mainstream economic research endeavours are not adequately helpful. The recommendations generally lack well considered and socially effective ideas, mainly because there remains some level of ignorance about the impacts that institutions have on economic and social systems. Some argue that this ignorance is reflected in (flawed) hedonistic and rationalist assumptions made about economic actors and in the methodological thinking of many research designs and economic analyses. The misuse of formal tools and statistical methods, for example, are some of the important factors, which have led to failures of the discipline of economics to provide effective policy solutions to problems of underdevelopment and poverty, especially in poor country environments. The thesis, having taken account of the majority of criticisms levelled against the classical and new-classical economic schools of thought, argues that the discipline as a whole lacks a paradigmatic integration of institutional and new-classical economic perspectives to offer appropriate guidelines for a methodology aimed at achieving socially responsive research outputs. The lack of this integration has resulted in a skewed selection of methods by economists, which are employed in research without a supportive and in-depth understanding of institutional and social factors. To support the thesis, a more effective and integrated framework for economic research is developed and presented with case study illustrations in a cumulative manner. The 20th century history of agricultural policies in South Africa, the agricultural and institutional case studies from the Eastern Cape Province alongside reviews of other agricultural studies are all used in presenting a case for rigorous institutional investigations in general economic research. These are also used in developing the proposed integrated framework, which aims to give guidance in developing research methods, which are more socially responsive. Having shown the usefulness of the proposed research framework, the thesis recommends that public policy interventions (at national and local levels) should aim to eliminate all types of institutions which have high associated transactional costs. The interventions should also encourage the emergence and growth of the types of institutions, which present the lowest costs to initiatives of economic development. In the primary case studies from the Eastern Cape Province, the insecurity of land tenure and the various local initiatives of business ventures are highlighted as two examples of the types of institutions, which respectively present high and low transactional costs to local initiatives of agricultural and economic development.
- Full Text:
- Date Issued: 2008
Synthetic, spectrometric and computer modelling studies of novel ATP analogues
- Gxoyiya, Babalwa Siliziwe Blossom
- Authors: Gxoyiya, Babalwa Siliziwe Blossom
- Date: 2008
- Subjects: Spectrum analysis Tuberculosis -- Treatment Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Adenosine triphosphate -- Computer simulation Adenosine triphosphate -- Spectrometric imaging Glutamine synthetase Tuberculosis -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4386 , http://hdl.handle.net/10962/d1005051
- Description: This study has been concerned with the design and synthesis of A TP analogues with the potential to act as inhibitors of glutamine synthetase - a novel target for therapeutic intervention in the treatment of tuberculosis. Using a structural -analogy approach, various 3-indolylalkanoic acid, benzimidazole and pyrazolo[3,4-dJpyrimidine derivatives have been prepared and characterized. Alkylation of the heterocyclic bases using 4-(bromomethyl)-2,2-dimethyl-1 ,3-d ioxolane, 2-(bromomethoxy)ethyl acetate and 2-(chloroethoxy)ethanol in the presence of either NaH or BulOK afforded the corresponding N-alkylated derivatives of benzimidazole and 4-aminopyrazolo[3,4-dJpyrimidine (4-APP). Similar reactions with 3-indo lylalkanoic esters resulted in O-alkyl cleavage with the formation of new esters. Alkylation of benzimidazole with allyl bromide, 4-bromobutene and 2-methylbut-2-ene has also been shown to afford the corresponding l-alkenylbenzimidazoles in moderate to excellent yield (43-96%). Subsequent oxidation of these products using CTAP, gave the dihydroxy derivatives in poor to good yields (26-77%). Phosphorylation of various hydroxy derivatives of benzimidazole and 4-APP has been achieved using diethyl chlorophosphate to afford the corresponding monophosphate and 1,2-diphosphate esters. Glycosylation of each of the heterocyclic bases has been successfully achieved using 1,2,3,4,6-penta-O-acetyl-D-glucopyranose and SnCl4 in acetonitri le, while methanolysis of the resulting tetraacetates, using methanolic NaOMe, afforded the hydroxy derivatives in good yield (50-70%). Various 1- and 2-dimensional NMR spectroscopic methods (e.g., IH, 13C, lip, COSY, HSQC and HMBC) have been used to confirm the structures of the synthesized A IP analogues. The application of NMR prediction programmes has been explored, permitting assessment of their agreement with the experimental data and confirmation of assigned structures. High-resolution electron impact (EI) mass spectrometric data have been used to explore the mass fragmentation pathways exhibited by selected derivatives, and certain common fragmentations have been identified. Molecular modelling of selected products as potential glutamine synthetase ligands has been performed on the Accelrys Cerius2 platform, and interactive receptor-ligand docking studies have been conducted using the Ligand-Fit module. These studies have revealed possible hydrogen-boding interactions between the selected analogues and various amino acid residues in the glutamine synthetase active site.
- Full Text:
- Date Issued: 2008
- Authors: Gxoyiya, Babalwa Siliziwe Blossom
- Date: 2008
- Subjects: Spectrum analysis Tuberculosis -- Treatment Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Adenosine triphosphate -- Computer simulation Adenosine triphosphate -- Spectrometric imaging Glutamine synthetase Tuberculosis -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4386 , http://hdl.handle.net/10962/d1005051
- Description: This study has been concerned with the design and synthesis of A TP analogues with the potential to act as inhibitors of glutamine synthetase - a novel target for therapeutic intervention in the treatment of tuberculosis. Using a structural -analogy approach, various 3-indolylalkanoic acid, benzimidazole and pyrazolo[3,4-dJpyrimidine derivatives have been prepared and characterized. Alkylation of the heterocyclic bases using 4-(bromomethyl)-2,2-dimethyl-1 ,3-d ioxolane, 2-(bromomethoxy)ethyl acetate and 2-(chloroethoxy)ethanol in the presence of either NaH or BulOK afforded the corresponding N-alkylated derivatives of benzimidazole and 4-aminopyrazolo[3,4-dJpyrimidine (4-APP). Similar reactions with 3-indo lylalkanoic esters resulted in O-alkyl cleavage with the formation of new esters. Alkylation of benzimidazole with allyl bromide, 4-bromobutene and 2-methylbut-2-ene has also been shown to afford the corresponding l-alkenylbenzimidazoles in moderate to excellent yield (43-96%). Subsequent oxidation of these products using CTAP, gave the dihydroxy derivatives in poor to good yields (26-77%). Phosphorylation of various hydroxy derivatives of benzimidazole and 4-APP has been achieved using diethyl chlorophosphate to afford the corresponding monophosphate and 1,2-diphosphate esters. Glycosylation of each of the heterocyclic bases has been successfully achieved using 1,2,3,4,6-penta-O-acetyl-D-glucopyranose and SnCl4 in acetonitri le, while methanolysis of the resulting tetraacetates, using methanolic NaOMe, afforded the hydroxy derivatives in good yield (50-70%). Various 1- and 2-dimensional NMR spectroscopic methods (e.g., IH, 13C, lip, COSY, HSQC and HMBC) have been used to confirm the structures of the synthesized A IP analogues. The application of NMR prediction programmes has been explored, permitting assessment of their agreement with the experimental data and confirmation of assigned structures. High-resolution electron impact (EI) mass spectrometric data have been used to explore the mass fragmentation pathways exhibited by selected derivatives, and certain common fragmentations have been identified. Molecular modelling of selected products as potential glutamine synthetase ligands has been performed on the Accelrys Cerius2 platform, and interactive receptor-ligand docking studies have been conducted using the Ligand-Fit module. These studies have revealed possible hydrogen-boding interactions between the selected analogues and various amino acid residues in the glutamine synthetase active site.
