Camphor derivatives in asymmetric synthesis: a synthetic, mechanistic and theoretical study
- Authors: Lobb, Kevin Alan
- Date: 2008
- Subjects: Chemistry, Organic -- Research Esters Organic compounds -- Synthesis Alkylation Chemical reactions -- Computer simulation Chemical kinetics Camphor Cinnamomum
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4414 , http://hdl.handle.net/10962/d1006770
- Description: A series of 3,3-ethylenedioxy-exo- and endo- bornyl esters have been prepared and subjected to α-benzylation using lithium diisopropylamide and benzyl bromide. In the exo-series of esters the diastereofacial selectivity of benzylation was found to improve (up to 34% d.e.) as the steric bulk of the O-alkyl group increased, whereas in the endo-series, a surprising decrease in stereoselectivity was observed as the steric bulk increased – an observation attributed to flexibility of the metal-coordinated endo-enolate system, compared to the relative rigidity of the exo analogues. The conformational options for each series was explored at the density functional theory level. Reductive cyclization of a range of specially prepared N-carbobenzyloxy-amino acid esters has been shown to afford the corresponding derivatives, contrary to previous reports that the cyclization is limited to the glycine derivative. The cyclization sequence has been explored in detail, and the yield has been shown to be critically dependent on the stereochemistry of the α-amino acid moiety. Moreover, it seems that reductive cyclization occurs more readily with the endo- rather than the exo-bornyl N-CBZ-amino acid esters. Molecular modelling of relevant transition states at the DFT levels indicates that L-amino acid-derived systems should cyclize preferably in the exo-series and D-amino acid-derived systems should cyclize preferably in the endo series. Studies of alkylation of an iminolactone system have reported an interesting anomaly - exo-methylation is observed while endo-alkylation predominates for larger alkyl groups. This has been studied in detail at the DFT level, and the anomaly is attributed to thermodynamic control in the methyl case, whereas kinetic control is the norm in this system. Preliminary computer modelling of the intramolecular rearrangement of a 3,3-xylylbornyl system at the HF/STO-3G level raised doubts concerning the structure assigned by Evans to one of the rearrangement products, prompting an X-ray crystallographic analysis and leading to the revision of its structure from a pinene to a camphene derivative. The previously elusive spiro[bornane-3,2’-indan]-2-exo-tosylate has been successfully isolated, and the kinetics of its ready decomposition to the two camphene products has been followed by 1H NMR spectroscopy. The endo-tosylate analogue, on the other hand, was found to be remarkably stable. Kinetic data obtained for rearrangement of this exo-bornyl tosylate have indicated the operation of tandem autocatalytic and pseudo-first-order transformations leading sequentially to the two isomeric camphene products. An extensive coset analysis of all possible rearrangement processes of the initially-formed cation formed from decomposition of the exo-tosylate has afforded a graph containing 336 classical cations (modelled at the AM1 and B3LYP levels) and 526 transition-state complexes (modelled at the AM1 level). This analysis afforded a viable 4-step classical mechanism connecting the first camphene product with the second. A more realistic study, involving non-classical carbocations, has afforded a graph of all possible (classical and non-classical) cations that could be formed by rearrangment of the initiallyformed cation. The resulting graph confirms that the only energetically feasible path corresponds to the classical mechanism, but simply involves two steps, including a novel, concerted Wagner-Meerwein – 6,2-hydride shift – Wagner-Meerwein rearrangement.
- Full Text:
- Date Issued: 2008
- Authors: Lobb, Kevin Alan
- Date: 2008
- Subjects: Chemistry, Organic -- Research Esters Organic compounds -- Synthesis Alkylation Chemical reactions -- Computer simulation Chemical kinetics Camphor Cinnamomum
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4414 , http://hdl.handle.net/10962/d1006770
- Description: A series of 3,3-ethylenedioxy-exo- and endo- bornyl esters have been prepared and subjected to α-benzylation using lithium diisopropylamide and benzyl bromide. In the exo-series of esters the diastereofacial selectivity of benzylation was found to improve (up to 34% d.e.) as the steric bulk of the O-alkyl group increased, whereas in the endo-series, a surprising decrease in stereoselectivity was observed as the steric bulk increased – an observation attributed to flexibility of the metal-coordinated endo-enolate system, compared to the relative rigidity of the exo analogues. The conformational options for each series was explored at the density functional theory level. Reductive cyclization of a range of specially prepared N-carbobenzyloxy-amino acid esters has been shown to afford the corresponding derivatives, contrary to previous reports that the cyclization is limited to the glycine derivative. The cyclization sequence has been explored in detail, and the yield has been shown to be critically dependent on the stereochemistry of the α-amino acid moiety. Moreover, it seems that reductive cyclization occurs more readily with the endo- rather than the exo-bornyl N-CBZ-amino acid esters. Molecular modelling of relevant transition states at the DFT levels indicates that L-amino acid-derived systems should cyclize preferably in the exo-series and D-amino acid-derived systems should cyclize preferably in the endo series. Studies of alkylation of an iminolactone system have reported an interesting anomaly - exo-methylation is observed while endo-alkylation predominates for larger alkyl groups. This has been studied in detail at the DFT level, and the anomaly is attributed to thermodynamic control in the methyl case, whereas kinetic control is the norm in this system. Preliminary computer modelling of the intramolecular rearrangement of a 3,3-xylylbornyl system at the HF/STO-3G level raised doubts concerning the structure assigned by Evans to one of the rearrangement products, prompting an X-ray crystallographic analysis and leading to the revision of its structure from a pinene to a camphene derivative. The previously elusive spiro[bornane-3,2’-indan]-2-exo-tosylate has been successfully isolated, and the kinetics of its ready decomposition to the two camphene products has been followed by 1H NMR spectroscopy. The endo-tosylate analogue, on the other hand, was found to be remarkably stable. Kinetic data obtained for rearrangement of this exo-bornyl tosylate have indicated the operation of tandem autocatalytic and pseudo-first-order transformations leading sequentially to the two isomeric camphene products. An extensive coset analysis of all possible rearrangement processes of the initially-formed cation formed from decomposition of the exo-tosylate has afforded a graph containing 336 classical cations (modelled at the AM1 and B3LYP levels) and 526 transition-state complexes (modelled at the AM1 level). This analysis afforded a viable 4-step classical mechanism connecting the first camphene product with the second. A more realistic study, involving non-classical carbocations, has afforded a graph of all possible (classical and non-classical) cations that could be formed by rearrangment of the initiallyformed cation. The resulting graph confirms that the only energetically feasible path corresponds to the classical mechanism, but simply involves two steps, including a novel, concerted Wagner-Meerwein – 6,2-hydride shift – Wagner-Meerwein rearrangement.