- Full Text:
- Date Issued: 2008
ATP mimics as glutamine synthetase inhibitors : an exploratory synthetic study
- Authors: Salisu, Sheriff Tomilola
- Date: 2008
- Subjects: Glutamine synthetase Tuberculosis -- Treatment Tuberculosis -- Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Drug development
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4408 , http://hdl.handle.net/10962/d1006715
- Description: Using a mechanism-based approach to drug discovery, efforts have been directed towards developing novel ATP mimics that can act as GS inhibitors. The purine-based systems, adenosine, adenine and allopurinol, were identified as possible scaffolds for potential ATP mimics, while various meta-disubstituted benzenoid compounds, 3-aminobenzonitrile, 3-aminophenol, resorcinol, 3-aminobenzyl alcohol, 3-hydroxybenzoic acid and 3-aminobenzoic acid have been explored as adenine analogues. These compounds were treated with different alkylating and acylating agents. Allylation of all the substrates was achieved using allyl bromide and N-9 alkylation of protected allopurinol was effected using a number of specially prepared Baylis-Hillman adducts. Acylation of the benzenoid precursors with chloroacetyl chloride, acetoxyacetyl chloride, acryloyl chloride and specially prepared 2,3,4,5,6-pentaacetylgluconoyl chloride afforded the corresponding mono- and /or diacylated products in varying yields (4-96%). Elaboration of the alkylated and acylated products has involved the reaction of hydroxy systems with diethyl chloro phosphate and chloro derivatives with triethyl phosphite in Arbuzov-type reactions to afford phosphorylated products. In all cases, products were fully characterized using 1- and 2-D NMR analysis and, where appropriate, high-resolution mass spectrometry. The application of Modgraph and ChemWindow NMR prediction programmes has been explored and the resulting data have been compared with experimental chemical shift assignments to confirm chemical structures and, in some cases, to establish the position of allylation or acylation. Experimental assignments were found to be generally comparable with the Modgraph data, but not always with the ChemWindow values. The docking of selected products in the 'active-site' of GS and their structural homology with ATP, both in their free and bound conformations have been studied using the ACCELERYS Cerius² platform. All the selected ATP mimics exhibit some form of interaction with the 'active-site' residues, and a number of them appear to be promising GS ligands.
- Full Text:
- Date Issued: 2008
- Authors: Salisu, Sheriff Tomilola
- Date: 2008
- Subjects: Glutamine synthetase Tuberculosis -- Treatment Tuberculosis -- Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Drug development
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4408 , http://hdl.handle.net/10962/d1006715
- Description: Using a mechanism-based approach to drug discovery, efforts have been directed towards developing novel ATP mimics that can act as GS inhibitors. The purine-based systems, adenosine, adenine and allopurinol, were identified as possible scaffolds for potential ATP mimics, while various meta-disubstituted benzenoid compounds, 3-aminobenzonitrile, 3-aminophenol, resorcinol, 3-aminobenzyl alcohol, 3-hydroxybenzoic acid and 3-aminobenzoic acid have been explored as adenine analogues. These compounds were treated with different alkylating and acylating agents. Allylation of all the substrates was achieved using allyl bromide and N-9 alkylation of protected allopurinol was effected using a number of specially prepared Baylis-Hillman adducts. Acylation of the benzenoid precursors with chloroacetyl chloride, acetoxyacetyl chloride, acryloyl chloride and specially prepared 2,3,4,5,6-pentaacetylgluconoyl chloride afforded the corresponding mono- and /or diacylated products in varying yields (4-96%). Elaboration of the alkylated and acylated products has involved the reaction of hydroxy systems with diethyl chloro phosphate and chloro derivatives with triethyl phosphite in Arbuzov-type reactions to afford phosphorylated products. In all cases, products were fully characterized using 1- and 2-D NMR analysis and, where appropriate, high-resolution mass spectrometry. The application of Modgraph and ChemWindow NMR prediction programmes has been explored and the resulting data have been compared with experimental chemical shift assignments to confirm chemical structures and, in some cases, to establish the position of allylation or acylation. Experimental assignments were found to be generally comparable with the Modgraph data, but not always with the ChemWindow values. The docking of selected products in the 'active-site' of GS and their structural homology with ATP, both in their free and bound conformations have been studied using the ACCELERYS Cerius² platform. All the selected ATP mimics exhibit some form of interaction with the 'active-site' residues, and a number of them appear to be promising GS ligands.
- Full Text:
- Date Issued: 2008
The ecology and conservation of Mackinder's eagle owls (Bubo capensis mackinderi) in central Kenya in relation to agricultural land-use and cultural attitudes
- Authors: Ogada, Darcy L
- Date: 2008
- Subjects: Cape eagle owl -- Kenya Cape eagle owl -- Habitat -- Kenya Cape eagle owl -- Breeding -- Kenya Cape eagle owl -- Nutrition -- Kenya Bubo -- Kenya Wildlife conservation -- Kenya Biodiversity conservation -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5668 , http://hdl.handle.net/10962/d1005353
- Description: The loss of habitat to agriculture is a worldwide problem for biodiversity conservation. One species that has seemingly been able to adapt to the conversion of forests to farmlands is Mackinder’s eagle owl (Bubo capensis mackinderi), which inhabits highland areas, but little is known of its ecology, especially outside of protected areas. This study examined the impact of agricultural practices and farmer’s attitudes on the foraging and population ecology of the Mackinder’s eagle owl in central Kenya. Owl territories were monitored monthly from June 2004- October 2006 for signs of occupancy, breeding activity, mortality and to collect data on food resources. Nest site characteristics were measured for all known nests. Because previous studies showed an affinity for rodents, small mammals were trapped monthly using mark-recapture methodology. In each territory, the type and amount of farm crops were measured each month and farmers were interviewed about their knowledge and beliefs about owls. Mackinder’s eagle owls in central Kenya lived at extremely high density 0.87 owl pairs/km². This density was high compared to other populations of Mackinder’s eagle owl and to Eurasian eagle owl (Bubo bubo) populations in Europe. Breeding success was 48% over three years and this compared well with other species of eagle owl inhabiting human-disturbed areas. All nests and roosts were located in river valleys, and all successful nest sites were located on cliffs or other inaccessible rocky terrain. Nest sites were located adjacent to farms, which provided for both open hunting and an abundance of prey. Breeding activity was concentrated after the rainy seasons and this was likely linked to prey availability after the rains. Agricultural activities generally had a positive effect on rodent populations. Small mammal trapping results revealed that rodents were over 14 times more abundant in farms than in adjacent grassland habitat. This population of Mackinder’s eagle owl had a very catholic diet and consumed mostly mammalian prey species including hares, giant rats, root rats, grooved-tooth rats and small rodents. Small rodents accounted for almost half of the owls’ diet and when their numbers increased, owls responded by consuming more of them, indicating the importance of farming activities to this population of owls. Other populations of eagle owl inhabiting human-disturbed areas had diet widths positively related to levels of habitat disturbance. This result supported optimal foraging theory that more productive environments have predators with more specialized diets, while patchy environments have generalist predators. The ecology of this population of Mackinder’s eagle owls was heavily influenced by human agricultural activities, which generally had a positive effect on their population. Farming activities changed rapidly both within and between seasons as plots were small and neighbouring farmers planted various crops at different times of the year and this was enhanced by irrigation in some areas. Year-round availability of forage within farms had a positive effect on owl prey species, some of which increased relative to the type and amount of crops found in farms. However, 57% of owl injuries and mortalities that occurred were related either directly or indirectly to human activities. Cultural prejudices against owls remain the biggest threat to this population’s long-term persistence. Farmer education was shown to play a significant role in overcoming negative beliefs about owls. Because Mackinder’s eagle owls are highly adaptable to anthropomorphic landscape changes, largely due to their adaptability as food generalists, they are one of the few top predators remaining in this highly disturbed agricultural system. However, populations within agricultural areas remain especially vulnerable to negative human attitudes towards owls due to their close association with human activities.
- Full Text:
- Date Issued: 2008
- Authors: Ogada, Darcy L
- Date: 2008
- Subjects: Cape eagle owl -- Kenya Cape eagle owl -- Habitat -- Kenya Cape eagle owl -- Breeding -- Kenya Cape eagle owl -- Nutrition -- Kenya Bubo -- Kenya Wildlife conservation -- Kenya Biodiversity conservation -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5668 , http://hdl.handle.net/10962/d1005353
- Description: The loss of habitat to agriculture is a worldwide problem for biodiversity conservation. One species that has seemingly been able to adapt to the conversion of forests to farmlands is Mackinder’s eagle owl (Bubo capensis mackinderi), which inhabits highland areas, but little is known of its ecology, especially outside of protected areas. This study examined the impact of agricultural practices and farmer’s attitudes on the foraging and population ecology of the Mackinder’s eagle owl in central Kenya. Owl territories were monitored monthly from June 2004- October 2006 for signs of occupancy, breeding activity, mortality and to collect data on food resources. Nest site characteristics were measured for all known nests. Because previous studies showed an affinity for rodents, small mammals were trapped monthly using mark-recapture methodology. In each territory, the type and amount of farm crops were measured each month and farmers were interviewed about their knowledge and beliefs about owls. Mackinder’s eagle owls in central Kenya lived at extremely high density 0.87 owl pairs/km². This density was high compared to other populations of Mackinder’s eagle owl and to Eurasian eagle owl (Bubo bubo) populations in Europe. Breeding success was 48% over three years and this compared well with other species of eagle owl inhabiting human-disturbed areas. All nests and roosts were located in river valleys, and all successful nest sites were located on cliffs or other inaccessible rocky terrain. Nest sites were located adjacent to farms, which provided for both open hunting and an abundance of prey. Breeding activity was concentrated after the rainy seasons and this was likely linked to prey availability after the rains. Agricultural activities generally had a positive effect on rodent populations. Small mammal trapping results revealed that rodents were over 14 times more abundant in farms than in adjacent grassland habitat. This population of Mackinder’s eagle owl had a very catholic diet and consumed mostly mammalian prey species including hares, giant rats, root rats, grooved-tooth rats and small rodents. Small rodents accounted for almost half of the owls’ diet and when their numbers increased, owls responded by consuming more of them, indicating the importance of farming activities to this population of owls. Other populations of eagle owl inhabiting human-disturbed areas had diet widths positively related to levels of habitat disturbance. This result supported optimal foraging theory that more productive environments have predators with more specialized diets, while patchy environments have generalist predators. The ecology of this population of Mackinder’s eagle owls was heavily influenced by human agricultural activities, which generally had a positive effect on their population. Farming activities changed rapidly both within and between seasons as plots were small and neighbouring farmers planted various crops at different times of the year and this was enhanced by irrigation in some areas. Year-round availability of forage within farms had a positive effect on owl prey species, some of which increased relative to the type and amount of crops found in farms. However, 57% of owl injuries and mortalities that occurred were related either directly or indirectly to human activities. Cultural prejudices against owls remain the biggest threat to this population’s long-term persistence. Farmer education was shown to play a significant role in overcoming negative beliefs about owls. Because Mackinder’s eagle owls are highly adaptable to anthropomorphic landscape changes, largely due to their adaptability as food generalists, they are one of the few top predators remaining in this highly disturbed agricultural system. However, populations within agricultural areas remain especially vulnerable to negative human attitudes towards owls due to their close association with human activities.
- Full Text:
- Date Issued: 2008
An adaptive approach for optimized opportunistic routing over Delay Tolerant Mobile Ad hoc Networks
- Authors: Zhao, Xiaogeng
- Date: 2008
- Subjects: Ad hoc networks (Computer networks) Computer network architectures Computer networks Routing protocols (Computer network protocols)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4588 , http://hdl.handle.net/10962/d1004822
- Description: This thesis presents a framework for investigating opportunistic routing in Delay Tolerant Mobile Ad hoc Networks (DTMANETs), and introduces the concept of an Opportunistic Confidence Index (OCI). The OCI enables multiple opportunistic routing protocols to be applied as an adaptive group to improve DTMANET routing reliability, performance, and efficiency. The DTMANET is a recently acknowledged networkarchitecture, which is designed to address the challenging and marginal environments created by adaptive, mobile, and unreliable network node presence. Because of its ad hoc and autonomic nature, routing in a DTMANET is a very challenging problem. The design of routing protocols in such environments, which ensure a high percentage delivery rate (reliability), achieve a reasonable delivery time (performance), and at the same time maintain an acceptable communication overhead (efficiency), is of fundamental consequence to the usefulness of DTMANETs. In recent years, a number of investigations into DTMANET routing have been conducted, resulting in the emergence of a class of routing known as opportunistic routing protocols. Current research into opportunistic routing has exposed opportunities for positive impacts on DTMANET routing. To date, most investigations have concentrated upon one or other of the quality metrics of reliability, performance, or efficiency, while some approaches have pursued a balance of these metrics through assumptions of a high level of global knowledge and/or uniform mobile device behaviours. No prior research that we are aware of has studied the connection between multiple opportunistic elements and their influences upon one another, and none has demonstrated the possibility of modelling and using multiple different opportunistic elements as an adaptive group to aid the routing process in a DTMANET. This thesis investigates OCI opportunities and their viability through the design of an extensible simulation environment, which makes use of methods and techniques such as abstract modelling, opportunistic element simplification and isolation, random attribute generation and assignment, localized knowledge sharing, automated scenario generation, intelligent weight assignment and/or opportunistic element permutation. These methods and techniques are incorporated at both data acquisition and analysis phases. Our results show a significant improvement in all three metric categories. In one of the most applicable scenarios tested, OCI yielded a 31.05% message delivery increase (reliability improvement), 22.18% message delivery time reduction (performance improvement), and 73.64% routing depth decrement (efficiency improvement). We are able to conclude that the OCI approach is feasible across a range of scenarios, and that the use of multiple opportunistic elements to aid decision-making processes in DTMANET environments has value.