- 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
Bioprocess development for removal of nitrogenous compounds from precious metal refinery wastewater
- Manipura, Walappuly Mudiyanselage Janakasiri Aruna Shantha Bandara
- Authors: Manipura, Walappuly Mudiyanselage Janakasiri Aruna Shantha Bandara
- Date: 2008
- Subjects: Factory and trade waste Centralized industrial waste treatment facilities Metals -- Absorption and adsorption Metals -- Environmental aspects Water -- Purification -- Mathematical models Water quality management Water reuse Metals -- Refining Microbiology -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4076 , http://hdl.handle.net/10962/d1007341
- Description: Removal of nitrogenous compounds from precious metal refinery (PMR) wastewater is important in terms of avoiding eutrophication (environmental protection), metal recovery (increased overall process efficiency and value recovery) and reuse of treated water (maximum use of natural resources). Extreme pH conditions (4 to 13 depending on the wastewater stream), high chemical oxygen demand (> 10,000 mg/I), numerous metals and high concentrations of those metals (> 20 mg/l of platinum group metals) in the wastewater are the main challenges for biological removal of nitrogenous compounds from PMR wastewater. Nitrogenous compounds such as NH₄⁺-N and N0₃-N are strong metal ligands, which make it difficult to recover metals from the wastewater. Therefore, a bioprocess was developed for removal of nitrogenous compounds from carefully simulated PMR wastewater. A preliminary investigation of metal wastewater was carried out to determine its composition and physico-chemical properties, the ability to nitrify and denitrify under different pH conditions and denitrification with different carbon Source compounds and amounts. Even at pH 4, nitrification could be carried out. A suitable hydraulic retention time was found to be 72 hours. There was no significant difference between sodium acetate and sodium lactate as carbon sources for denitrification. Based on these results, a reactor comparison study was carried out using simulated PMR wastewater in three types of reactors: continuously stirred tank reactor (CSTR), packed-bed reactor (PBR) and airlift suspension reactor (ALSR). These reactors were fed with 30 mg/l of Rh bound in an NH₄⁺ based compound (Claus salt: pentaaminechlororhodium (III) dichloride). Total nitrogen removal efficiencies of > 68 % , > 79 % and > 45 % were obtained in the CSTR, PBR and ALSR, respectively. Serially connected CSTR-PBR and PBR-CSTR reactor configurations were then studied to determine the best configuration for maximum removal of nitrogenous compounds from the wastewater. The PBR-CSTR configuration gave consistent biomass retention and automatic pH control in the CSTR. Ammonium removal efficiencies > 95 % were achieved in both reactors. As poor nitrate removal was observed a toxicity study was carried out using respirometry and the half saturation inhibition coefficients for Pt, Pd, Rh and Ru were found to be 15.81, 25.00, 33.34 and 39.25 mg/l, respectively. A mathematical model was developed to describe the nitrogen removal in PMR wastewater using activated sludge model number 1 (ASMl), two step nitrification and metal toxicity. An operational protocol was developed based on the literature review, experimental work and simulation results. The optimum reactor configuration under the set conditions (20 mg/I of Rh and < 100 mg/I of NH₄⁺-N) was found to be PBR-CSTR-PBR process, which achieved overall NH₄⁺-N and N0₃⁻-N removal efficiencies of > 90 % and 95 %, respectively. Finally, a rudimentary microbial characterisation was carried out on subsamples from the CSTR and PBRsecondary. It was found that the CSTR biomass consisted of both rods and cocci while PBRsecondary consisted of rods only. Based on these experimental works, further research needs and recommendations were made for optimisation of the developed bioprocess for removal of nitrogenous compounds from PMR wastewater.