- Full Text:
- Date Issued: 2008
- Authors: Zhao, Xiaogeng
- Date: 2008
- Subjects: Ad hoc networks (Computer networks) Computer network architectures Computer networks Routing protocols (Computer network protocols)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4588 , http://hdl.handle.net/10962/d1004822
- Description: This thesis presents a framework for investigating opportunistic routing in Delay Tolerant Mobile Ad hoc Networks (DTMANETs), and introduces the concept of an Opportunistic Confidence Index (OCI). The OCI enables multiple opportunistic routing protocols to be applied as an adaptive group to improve DTMANET routing reliability, performance, and efficiency. The DTMANET is a recently acknowledged networkarchitecture, which is designed to address the challenging and marginal environments created by adaptive, mobile, and unreliable network node presence. Because of its ad hoc and autonomic nature, routing in a DTMANET is a very challenging problem. The design of routing protocols in such environments, which ensure a high percentage delivery rate (reliability), achieve a reasonable delivery time (performance), and at the same time maintain an acceptable communication overhead (efficiency), is of fundamental consequence to the usefulness of DTMANETs. In recent years, a number of investigations into DTMANET routing have been conducted, resulting in the emergence of a class of routing known as opportunistic routing protocols. Current research into opportunistic routing has exposed opportunities for positive impacts on DTMANET routing. To date, most investigations have concentrated upon one or other of the quality metrics of reliability, performance, or efficiency, while some approaches have pursued a balance of these metrics through assumptions of a high level of global knowledge and/or uniform mobile device behaviours. No prior research that we are aware of has studied the connection between multiple opportunistic elements and their influences upon one another, and none has demonstrated the possibility of modelling and using multiple different opportunistic elements as an adaptive group to aid the routing process in a DTMANET. This thesis investigates OCI opportunities and their viability through the design of an extensible simulation environment, which makes use of methods and techniques such as abstract modelling, opportunistic element simplification and isolation, random attribute generation and assignment, localized knowledge sharing, automated scenario generation, intelligent weight assignment and/or opportunistic element permutation. These methods and techniques are incorporated at both data acquisition and analysis phases. Our results show a significant improvement in all three metric categories. In one of the most applicable scenarios tested, OCI yielded a 31.05% message delivery increase (reliability improvement), 22.18% message delivery time reduction (performance improvement), and 73.64% routing depth decrement (efficiency improvement). We are able to conclude that the OCI approach is feasible across a range of scenarios, and that the use of multiple opportunistic elements to aid decision-making processes in DTMANET environments has value.
- Full Text:
- Date Issued: 2008
"The struggle of memory against forgetting" contemporary fictions and rewriting of histories
- Authors: Patchay, Sheenadevi
- Date: 2008
- Subjects: Morrison, Toni. Beloved Dangarembga, Tsitsi. Nevous conditions Høeg, Peter, 1957- Frøken Smillas fornemmelse for sne Nahai, Gina Barkhordar. Moonlight on the avenue of faith Roy, Arundhati. God of small things Fiction -- History and criticism History in literature Contemporary, The, in literature Postcolonialism in literature Psychic trauma in literature
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2210 , http://hdl.handle.net/10962/d1002253
- Description: This thesis argues that a prominent concern among contemporary writers of fiction is the recuperation of lost or occluded histories. Increasingly, contemporary writers, especially postcolonial writers, are using the medium of fiction to explore those areas of political and cultural history that have been written over or unwritten by the dominant narrative of “official” History. The act of excavating these past histories is simultaneously both traumatic and liberating – which is not to suggest that liberation itself is without pain and trauma. The retelling of traumatic pasts can lead, as is portrayed in The God of Small Things (1997), to further trauma and pain. Postcolonial writers (and much of the world today can be construed as postcolonial in one way or another) are seeking to bring to the fore stories of the past which break down the rigid binaries upon which colonialism built its various empires, literal and ideological. Such writing has in a sense been enabled by the collapse, in postcolonial and postmodernist discourse, of the Grand Narrative of History, and its fragmentation into a plurality of competing discourses and histories. The associated collapse of the boundary between history and fiction is recognized in the useful generic marker “historiographic metafiction,” coined by Linda Hutcheon. The texts examined in this study are all variants of this emerging contemporary genre. What they also have in common is a concern with the consequences of exile or diaspora. This study thus explores some of the representations of how the exilic experience impinges on the development of identity in the postcolonial world. The identities of “displaced” people must undergo constant change in order to adjust to the new spaces into which they move, both literal and metaphorical, and yet critical to this adjustment is the cultural continuity provided by psychologically satisfying stories about the past. The study shows that what the chosen texts share at bottom is their mutual need to retell the lost pasts of their characters, the trauma that such retelling evokes and the new histories to which they give birth. These texts generate new histories which subvert, enrich, and pre-empt formal closure for the narratives of history which determine the identities of nations.
- Full Text:
- Date Issued: 2008
- Authors: Patchay, Sheenadevi
- Date: 2008
- Subjects: Morrison, Toni. Beloved Dangarembga, Tsitsi. Nevous conditions Høeg, Peter, 1957- Frøken Smillas fornemmelse for sne Nahai, Gina Barkhordar. Moonlight on the avenue of faith Roy, Arundhati. God of small things Fiction -- History and criticism History in literature Contemporary, The, in literature Postcolonialism in literature Psychic trauma in literature
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2210 , http://hdl.handle.net/10962/d1002253
- Description: This thesis argues that a prominent concern among contemporary writers of fiction is the recuperation of lost or occluded histories. Increasingly, contemporary writers, especially postcolonial writers, are using the medium of fiction to explore those areas of political and cultural history that have been written over or unwritten by the dominant narrative of “official” History. The act of excavating these past histories is simultaneously both traumatic and liberating – which is not to suggest that liberation itself is without pain and trauma. The retelling of traumatic pasts can lead, as is portrayed in The God of Small Things (1997), to further trauma and pain. Postcolonial writers (and much of the world today can be construed as postcolonial in one way or another) are seeking to bring to the fore stories of the past which break down the rigid binaries upon which colonialism built its various empires, literal and ideological. Such writing has in a sense been enabled by the collapse, in postcolonial and postmodernist discourse, of the Grand Narrative of History, and its fragmentation into a plurality of competing discourses and histories. The associated collapse of the boundary between history and fiction is recognized in the useful generic marker “historiographic metafiction,” coined by Linda Hutcheon. The texts examined in this study are all variants of this emerging contemporary genre. What they also have in common is a concern with the consequences of exile or diaspora. This study thus explores some of the representations of how the exilic experience impinges on the development of identity in the postcolonial world. The identities of “displaced” people must undergo constant change in order to adjust to the new spaces into which they move, both literal and metaphorical, and yet critical to this adjustment is the cultural continuity provided by psychologically satisfying stories about the past. The study shows that what the chosen texts share at bottom is their mutual need to retell the lost pasts of their characters, the trauma that such retelling evokes and the new histories to which they give birth. These texts generate new histories which subvert, enrich, and pre-empt formal closure for the narratives of history which determine the identities of nations.
- Full Text:
- Date Issued: 2008
Reconstructing ionospheric TEC over South Africa using signals from a regional GPS network
- Authors: Opperman, B D L
- Date: 2008
- Subjects: Global Positioning System Global Positioning System -- Data processing Electrons -- South Africa Ionosphere -- South Africa Ionospheric radio wave propagation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5487 , http://hdl.handle.net/10962/d1005273
- Description: Radio signals transmitted by GPS satellites orbiting the Earth are modulated as they propagate through the electrically charged plasmasphere and ionosphere in the near-Earth space environment. Through a linear combination of GPS range and phase measurements observed on two carrier frequencies by terrestrial-based GPS receivers, the ionospheric total electron content (TEC) along oblique GPS signal paths may be quantified. Simultaneous observations of signals transmitted by multiple GPS satellites and observed from a network of South African dual frequency GPS receivers, constitute a spatially dense ionospheric measurement source over the region. A new methodology, based on an adjusted spherical harmonic (ASHA) expansion, was developed to estimate diurnal vertical TEC over the region using GPS observations over the region. The performance of the ASHA methodology to estimate diurnal TEC and satellite and receiver differential clock biases (DCBs) for a single GPS receiver was first tested with simulation data and subsequently applied to observed GPS data. The resulting diurnal TEC profiles estimated from GPS observations compared favourably to measurements from three South African ionosondes and two other GPS-based methodologies for 2006 solstice and equinox dates. The ASHA methodology was applied to calculating diurnal two-dimensional TEC maps from multiple receivers in the South African GPS network. The space physics application of the newly developed methodology was demonstrated by investigating the ionosphere’s behaviour during a severe geomagnetic storm and investigating the long-term ionospheric stability in support of the proposed Square Kilometre Array (SKA) radio astronomy project. The feasibility of employing the newly developed technique in an operational near real-time system for estimating and dissimenating TEC values over Southern Africa using observations from a regional GPS receiver network, was investigated.
- Full Text:
- Date Issued: 2008
- Authors: Opperman, B D L
- Date: 2008
- Subjects: Global Positioning System Global Positioning System -- Data processing Electrons -- South Africa Ionosphere -- South Africa Ionospheric radio wave propagation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5487 , http://hdl.handle.net/10962/d1005273
- Description: Radio signals transmitted by GPS satellites orbiting the Earth are modulated as they propagate through the electrically charged plasmasphere and ionosphere in the near-Earth space environment. Through a linear combination of GPS range and phase measurements observed on two carrier frequencies by terrestrial-based GPS receivers, the ionospheric total electron content (TEC) along oblique GPS signal paths may be quantified. Simultaneous observations of signals transmitted by multiple GPS satellites and observed from a network of South African dual frequency GPS receivers, constitute a spatially dense ionospheric measurement source over the region. A new methodology, based on an adjusted spherical harmonic (ASHA) expansion, was developed to estimate diurnal vertical TEC over the region using GPS observations over the region. The performance of the ASHA methodology to estimate diurnal TEC and satellite and receiver differential clock biases (DCBs) for a single GPS receiver was first tested with simulation data and subsequently applied to observed GPS data. The resulting diurnal TEC profiles estimated from GPS observations compared favourably to measurements from three South African ionosondes and two other GPS-based methodologies for 2006 solstice and equinox dates. The ASHA methodology was applied to calculating diurnal two-dimensional TEC maps from multiple receivers in the South African GPS network. The space physics application of the newly developed methodology was demonstrated by investigating the ionosphere’s behaviour during a severe geomagnetic storm and investigating the long-term ionospheric stability in support of the proposed Square Kilometre Array (SKA) radio astronomy project. The feasibility of employing the newly developed technique in an operational near real-time system for estimating and dissimenating TEC values over Southern Africa using observations from a regional GPS receiver network, was investigated.
- Full Text:
- Date Issued: 2008
Harvesting strategies of fuelwood and kraalwood users at Machibi : identifying the driving factors and feedbacks
- Authors: Scheepers, Kelly
- Date: 2008
- Subjects: Fuelwood -- South Africa -- Eastern Cape Forest ecology -- South Africa -- Eastern Cape Natural resources -- South Africa -- Eastern Cape Natural resources -- Management -- South Africa -- Eastern Cape Conservation of natural resources -- South Africa -- Eastern Cape Landscape protection -- Economic aspects -- South Africa -- Eastern Cape Fuelwood consumption -- South Africa -- Eastern Cape Fuelwood consumption -- Economic aspects -- South Africa -- Eastern Cape Forests and forestry -- South Africa -- Eastern Cape Fuelwood conservation -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4765 , http://hdl.handle.net/10962/d1007167
- Description: Forest and woodland ecosystems provide a variety of natural resources such as fuelwood, brushwood and kraal posts to local communities, as well as possess important cultural and spiritual value. However, many forests and woodlands worldwide have been unsustainably used and managed. Thus, under pressure from the international conservation community to recognise the importance of people's relationships with their surrounding natural environment, particularly for the natural resources it can provide, and given a move away from the management of forests and woodlands for sustained yields, and according to simple cause and effect models, in favour of systems approaches, South Africa has developed some of the most progressive natural resource management policies in the world. Nevertheless, for these policies to be sensitive to local contexts, there remains a need for a better understanding of how local people in different contexts, determine forest and woodland ecosystems to be of use to them, and what 'usefulness' means to different groups of resources users. This is a case study, which examines the role of fuelwood, brushwood and kraal posts in the rural livelihoods of the people of Machibi village, located in the Eastern Cape province of South Africa, through people's preferences for particular landscapes and species, accessed for these purposes, and the trade-offs people make between resource availability and resource accessibility. Key objectives of the study are to 1) determine the preferred landscapes and species for fuelwood, brushwood and kraal posts at Machibi, 2) determine the landscapes and species actually used for fuelwood, brushwood and kraal posts, and 3) with the help of a conceptual model, and using iterative modelling as a tool, determine the factors that influence people's harvesting strategies in terms of the costs and benefits associated with the different landscape and species options. On the basis of this knowledge, the study provides some guiding principles for the better use and management of these landscapes and species for fuelwood, brushwood and kraal posts. An innovative research approach and methodology that integrates social and ecological systems, works across disciplines, and draws on different types of knowledge is used to develop and test a conceptual model of the harvesting strategies of fuelwood and kraalwood users at Machibi. Participatory methods such as workshops, participatory resource mapping, ranking exercises and trend-lines were used to tap into local knowledge while plotless vegetation sampling and GIS maps were used to capture the scientific information. Results showed that people did not always use the landscapes and species they preferred. However, the local people did behave in a rational manner by weighing up the returns from harvesting and accessibility costs associated with the respective options available to them, before selecting the option(s) associated with the greatest net benefits. At the landscape level, people made trade-offs between the returns from harvesting and the accessibility costs of using particular landscapes in addition to costs associated with the physical work of harvesting fuelwood, brushwood or kraal posts from these landscapes. At the species level, people made trade-offs between the returns from harvesting and the accessibility costs of harvesting particular species for fuelwood, brushwood and kraal posts, or the costs of commercial alternatives. Costbenefit factors that influenced people's resource use patterns also differed across landscapes and species for fuelwood, brushwood and kraal posts, respectively. Consequently, a range of diverse and flexible management options and strategies is recommended for the wise use and management of these landscapes and species, focused on short, medium and long term goals. These strategies examine the use of cost - benefit incentives to influence people’s landscape and species use patterns.