- Full Text:
- Date Issued: 2008
- Authors: Manipura, Walappuly Mudiyanselage Janakasiri Aruna Shantha Bandara
- Date: 2008
- Subjects: Factory and trade waste Centralized industrial waste treatment facilities Metals -- Absorption and adsorption Metals -- Environmental aspects Water -- Purification -- Mathematical models Water quality management Water reuse Metals -- Refining Microbiology -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4076 , http://hdl.handle.net/10962/d1007341
- Description: Removal of nitrogenous compounds from precious metal refinery (PMR) wastewater is important in terms of avoiding eutrophication (environmental protection), metal recovery (increased overall process efficiency and value recovery) and reuse of treated water (maximum use of natural resources). Extreme pH conditions (4 to 13 depending on the wastewater stream), high chemical oxygen demand (> 10,000 mg/I), numerous metals and high concentrations of those metals (> 20 mg/l of platinum group metals) in the wastewater are the main challenges for biological removal of nitrogenous compounds from PMR wastewater. Nitrogenous compounds such as NH₄⁺-N and N0₃-N are strong metal ligands, which make it difficult to recover metals from the wastewater. Therefore, a bioprocess was developed for removal of nitrogenous compounds from carefully simulated PMR wastewater. A preliminary investigation of metal wastewater was carried out to determine its composition and physico-chemical properties, the ability to nitrify and denitrify under different pH conditions and denitrification with different carbon Source compounds and amounts. Even at pH 4, nitrification could be carried out. A suitable hydraulic retention time was found to be 72 hours. There was no significant difference between sodium acetate and sodium lactate as carbon sources for denitrification. Based on these results, a reactor comparison study was carried out using simulated PMR wastewater in three types of reactors: continuously stirred tank reactor (CSTR), packed-bed reactor (PBR) and airlift suspension reactor (ALSR). These reactors were fed with 30 mg/l of Rh bound in an NH₄⁺ based compound (Claus salt: pentaaminechlororhodium (III) dichloride). Total nitrogen removal efficiencies of > 68 % , > 79 % and > 45 % were obtained in the CSTR, PBR and ALSR, respectively. Serially connected CSTR-PBR and PBR-CSTR reactor configurations were then studied to determine the best configuration for maximum removal of nitrogenous compounds from the wastewater. The PBR-CSTR configuration gave consistent biomass retention and automatic pH control in the CSTR. Ammonium removal efficiencies > 95 % were achieved in both reactors. As poor nitrate removal was observed a toxicity study was carried out using respirometry and the half saturation inhibition coefficients for Pt, Pd, Rh and Ru were found to be 15.81, 25.00, 33.34 and 39.25 mg/l, respectively. A mathematical model was developed to describe the nitrogen removal in PMR wastewater using activated sludge model number 1 (ASMl), two step nitrification and metal toxicity. An operational protocol was developed based on the literature review, experimental work and simulation results. The optimum reactor configuration under the set conditions (20 mg/I of Rh and < 100 mg/I of NH₄⁺-N) was found to be PBR-CSTR-PBR process, which achieved overall NH₄⁺-N and N0₃⁻-N removal efficiencies of > 90 % and 95 %, respectively. Finally, a rudimentary microbial characterisation was carried out on subsamples from the CSTR and PBRsecondary. It was found that the CSTR biomass consisted of both rods and cocci while PBRsecondary consisted of rods only. Based on these experimental works, further research needs and recommendations were made for optimisation of the developed bioprocess for removal of nitrogenous compounds from PMR wastewater.
- 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
Assembly of Omegatetravirus virus-like particles in the yeast Saccharomyces cerevisiae
- Authors: Tomasicchio, Michele
- Date: 2008
- Subjects: Helicoverpa armigera Imbrasia cytherea Viruses RNA viruses Insects -- Viruses Lepidoptera -- Viruses Saccharomyces cerevisiae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3930 , http://hdl.handle.net/10962/d1003989
- Description: The Tetraviridae are a family of ss (+) RNA viruses that specifically infect lepidopteran insects. Their icosahedral capsids are non-enveloped and approximately 40 nm in diameter with T=4 quasi-equivalent symmetry. The omegatetraviruses, which are structurally the best characterised in the family, include Helicoverpa armigera stunt virus (HaSV) and Nudaurelia capensis omega virus (NwV). The omegatetravirus procapsid is composed of 240 identical copies of the capsid precursor proteins, which undergo autoproteolytic cleavage at its carboxyl-terminus generating the mature capsid protein (b) and γ-peptide. This process occurs in vitro following a shift from pH 7.6 to pH 6.0. The viral capsid encapsidates two ss genomic RNAs: The larger RNA1 encodes the viral replicase as well as three small ORFs while RNA2 encodes the capsid precursor protein together with an overlapping ORF designated P17. While a wealth of structural data pertaining to the assembly and maturation of omegatetraviruses is available, little is known about how this relates to their lifecycle. The principle aim of the research described in this thesis was to use an experimental system developed in the yeast, Saccharomyces cerevisiae, to investigate the assembly of HaSV and NwV virus-like particles (VLPs) in terms of maturation and encapsidation of viral RNAs, in vivo. The yeast expression system used two promoter systems for expression of capsid precursor protein: in the first, a hybrid promoter (PGADH) was used for high-level expression, while the second, PGAL1, produced substantially lower levels of the virus capsid protein precursors. An increase in the level of HaSV capsid protein precursor (p71) via the PGADH promoter resulted in a dramatic increase in VLP assembly as compared with the PGAL system. A protein equivalent to the mature capsid protein (p64) appeared at later time intervals following induction of transcription. Transmission electron microscopic studies showed that p64 correlated with the presence of mature VLPs as opposed to procapsids in cells containing p71. This confirmed that the presence of p64 denoted maturation of VLPs in vivo. Further investigation indicated that maturation correlated with cell aging and the onset of apoptosis. It was shown that induction of apoptosis resulted in VLP maturation while inhibition of apoptosis prevented maturation. These results suggested that the process of apoptosis might be the trigger for maturation of virus procapsids in their host cells. The increase in the efficiency of VLP assembly observed in the high-level expression system was proposed to be due to an increase in the cellular concentrations of viral RNA. To test this hypothesis, HaSV P71 was co-expressed with either P71 mRNA or full length RNA2. An increase in the solubility of p71 was observed in cells expressing increased levels of both RNAs, but there was no increase in the efficiency of VLP assembly. Northern analysis of encapsidated RNAs revealed that there was no selective encapsidation of either P71 mRNA or viral RNA2. This data indicated that the increase in viral RNA was not the reason for increased efficiency of VLP assembly, but most likely resulted from higher concentrations of p71 itself. It was decided to determine whether a highly efficient nodavirus replication system developed in yeast for heterologous production of proteins, could be used as a method for expressing the capsid protein precursor. The aim of using this system was to determine if VLPs assembled in a replication system specifically encapsidated viral RNA. Transcripts encoding the NwV capsid protein precursor (p70) were generated in yeast cells by replication of a hybrid RNA template by the Nodamura virus (NoV) replicase. Western analysis confirmed the presence of p70 as well as a protein of 62 kDa corresponding to the mature NwV capsid protein. Northern analysis of purified VLPs showed that NoV RNA1 and RNA3 were encapsidated, but no RNA2 was detected. Taken together, the data lead to the conclusion that specific encapsidation of tetraviral RNAs required more than close proximity of the viral RNAs and assembling virus-like particles. Encapsidation specificity in the omegatetraviruses may require additional viral proteins such as p17 during encapsidation or specific viral RNA encapsidation was replication-dependent. Replication-dependent assembly has been shown in the nodaviruses.
- Full Text:
- Date Issued: 2008
- Authors: Tomasicchio, Michele
- Date: 2008
- Subjects: Helicoverpa armigera Imbrasia cytherea Viruses RNA viruses Insects -- Viruses Lepidoptera -- Viruses Saccharomyces cerevisiae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3930 , http://hdl.handle.net/10962/d1003989
- Description: The Tetraviridae are a family of ss (+) RNA viruses that specifically infect lepidopteran insects. Their icosahedral capsids are non-enveloped and approximately 40 nm in diameter with T=4 quasi-equivalent symmetry. The omegatetraviruses, which are structurally the best characterised in the family, include Helicoverpa armigera stunt virus (HaSV) and Nudaurelia capensis omega virus (NwV). The omegatetravirus procapsid is composed of 240 identical copies of the capsid precursor proteins, which undergo autoproteolytic cleavage at its carboxyl-terminus generating the mature capsid protein (b) and γ-peptide. This process occurs in vitro following a shift from pH 7.6 to pH 6.0. The viral capsid encapsidates two ss genomic RNAs: The larger RNA1 encodes the viral replicase as well as three small ORFs while RNA2 encodes the capsid precursor protein together with an overlapping ORF designated P17. While a wealth of structural data pertaining to the assembly and maturation of omegatetraviruses is available, little is known about how this relates to their lifecycle. The principle aim of the research described in this thesis was to use an experimental system developed in the yeast, Saccharomyces cerevisiae, to investigate the assembly of HaSV and NwV virus-like particles (VLPs) in terms of maturation and encapsidation of viral RNAs, in vivo. The yeast expression system used two promoter systems for expression of capsid precursor protein: in the first, a hybrid promoter (PGADH) was used for high-level expression, while the second, PGAL1, produced substantially lower levels of the virus capsid protein precursors. An increase in the level of HaSV capsid protein precursor (p71) via the PGADH promoter resulted in a dramatic increase in VLP assembly as compared with the PGAL system. A protein equivalent to the mature capsid protein (p64) appeared at later time intervals following induction of transcription. Transmission electron microscopic studies showed that p64 correlated with the presence of mature VLPs as opposed to procapsids in cells containing p71. This confirmed that the presence of p64 denoted maturation of VLPs in vivo. Further investigation indicated that maturation correlated with cell aging and the onset of apoptosis. It was shown that induction of apoptosis resulted in VLP maturation while inhibition of apoptosis prevented maturation. These results suggested that the process of apoptosis might be the trigger for maturation of virus procapsids in their host cells. The increase in the efficiency of VLP assembly observed in the high-level expression system was proposed to be due to an increase in the cellular concentrations of viral RNA. To test this hypothesis, HaSV P71 was co-expressed with either P71 mRNA or full length RNA2. An increase in the solubility of p71 was observed in cells expressing increased levels of both RNAs, but there was no increase in the efficiency of VLP assembly. Northern analysis of encapsidated RNAs revealed that there was no selective encapsidation of either P71 mRNA or viral RNA2. This data indicated that the increase in viral RNA was not the reason for increased efficiency of VLP assembly, but most likely resulted from higher concentrations of p71 itself. It was decided to determine whether a highly efficient nodavirus replication system developed in yeast for heterologous production of proteins, could be used as a method for expressing the capsid protein precursor. The aim of using this system was to determine if VLPs assembled in a replication system specifically encapsidated viral RNA. Transcripts encoding the NwV capsid protein precursor (p70) were generated in yeast cells by replication of a hybrid RNA template by the Nodamura virus (NoV) replicase. Western analysis confirmed the presence of p70 as well as a protein of 62 kDa corresponding to the mature NwV capsid protein. Northern analysis of purified VLPs showed that NoV RNA1 and RNA3 were encapsidated, but no RNA2 was detected. Taken together, the data lead to the conclusion that specific encapsidation of tetraviral RNAs required more than close proximity of the viral RNAs and assembling virus-like particles. Encapsidation specificity in the omegatetraviruses may require additional viral proteins such as p17 during encapsidation or specific viral RNA encapsidation was replication-dependent. Replication-dependent assembly has been shown in the nodaviruses.
- Full Text:
- Date Issued: 2008
Application of dermal microdialysis and tape stripping methods to determine the bioavailability and/or bioequivalence of topical ketoprofen formulations
- Tettey-Amlalo, Ralph Nii Okai
- Authors: Tettey-Amlalo, Ralph Nii Okai
- Date: 2008
- Subjects: Drugs -- Therapeutic equivalency Transdermal medication High performance liquid chromatography Nonsteroidal anti-inflammatory agents -- Bioavailability Nonsteroidal anti-inflammatory agents -- Effectiveness Nonsteroidal anti-inflammatory agents -- Testing Nonsteroidal anti-inflammatory agents -- Side effects
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3796 , http://hdl.handle.net/10962/d1003274
- Description: The widespread acceptance of topical formulations intended for local and/or regional activity has prompted renewed interest in developing a model to determine the bioavailability of drugs in order to establish bioequivalence as a means of evaluating formulation performance of multisource products and also for use during formulation development. Current in vivo techniques such as blister suction and skin biopsy amongst others used to determine the bioavailability and/or bioequivalence of topical formulations are either too invasive to generate appropriate concentration-time profiles or require large numbers of study subjects thereby making the study expensive and time-consuming. Moreover, there are currently no sampling techniques that can demonstrate dermal bioavailability and/or bioequivalence of topical formulations intended for local and/or regional activity. Dermal microdialysis is a relatively new application of microdialysis that permits continuous monitoring of endogenous and/or exogenous solutes in the interstitial fluid. The technique is involves the implantation of semi-permeable membranes which are perfused with an isotonic medium at extremely slow flow rates and collection of microlitre sample volumes containing diffused drugs. Tape stripping, a relatively older technique, has been extensively used in comparative bioavailability studies of various topical formulations. However, due to shortcomings arising from reproducibility and inter-subject variation amongst others, the published FDA guidance outlining the initial protocol was subsequently withdrawn. The incorporation of transepidermal water loss with tape stripping has garnered renewed interest and has been used for the determination of drug bioavailability from a number of topical formulations. Hence the primary objective of this research is to develop and evaluate microdialysis sampling and tape stripping techniques, including the incorporation of the determination of transepidermal water loss, to assess the dermal bioavailability of ketoprofen from topical gel formulations and to develop models for bioequivalence assessment. A rapid UPLC-MS/MS method with requisite sensitivity for the analysis of samples generated from dermal microdialysis was developed and validated which accommodated the microlitre sample volumes collected. An HPLC-UV method was developed and validated for the analysis of samples generated from the in vitro microdialysis and in vivo tape stripping studies. The work presented herein contributes to a growing body of scientific knowledge seeking to develop a model for the determination of bioequivalence of pharmaceutically equivalent topical formulations intended for local and/or regional activity in human subjects.