- Full Text:
- Date Issued: 2008
- Authors: Scheepers, Kelly
- Date: 2008
- Subjects: Fuelwood -- South Africa -- Eastern Cape Forest ecology -- South Africa -- Eastern Cape Natural resources -- South Africa -- Eastern Cape Natural resources -- Management -- South Africa -- Eastern Cape Conservation of natural resources -- South Africa -- Eastern Cape Landscape protection -- Economic aspects -- South Africa -- Eastern Cape Fuelwood consumption -- South Africa -- Eastern Cape Fuelwood consumption -- Economic aspects -- South Africa -- Eastern Cape Forests and forestry -- South Africa -- Eastern Cape Fuelwood conservation -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4765 , http://hdl.handle.net/10962/d1007167
- Description: Forest and woodland ecosystems provide a variety of natural resources such as fuelwood, brushwood and kraal posts to local communities, as well as possess important cultural and spiritual value. However, many forests and woodlands worldwide have been unsustainably used and managed. Thus, under pressure from the international conservation community to recognise the importance of people's relationships with their surrounding natural environment, particularly for the natural resources it can provide, and given a move away from the management of forests and woodlands for sustained yields, and according to simple cause and effect models, in favour of systems approaches, South Africa has developed some of the most progressive natural resource management policies in the world. Nevertheless, for these policies to be sensitive to local contexts, there remains a need for a better understanding of how local people in different contexts, determine forest and woodland ecosystems to be of use to them, and what 'usefulness' means to different groups of resources users. This is a case study, which examines the role of fuelwood, brushwood and kraal posts in the rural livelihoods of the people of Machibi village, located in the Eastern Cape province of South Africa, through people's preferences for particular landscapes and species, accessed for these purposes, and the trade-offs people make between resource availability and resource accessibility. Key objectives of the study are to 1) determine the preferred landscapes and species for fuelwood, brushwood and kraal posts at Machibi, 2) determine the landscapes and species actually used for fuelwood, brushwood and kraal posts, and 3) with the help of a conceptual model, and using iterative modelling as a tool, determine the factors that influence people's harvesting strategies in terms of the costs and benefits associated with the different landscape and species options. On the basis of this knowledge, the study provides some guiding principles for the better use and management of these landscapes and species for fuelwood, brushwood and kraal posts. An innovative research approach and methodology that integrates social and ecological systems, works across disciplines, and draws on different types of knowledge is used to develop and test a conceptual model of the harvesting strategies of fuelwood and kraalwood users at Machibi. Participatory methods such as workshops, participatory resource mapping, ranking exercises and trend-lines were used to tap into local knowledge while plotless vegetation sampling and GIS maps were used to capture the scientific information. Results showed that people did not always use the landscapes and species they preferred. However, the local people did behave in a rational manner by weighing up the returns from harvesting and accessibility costs associated with the respective options available to them, before selecting the option(s) associated with the greatest net benefits. At the landscape level, people made trade-offs between the returns from harvesting and the accessibility costs of using particular landscapes in addition to costs associated with the physical work of harvesting fuelwood, brushwood or kraal posts from these landscapes. At the species level, people made trade-offs between the returns from harvesting and the accessibility costs of harvesting particular species for fuelwood, brushwood and kraal posts, or the costs of commercial alternatives. Costbenefit factors that influenced people's resource use patterns also differed across landscapes and species for fuelwood, brushwood and kraal posts, respectively. Consequently, a range of diverse and flexible management options and strategies is recommended for the wise use and management of these landscapes and species, focused on short, medium and long term goals. These strategies examine the use of cost - benefit incentives to influence people’s landscape and species use patterns.
- Full Text:
- Date Issued: 2008
Fungal remediation of winery and distillery wastewaters using Trametes pubescens MB 89 and the enhanced production of a high-value enzyme therein
- Authors: Strong, Peter James
- Date: 2008
- Subjects: Fungal remediation Distilleries -- Waste disposal Wine and wine making -- Waste disposal Bioremediation Laccase Enzymes -- Biotechnology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3932 , http://hdl.handle.net/10962/d1003991
- Description: In this study white-rot fungi were investigated for their efficiency at distillery wastewater remediation and the production of laccase as a valuable by-product. Distillery wastewaters are high in organic load and low in pH. The presence of phenolic compounds can lead to extremely colour-rich wastewaters and can be toxic to microorganisms. The presence of the inorganic ions may also affect biological treatment. White-rot fungi are unique among eukaryotic or prokaryotic microbes in possessing powerful oxidative enzyme systems that can degrade lignin to carbon dioxide. These ligninolytic enzymes, such as lignin peroxidase, manganese peroxidase and laccase, are capable of degrading a vast range of toxic, recalcitrant environmental pollutants and this makes the white-rot fungi strong candidates for the bioremediation of polluted soils and waters. The laccase enzyme alone has shown remediation potential in wastewaters such as beer production effluent, olive mill wastewater, alcohol distillery wastes, dye-containing wastewaters from the textile industry as well as wastewaters from the paper and pulp industry. It has been shown to be capable of remediating soils and waters polluted with chlorinated phenolic compounds, polyaromatic hydrocarbons, nitrosubstituted compounds and fungicides, herbicides and insecticides.
- Full Text:
- Date Issued: 2008
- Authors: Strong, Peter James
- Date: 2008
- Subjects: Fungal remediation Distilleries -- Waste disposal Wine and wine making -- Waste disposal Bioremediation Laccase Enzymes -- Biotechnology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3932 , http://hdl.handle.net/10962/d1003991
- Description: In this study white-rot fungi were investigated for their efficiency at distillery wastewater remediation and the production of laccase as a valuable by-product. Distillery wastewaters are high in organic load and low in pH. The presence of phenolic compounds can lead to extremely colour-rich wastewaters and can be toxic to microorganisms. The presence of the inorganic ions may also affect biological treatment. White-rot fungi are unique among eukaryotic or prokaryotic microbes in possessing powerful oxidative enzyme systems that can degrade lignin to carbon dioxide. These ligninolytic enzymes, such as lignin peroxidase, manganese peroxidase and laccase, are capable of degrading a vast range of toxic, recalcitrant environmental pollutants and this makes the white-rot fungi strong candidates for the bioremediation of polluted soils and waters. The laccase enzyme alone has shown remediation potential in wastewaters such as beer production effluent, olive mill wastewater, alcohol distillery wastes, dye-containing wastewaters from the textile industry as well as wastewaters from the paper and pulp industry. It has been shown to be capable of remediating soils and waters polluted with chlorinated phenolic compounds, polyaromatic hydrocarbons, nitrosubstituted compounds and fungicides, herbicides and insecticides.