- Full Text:
- Date Issued: 2008
- Authors: Tettey-Amlalo, Ralph Nii Okai
- Date: 2008
- Subjects: Drugs -- Therapeutic equivalency Transdermal medication High performance liquid chromatography Nonsteroidal anti-inflammatory agents -- Bioavailability Nonsteroidal anti-inflammatory agents -- Effectiveness Nonsteroidal anti-inflammatory agents -- Testing Nonsteroidal anti-inflammatory agents -- Side effects
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3796 , http://hdl.handle.net/10962/d1003274
- Description: The widespread acceptance of topical formulations intended for local and/or regional activity has prompted renewed interest in developing a model to determine the bioavailability of drugs in order to establish bioequivalence as a means of evaluating formulation performance of multisource products and also for use during formulation development. Current in vivo techniques such as blister suction and skin biopsy amongst others used to determine the bioavailability and/or bioequivalence of topical formulations are either too invasive to generate appropriate concentration-time profiles or require large numbers of study subjects thereby making the study expensive and time-consuming. Moreover, there are currently no sampling techniques that can demonstrate dermal bioavailability and/or bioequivalence of topical formulations intended for local and/or regional activity. Dermal microdialysis is a relatively new application of microdialysis that permits continuous monitoring of endogenous and/or exogenous solutes in the interstitial fluid. The technique is involves the implantation of semi-permeable membranes which are perfused with an isotonic medium at extremely slow flow rates and collection of microlitre sample volumes containing diffused drugs. Tape stripping, a relatively older technique, has been extensively used in comparative bioavailability studies of various topical formulations. However, due to shortcomings arising from reproducibility and inter-subject variation amongst others, the published FDA guidance outlining the initial protocol was subsequently withdrawn. The incorporation of transepidermal water loss with tape stripping has garnered renewed interest and has been used for the determination of drug bioavailability from a number of topical formulations. Hence the primary objective of this research is to develop and evaluate microdialysis sampling and tape stripping techniques, including the incorporation of the determination of transepidermal water loss, to assess the dermal bioavailability of ketoprofen from topical gel formulations and to develop models for bioequivalence assessment. A rapid UPLC-MS/MS method with requisite sensitivity for the analysis of samples generated from dermal microdialysis was developed and validated which accommodated the microlitre sample volumes collected. An HPLC-UV method was developed and validated for the analysis of samples generated from the in vitro microdialysis and in vivo tape stripping studies. The work presented herein contributes to a growing body of scientific knowledge seeking to develop a model for the determination of bioequivalence of pharmaceutically equivalent topical formulations intended for local and/or regional activity in human subjects.
- Full Text:
- Date Issued: 2008
An interpretive inquiry into girls' educational choices and aspirations: a case study of Murang'a district, Kenya
- Authors: Mwingi, Mweru P
- Date: 2008
- Subjects: Education -- Kenya -- Case studies Education -- Economic aspects -- Kenya -- Case studies Student aspirations -- Kenya -- Case studies Women -- Vocational guidance -- Kenya -- Case studies Sex discrimination in education -- Kenya -- Case studies Sex discrimination against women -- Kenya -- Case studies Sexism in education -- Kenya -- Case studies Women -- Education -- Kenya -- Case studies Educational equalization -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1583 , http://hdl.handle.net/10962/d1003465
- Description: Global consensus on the importance of gender equity in education is perhaps one of the greatest agreements reached in the twentieth century. However, for countries in the sub Saharan African region where disparities of gender are wide and primary education takes priority, secondary education continues to remain in the periphery. As countries make progress towards the attainment of Universal Primary Education (UPE), the concerns for gender equity and equality have become associated with school access and pupil retention. Yet, patterns and trends in school enrollment suggest that disparities of gender are more complex. As lessons are learned from the achievements and challenges of attaining UPE, it is increasingly apparent that gender disparities within education occur in, within and beyond access to schooling. In other words, the challenge of making education gender equal goes beyond school access and school enrollment. Kenya is a signatory to the 1990 Jomtein Declaration on Education For All (EFA). It is also among the few countries in the sub Saharan Africa region with a significantly reduced gender gap in primary and secondary education. This is in tandem with the third of the eight Millennium Development Goals whose aims bear a broad social and economic development agenda. While education equity is important in Kenya and tremendous progress has been made in primary education, beyond the attainment of Universal Primary Education (UPE) there is an even more significant target; gender equity in education both in primary and secondary education by 2015. The attainment of this target requires more than access to schooling and for this reason it poses great challenges to governments and schools. In light of the progress made in Kenya and the need for more equitable education beyond primary education, this study conceives a need for an incisive examination of education equity priority areas in Kenya. The study argues on the need for a shift of concern and debate from primary education to secondary education because the gains of UPE only become meaningful when education equity is secured in secondary education. The study underscores that beyond school access and retention, education output and outcomes need to become prominent variables because they gauge trends and patterns and the quality of gains made where education is claimed to be both accessible and equitable. Using case study method, the study makes a critical interpretation of the schooling experiences, educational choices, preferences and aspirations of girls taking secondary education in single-sex schools in Murang’a district, Kenya. The study shows that girls schooling experiences are not homogenous and that there are contradictions in the ways that girls experience their schooling and make educational choices. It also shows that girls do not necessarily stand good chances with their education simply because they are enrolled in single-sex schools. The study reveals individual subjectivities and schooling culture to be at the centre of the differences between schools and the schooling experiences that girls have. The two have impact on how girls perceive themselves and their abilities, the preferences they nurture and the educational choices they make. The study draws attention to nuances in access and equity within girls’ education. It draws out issues and nuances linked to gender access, equity and equality with respect to school, teacher and subject access. Though the study is not generaliseable, it shows that in contexts where female access and survival is secured, there is need for attention to be paid to the environments that nurture educational choices and preferences so that the high rates in school access become translated into equally high educational output and outcomes.