- Full Text:
- Date Issued: 2008
Queens, pseudoqueens and laying workers reproductive competition in the Cape Honeybee (Apis mellifera capensis Eschscholtz)
- Authors: Muerrle, Thomas Martin
- Date: 2008
- Subjects: Honeybee Honeybee -- Reproduction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5750 , http://hdl.handle.net/10962/d1005437
- Description: In honeybees (Apis mellifera L.) the queen monopolises reproduction. However, especially after queen loss, workers can lay eggs, but are unable to mate. They produce haploid male offspring (drones) from unfertilised eggs via arrhenotokous parthenogenesis. In contrast, workers of the honeybee subspecies Apis mellifera capensis Eschscholtz typically produce diploid female offspring from unfertilised eggs thelytokously. After queen loss and without queen-derived brood A. m. capensis colonies can successfully requeen from worker-derived brood. This, however, is a relatively rare event in wild populations. Moreover, workerderived queens were described to be smaller, more worker-like and reproductively inferior. On the other hand, the fixation of the thelytokous trait relies mainly on sufficient numbers of viable drones produced by worker-derived queens. Small numbers of reproductively inferior worker-derived queens in A. m. capensis populations would be clearly counterintuitive. It is therefore necessary to quantify the significance of worker-dependant queen rearing pathways on the individual (queen) and on population level.Reproductive inferiority of worker-derived queens could not be confirmed on the individual (queen) level when comparing parameters indicating potential reproductive success of queen- and worker-derived queens. Queen- and worker-derived queens clearly showed a congruent range of reproductive performance. In queen rearing preference tests, increased acceptance of worker-derived female larvae was exactly counterbalanced by increased mortality, resulting in an equal number of eclosing virgin queens from an equal number of grafts in both test groups. Larval survival and successful eclosion is a prerequisite for a queen’s reproductive success. I found no difference in eclosion success for queen- and worker-derived virgin queens, indicating a similar potential for reproductive success in both queen types. Assessments of the developmental patterns of colonies headed by both queen and worker-derived queens in long-term experiments revealed no significant differences in reproductive success. Colonies headed by queen-derived queens and colonies headed by worker-derived queens could not be separated when comparing the different developmental pathways observed or from differences in worker-force. Reproductive dominance in A. m. capensis appeared tobe determined by a function of relative compositional and absolute quantitative pheromonal patterns, where individuals, which produce compositionally most queen-like blends in highest quantities, occupy top positions. Queen- and worker-derived virgin queens occupied intermediate positions between pseudoqueens and mated queens. However, no significant differences between the pheromonal status of queen- and worker-derived virgin queens were observed, suggesting a similar range of reproductive dominance for both queen types. In behavioural bioassays queen- and worker-derived virgin queens appeared to be similarly attractive to clustering workers and to drones in a drone congregation area, indicating no differences in potential reproductive success for queens from both origins for those parameters. The significant influence of the queen substance 9-ODA on attractiveness to workers and drones was confirmed. Rare requeening events from worker-derived female brood in queenless A.m. capensis do not satisfactorily explain the fixation of the thelytokous trait at a population level. I observed A. m. capensis worker ovipositing into empty artificial queen cell cups in queen-right colonies. The queen was confined behind a queen excluder grid in a separate compartment of the colony, to imitate reduced pheromonal flow, similar to swarming or superseding colonies. Eggs oviposited by workers in artificial queen cell cups were readily accepted for queen rearing and successful eclosion of viable virgin queens was observed. Consequently I suggested an alternative worker-dependant reproductive pathway in A. m. capensis, which was never described before: In swarming or superseding queenright colonies, laying workers may directly compete with the queen for reproductive success by ovipositing (instead of the queen) into natural queen cell cups. At a population level this reproductive tactic may result in large numbers of worker-derived queens of high reproductive quality in natural populations of A. m. capensis.
- Full Text:
- Date Issued: 2008
- Authors: Muerrle, Thomas Martin
- Date: 2008
- Subjects: Honeybee Honeybee -- Reproduction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5750 , http://hdl.handle.net/10962/d1005437
- Description: In honeybees (Apis mellifera L.) the queen monopolises reproduction. However, especially after queen loss, workers can lay eggs, but are unable to mate. They produce haploid male offspring (drones) from unfertilised eggs via arrhenotokous parthenogenesis. In contrast, workers of the honeybee subspecies Apis mellifera capensis Eschscholtz typically produce diploid female offspring from unfertilised eggs thelytokously. After queen loss and without queen-derived brood A. m. capensis colonies can successfully requeen from worker-derived brood. This, however, is a relatively rare event in wild populations. Moreover, workerderived queens were described to be smaller, more worker-like and reproductively inferior. On the other hand, the fixation of the thelytokous trait relies mainly on sufficient numbers of viable drones produced by worker-derived queens. Small numbers of reproductively inferior worker-derived queens in A. m. capensis populations would be clearly counterintuitive. It is therefore necessary to quantify the significance of worker-dependant queen rearing pathways on the individual (queen) and on population level.Reproductive inferiority of worker-derived queens could not be confirmed on the individual (queen) level when comparing parameters indicating potential reproductive success of queen- and worker-derived queens. Queen- and worker-derived queens clearly showed a congruent range of reproductive performance. In queen rearing preference tests, increased acceptance of worker-derived female larvae was exactly counterbalanced by increased mortality, resulting in an equal number of eclosing virgin queens from an equal number of grafts in both test groups. Larval survival and successful eclosion is a prerequisite for a queen’s reproductive success. I found no difference in eclosion success for queen- and worker-derived virgin queens, indicating a similar potential for reproductive success in both queen types. Assessments of the developmental patterns of colonies headed by both queen and worker-derived queens in long-term experiments revealed no significant differences in reproductive success. Colonies headed by queen-derived queens and colonies headed by worker-derived queens could not be separated when comparing the different developmental pathways observed or from differences in worker-force. Reproductive dominance in A. m. capensis appeared tobe determined by a function of relative compositional and absolute quantitative pheromonal patterns, where individuals, which produce compositionally most queen-like blends in highest quantities, occupy top positions. Queen- and worker-derived virgin queens occupied intermediate positions between pseudoqueens and mated queens. However, no significant differences between the pheromonal status of queen- and worker-derived virgin queens were observed, suggesting a similar range of reproductive dominance for both queen types. In behavioural bioassays queen- and worker-derived virgin queens appeared to be similarly attractive to clustering workers and to drones in a drone congregation area, indicating no differences in potential reproductive success for queens from both origins for those parameters. The significant influence of the queen substance 9-ODA on attractiveness to workers and drones was confirmed. Rare requeening events from worker-derived female brood in queenless A.m. capensis do not satisfactorily explain the fixation of the thelytokous trait at a population level. I observed A. m. capensis worker ovipositing into empty artificial queen cell cups in queen-right colonies. The queen was confined behind a queen excluder grid in a separate compartment of the colony, to imitate reduced pheromonal flow, similar to swarming or superseding colonies. Eggs oviposited by workers in artificial queen cell cups were readily accepted for queen rearing and successful eclosion of viable virgin queens was observed. Consequently I suggested an alternative worker-dependant reproductive pathway in A. m. capensis, which was never described before: In swarming or superseding queenright colonies, laying workers may directly compete with the queen for reproductive success by ovipositing (instead of the queen) into natural queen cell cups. At a population level this reproductive tactic may result in large numbers of worker-derived queens of high reproductive quality in natural populations of A. m. capensis.