- Full Text:
- Date Issued: 2008
- Authors: Mwingi, Mweru P
- Date: 2008
- Subjects: Education -- Kenya -- Case studies Education -- Economic aspects -- Kenya -- Case studies Student aspirations -- Kenya -- Case studies Women -- Vocational guidance -- Kenya -- Case studies Sex discrimination in education -- Kenya -- Case studies Sex discrimination against women -- Kenya -- Case studies Sexism in education -- Kenya -- Case studies Women -- Education -- Kenya -- Case studies Educational equalization -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1583 , http://hdl.handle.net/10962/d1003465
- Description: Global consensus on the importance of gender equity in education is perhaps one of the greatest agreements reached in the twentieth century. However, for countries in the sub Saharan African region where disparities of gender are wide and primary education takes priority, secondary education continues to remain in the periphery. As countries make progress towards the attainment of Universal Primary Education (UPE), the concerns for gender equity and equality have become associated with school access and pupil retention. Yet, patterns and trends in school enrollment suggest that disparities of gender are more complex. As lessons are learned from the achievements and challenges of attaining UPE, it is increasingly apparent that gender disparities within education occur in, within and beyond access to schooling. In other words, the challenge of making education gender equal goes beyond school access and school enrollment. Kenya is a signatory to the 1990 Jomtein Declaration on Education For All (EFA). It is also among the few countries in the sub Saharan Africa region with a significantly reduced gender gap in primary and secondary education. This is in tandem with the third of the eight Millennium Development Goals whose aims bear a broad social and economic development agenda. While education equity is important in Kenya and tremendous progress has been made in primary education, beyond the attainment of Universal Primary Education (UPE) there is an even more significant target; gender equity in education both in primary and secondary education by 2015. The attainment of this target requires more than access to schooling and for this reason it poses great challenges to governments and schools. In light of the progress made in Kenya and the need for more equitable education beyond primary education, this study conceives a need for an incisive examination of education equity priority areas in Kenya. The study argues on the need for a shift of concern and debate from primary education to secondary education because the gains of UPE only become meaningful when education equity is secured in secondary education. The study underscores that beyond school access and retention, education output and outcomes need to become prominent variables because they gauge trends and patterns and the quality of gains made where education is claimed to be both accessible and equitable. Using case study method, the study makes a critical interpretation of the schooling experiences, educational choices, preferences and aspirations of girls taking secondary education in single-sex schools in Murang’a district, Kenya. The study shows that girls schooling experiences are not homogenous and that there are contradictions in the ways that girls experience their schooling and make educational choices. It also shows that girls do not necessarily stand good chances with their education simply because they are enrolled in single-sex schools. The study reveals individual subjectivities and schooling culture to be at the centre of the differences between schools and the schooling experiences that girls have. The two have impact on how girls perceive themselves and their abilities, the preferences they nurture and the educational choices they make. The study draws attention to nuances in access and equity within girls’ education. It draws out issues and nuances linked to gender access, equity and equality with respect to school, teacher and subject access. Though the study is not generaliseable, it shows that in contexts where female access and survival is secured, there is need for attention to be paid to the environments that nurture educational choices and preferences so that the high rates in school access become translated into equally high educational output and outcomes.
- 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
A stable isotope approach to trophic ecology resolving food webs in intertidal ecosystems
- Authors: Hill, Jaclyn Marie
- Date: 2008
- Subjects: Stable isotopes Food chains (Ecology) Stable isotopes in ecological research Intertidal ecology Mussels -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5771 , http://hdl.handle.net/10962/d1005459
- Description: There are broad differences in regional oceanography and primary production around the South African coast, which we might expect to give rise to major differences in trophic pathways. δ⁻¹³C and δ⁻¹⁵N isotopic ratios of suspended particulate matter (SPM), mussels, various intertidal consumers and common macroalgae along the South African coastline were explored using stable isotope analysis to investigate biogeographic and temporal variability of isotopic signatures of marine intertidal consumers and their food sources around the coast of South Africa, with a focus on evaluating the dependence of intertidal mussels on phytoplankton and macroalgal-derived organic carbon. Isotopic equilibration rates of four mussel tissues were determined through laboratory feeding experiments, which established that adductor tissue had the slowest isotopic turnover rate, and was subsequently used as an indication of overall mussel diet. Biogeographic, temporal and nearshore/offshore trends of isotopic ratios of SPM were investigated along 10km transects perpendicular to the coast and SPM exhibited overall trends of carbon depletion when moving from west to east along the coastline and from nearshore to offshore water, in both cases suggesting a shift from macrophyte detritus to a phytoplankton signature. δ⁻¹³C signatures of SPM also revealed temporal and biogeographic variation that had strong ties to local oceanography, being closely correlated to regional hydrographic features and tidal influences. Mixing models indicated filter feeders demonstrated over 50% dependence on nearshore SPM for organic carbon and it was possible to categorize them into geographic groups based on their carbon and nitrogen signatures, suggesting biogeographic shifts in resources. Biogeographic shifts in diet were also seen in some grazers. Difficulties in relating macroalgae to mussel diet led to investigations into the isotopic changes associated with macroalgal decomposition. Variation in photosynthetic fractionation, leaching and microbial mineralization are believed to have resulted from species-specific patterns of degradation. Although the strong links between carbon signatures and local oceanography indicate that stable isotope analysis is a powerful tool for the study of water mixing and coastal hydrography in relation to food-web analyses, substantial variation in fractionation of primary consumers, along with different periods of time integration between consumers and their food sources must be considered in future studies, to resolve trophic links in marine food webs successfully.