- Full Text:
- Date Issued: 2008
Studies directed towards the synthesis of chromone carbaldehyde-derived HIV-1 protease inhibitors
- Authors: Molefe, Duduzile Mabel
- Date: 2008
- Subjects: Protease Inhibitors , HIV infections , HIV (Viruses) , AIDS (Disease) , Proteolytic enzymes , Heterocyclic compounds -- Derivatives , Chemical kinetics , Nuclear magnetic resonance spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4526 , http://hdl.handle.net/10962/d1015542
- Description: A series of chromone-3-carbaldehydes have been prepared using Vilsmeier-Haack methodology while a corresponding series of chromone-2-carbaldeydes have been synthesized via the Kostanecki-Robinson reaction. Baylis-Hillman reactions have been conducted on both series of chromone carbaldehydes using three different catalysts, viz., 1,4-diazabicyclo(2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) and 3-hydroxyquinuclidine (3HQ), and acrylonitrile, methyl acrylate and methyl vinyl ketone as the activated alkenes. These reactions have typically (but not always!) afforded both normal Baylis-Hillman and dimeric products. Attention has also been given to the use of 1-methyl-2-pyrrolidine (1-NMP), an ionic liquid, to replace normal organic solvents, and it has been found that, in the presence of DABCO, chromone-3-carbaldehydes afford the dimeric products alone. Reactions of chromone-3-carbaldehydes with methyl vinyl ketone have yielded unexpected, novel adducts, which appear to arise from preferential attack at C(2) in the chromone nucleus. Research on chromone-2-carbaldeydes under Baylis-Hillman conditions has also resulted in the formation of some interesting products instead of the expected Baylis-Hillman adducts. The Baylis-Hillman products have been explored as substrates for aza-Michael reactions using various amino derivatives including protected amino acids in the presence of the tetrabutylammonium bromide (TBAB) and the ionic liquid, 3-butyl-1- methylimidazoleboranetetrafluoride (BmimBF₄), as catalysts. The aza-Michael products have been targeted as truncated ritonavir analogues for investigation as potential HIV -1 protease inhibitors, and representative compounds have been subjected to enzyme inhibition assays to explore the extent and type of inhibition. Lineweaver-Burk and Dixon plots have indicated competitive inhibition in one case as well as non-competitive inhibition in another, and the inhibition constants (Ki) have been compared with that of the ritonavir. Computer modelling studies have also been conducted on selected chromonecontaining derivatives, using the ACCELRYS Cerius² platform. Interactive docking of the chromone-containing ligands into the HIV -1 protease receptor site, using the Ligandfit module, has indicated the importance of hydrogen-bonding interactions mediated by bridging water molecules situated in the receptor cavity. NMR spectroscopy has been used to elucidate complex and competing mechanistic pathways involved in the Baylis-Hillman reactions of selected 2-nitrobenzaldehydes with MVK in the presence of DABCO - reactions which afford the normal BaylisHillman product, the MVK dimer and syn- and anti-Baylis-Hillman type diadducts. The kinetic data confirm the concomitant operation of two pathways and reveal that, in the initial stage of the reaction, the product distribution is kinetically controlled, whereas in the latter stage, thermodynamic control results in the consumption of the normal Baylis-Hillman product and predominance of the anti-diadduct.
- Full Text:
- Date Issued: 2008
- Authors: Molefe, Duduzile Mabel
- Date: 2008
- Subjects: Protease Inhibitors , HIV infections , HIV (Viruses) , AIDS (Disease) , Proteolytic enzymes , Heterocyclic compounds -- Derivatives , Chemical kinetics , Nuclear magnetic resonance spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4526 , http://hdl.handle.net/10962/d1015542
- Description: A series of chromone-3-carbaldehydes have been prepared using Vilsmeier-Haack methodology while a corresponding series of chromone-2-carbaldeydes have been synthesized via the Kostanecki-Robinson reaction. Baylis-Hillman reactions have been conducted on both series of chromone carbaldehydes using three different catalysts, viz., 1,4-diazabicyclo(2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) and 3-hydroxyquinuclidine (3HQ), and acrylonitrile, methyl acrylate and methyl vinyl ketone as the activated alkenes. These reactions have typically (but not always!) afforded both normal Baylis-Hillman and dimeric products. Attention has also been given to the use of 1-methyl-2-pyrrolidine (1-NMP), an ionic liquid, to replace normal organic solvents, and it has been found that, in the presence of DABCO, chromone-3-carbaldehydes afford the dimeric products alone. Reactions of chromone-3-carbaldehydes with methyl vinyl ketone have yielded unexpected, novel adducts, which appear to arise from preferential attack at C(2) in the chromone nucleus. Research on chromone-2-carbaldeydes under Baylis-Hillman conditions has also resulted in the formation of some interesting products instead of the expected Baylis-Hillman adducts. The Baylis-Hillman products have been explored as substrates for aza-Michael reactions using various amino derivatives including protected amino acids in the presence of the tetrabutylammonium bromide (TBAB) and the ionic liquid, 3-butyl-1- methylimidazoleboranetetrafluoride (BmimBF₄), as catalysts. The aza-Michael products have been targeted as truncated ritonavir analogues for investigation as potential HIV -1 protease inhibitors, and representative compounds have been subjected to enzyme inhibition assays to explore the extent and type of inhibition. Lineweaver-Burk and Dixon plots have indicated competitive inhibition in one case as well as non-competitive inhibition in another, and the inhibition constants (Ki) have been compared with that of the ritonavir. Computer modelling studies have also been conducted on selected chromonecontaining derivatives, using the ACCELRYS Cerius² platform. Interactive docking of the chromone-containing ligands into the HIV -1 protease receptor site, using the Ligandfit module, has indicated the importance of hydrogen-bonding interactions mediated by bridging water molecules situated in the receptor cavity. NMR spectroscopy has been used to elucidate complex and competing mechanistic pathways involved in the Baylis-Hillman reactions of selected 2-nitrobenzaldehydes with MVK in the presence of DABCO - reactions which afford the normal BaylisHillman product, the MVK dimer and syn- and anti-Baylis-Hillman type diadducts. The kinetic data confirm the concomitant operation of two pathways and reveal that, in the initial stage of the reaction, the product distribution is kinetically controlled, whereas in the latter stage, thermodynamic control results in the consumption of the normal Baylis-Hillman product and predominance of the anti-diadduct.
- Full Text:
- Date Issued: 2008