- Full Text:
- Date Issued: 2008
- Authors: Hill, Jaclyn Marie
- Date: 2008
- Subjects: Stable isotopes Food chains (Ecology) Stable isotopes in ecological research Intertidal ecology Mussels -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5771 , http://hdl.handle.net/10962/d1005459
- Description: There are broad differences in regional oceanography and primary production around the South African coast, which we might expect to give rise to major differences in trophic pathways. δ⁻¹³C and δ⁻¹⁵N isotopic ratios of suspended particulate matter (SPM), mussels, various intertidal consumers and common macroalgae along the South African coastline were explored using stable isotope analysis to investigate biogeographic and temporal variability of isotopic signatures of marine intertidal consumers and their food sources around the coast of South Africa, with a focus on evaluating the dependence of intertidal mussels on phytoplankton and macroalgal-derived organic carbon. Isotopic equilibration rates of four mussel tissues were determined through laboratory feeding experiments, which established that adductor tissue had the slowest isotopic turnover rate, and was subsequently used as an indication of overall mussel diet. Biogeographic, temporal and nearshore/offshore trends of isotopic ratios of SPM were investigated along 10km transects perpendicular to the coast and SPM exhibited overall trends of carbon depletion when moving from west to east along the coastline and from nearshore to offshore water, in both cases suggesting a shift from macrophyte detritus to a phytoplankton signature. δ⁻¹³C signatures of SPM also revealed temporal and biogeographic variation that had strong ties to local oceanography, being closely correlated to regional hydrographic features and tidal influences. Mixing models indicated filter feeders demonstrated over 50% dependence on nearshore SPM for organic carbon and it was possible to categorize them into geographic groups based on their carbon and nitrogen signatures, suggesting biogeographic shifts in resources. Biogeographic shifts in diet were also seen in some grazers. Difficulties in relating macroalgae to mussel diet led to investigations into the isotopic changes associated with macroalgal decomposition. Variation in photosynthetic fractionation, leaching and microbial mineralization are believed to have resulted from species-specific patterns of degradation. Although the strong links between carbon signatures and local oceanography indicate that stable isotope analysis is a powerful tool for the study of water mixing and coastal hydrography in relation to food-web analyses, substantial variation in fractionation of primary consumers, along with different periods of time integration between consumers and their food sources must be considered in future studies, to resolve trophic links in marine food webs successfully.
- 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
A bioinorganic study of some cobalt(II) Schiff base complexes of variously substituted hydroxybenzaldimines
- Authors: Shaibu, Rafiu Olarewaju
- Date: 2008
- Subjects: Cobalt Schiff bases Artemia Spectrum analysis Ligands -- Analysis Bioinorganic chemistry Antineoplastic agents Cancer -- Chemotherapy Ligands -- Toxicity
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4394 , http://hdl.handle.net/10962/d1006009
- Description: Syntheses of Schiff bases were carried out by reacting salicylaldyhde, ortho-vanillin, para-vanillin or vanillin with aniline, 1-aminonaphthalene, 4- and 3-aminopyridine, and also with 2- and 3-aminomethylpyridine. The various Schiff bases obtained from the condensation reaction were reacted with CoCl₂.6H₂0, triethylamine stripped CoCl₂.6H₂0 or Co(CH₃COO)₂ to form cobalt(Il) complexes of ratio 2:1. The complexes obtained from cobalt chloride designated as the "A series" are of the general formulae ML₂X₂.nH₂0 , (L = Schiff base, X = chlorine) while those obtained from cobalt acetate or triethylamine stripped cobalt chloride denoted as "B" and C" are of the general formulae ML₂. nH₂0. The few complexes that do not follow the general formulae highlighted above are: IA [M(HL)₃.Cl₂], (L = N-phenylsalicylaldimine), 4A = (MLCl₂), (L = N-phenylvanaldiminato), 7 A and 21 A (ML₂), (L = N-naphthyl-o-vanaldiminato, and N-methy-2-pyridylsalicylaldiminato respectively), 8A = MLCI, (L = N-naphthylvanaldiminato), 12A = M₂L₃Cl₂, (L = N-4-pyridylvanaldiminato), 15A (MLCI), (L = N-3-pyridyl-o-vanaldiminato). The ligands and their complexes were characterized using elemental analyses and cobalt analysis using ICP, FT-IR spectroscopy (mid and far-IR), NIR-UV/vis (diffuse reflectance), UV/vis in an aprotic and a protic solvents, while mass spectrometry, ¹HNMR and ¹³CNMR, was used to further characterized the ligands. The tautomeric nature of the Schiff bases were determined by examining the behaviour of Schiff bases and their complexes in a protic (e.g. MeOH) and non-protic (e.g. DMF) polar solvents. The effects of solvents on the electronic behaviour of the compounds were also examined. Using CDCl₃, the NMR technique was further used to confirm the structures of the Schiff bases. The tentative geometry of the complexes was determined using the spectra information obtained from the far infrared and the diffuse reflectance spectroscopy. With few exceptions, most of the "A" series are tetrahedral or distorted tetrahedral, while the "B + C" are octahedral or pseudooctahedral. A small number of complexes are assigned square-planar geometry owing to the characteristic spectral behaviour shown. In order to determine their biological activity, two biological assay methods (antimicrobial testing and brine shrimp lethality assay) were used. Using disc method, the bacteriostatic and fungicidal activities of the various Schiff bases and their respective complexes to Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa as well as Aspergillus niger, were measured and the average inhibition zones are tabulated and analysed. Both the Schiff bases and their complexes showed varying bacteriostatic and fungicidal activity against the bacteria and fungus tested. The inhibition activity is concentration dependent and potential antibiotic and fungicides are identified. To determine the toxicity of the ligands and their corresponding cobalt(II) complexes, brine shrimp lethality assay was used. The LD₅₀ of the tested compounds were calculated and the results obtained were tabulated for comparison.
- Full Text:
- Date Issued: 2008
- Authors: Shaibu, Rafiu Olarewaju
- Date: 2008
- Subjects: Cobalt Schiff bases Artemia Spectrum analysis Ligands -- Analysis Bioinorganic chemistry Antineoplastic agents Cancer -- Chemotherapy Ligands -- Toxicity
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4394 , http://hdl.handle.net/10962/d1006009
- Description: Syntheses of Schiff bases were carried out by reacting salicylaldyhde, ortho-vanillin, para-vanillin or vanillin with aniline, 1-aminonaphthalene, 4- and 3-aminopyridine, and also with 2- and 3-aminomethylpyridine. The various Schiff bases obtained from the condensation reaction were reacted with CoCl₂.6H₂0, triethylamine stripped CoCl₂.6H₂0 or Co(CH₃COO)₂ to form cobalt(Il) complexes of ratio 2:1. The complexes obtained from cobalt chloride designated as the "A series" are of the general formulae ML₂X₂.nH₂0 , (L = Schiff base, X = chlorine) while those obtained from cobalt acetate or triethylamine stripped cobalt chloride denoted as "B" and C" are of the general formulae ML₂. nH₂0. The few complexes that do not follow the general formulae highlighted above are: IA [M(HL)₃.Cl₂], (L = N-phenylsalicylaldimine), 4A = (MLCl₂), (L = N-phenylvanaldiminato), 7 A and 21 A (ML₂), (L = N-naphthyl-o-vanaldiminato, and N-methy-2-pyridylsalicylaldiminato respectively), 8A = MLCI, (L = N-naphthylvanaldiminato), 12A = M₂L₃Cl₂, (L = N-4-pyridylvanaldiminato), 15A (MLCI), (L = N-3-pyridyl-o-vanaldiminato). The ligands and their complexes were characterized using elemental analyses and cobalt analysis using ICP, FT-IR spectroscopy (mid and far-IR), NIR-UV/vis (diffuse reflectance), UV/vis in an aprotic and a protic solvents, while mass spectrometry, ¹HNMR and ¹³CNMR, was used to further characterized the ligands. The tautomeric nature of the Schiff bases were determined by examining the behaviour of Schiff bases and their complexes in a protic (e.g. MeOH) and non-protic (e.g. DMF) polar solvents. The effects of solvents on the electronic behaviour of the compounds were also examined. Using CDCl₃, the NMR technique was further used to confirm the structures of the Schiff bases. The tentative geometry of the complexes was determined using the spectra information obtained from the far infrared and the diffuse reflectance spectroscopy. With few exceptions, most of the "A" series are tetrahedral or distorted tetrahedral, while the "B + C" are octahedral or pseudooctahedral. A small number of complexes are assigned square-planar geometry owing to the characteristic spectral behaviour shown. In order to determine their biological activity, two biological assay methods (antimicrobial testing and brine shrimp lethality assay) were used. Using disc method, the bacteriostatic and fungicidal activities of the various Schiff bases and their respective complexes to Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa as well as Aspergillus niger, were measured and the average inhibition zones are tabulated and analysed. Both the Schiff bases and their complexes showed varying bacteriostatic and fungicidal activity against the bacteria and fungus tested. The inhibition activity is concentration dependent and potential antibiotic and fungicides are identified. To determine the toxicity of the ligands and their corresponding cobalt(II) complexes, brine shrimp lethality assay was used. The LD₅₀ of the tested compounds were calculated and the results obtained were tabulated for comparison.
- 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
"A complex and delicate web" : a comparative study of selected speculative novels by Margaret Atwood, Ursula K. Le Guin, Doris Lessing and Marge Piercy
- Authors: Glover, Jayne Ashleigh
- Date: 2008
- Subjects: Atwood, Margaret Eleanor, 1939- -- Criticism and interpretation Le Guin, Ursula K., 1929- -- Criticism and interpretation Lessing, Doris May, 1919- -- Criticism and interpretation Piercy, Marge Piercy, Marge -- Criticism and interpretation Utopias in literature Dystopias in literature Science fiction, English -- History and criticism Fantasy fiction -- History and criticism Fantasy literature -- History and criticism Women authors -- 20th Century Women authors -- 21st Century English fiction -- 20th Century English fiction -- 21st Century
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2199 , http://hdl.handle.net/10962/d1002241
- Description: This thesis examines selected speculative novels by Margaret Atwood, Ursula K. Le Guin, Doris Lessing and Marge Piercy. It argues that a specifiable ecological ethic can be traced in their work – an ethic which is explored by them through the tensions between utopian and dystopian discourses. The first part of the thesis begins by theorising the concept of an ecological ethic of respect for the Other through current ecological philosophies, such as those developed by Val Plumwood. Thereafter, it contextualises the novels within the broader field of science fiction, and speculative fiction in particular, arguing that the shift from a critical utopian to a critical dystopian style evinces their changing treatment of this ecological ethic within their work. The remainder of the thesis is divided into two parts, each providing close readings of chosen novels in the light of this argument. Part Two provides a reading of Le Guin’s early Hainish novels, The Left Hand of Darkness, The Word for World is Forest and The Dispossessed, followed by an examination of Piercy’s Woman on the Edge of Time, Lessing’s The Marriages Between Zones Three, Four and Five, and Atwood’s The Handmaid’s Tale. The third, and final, part of the thesis consists of individual chapters analysing the later speculative novels of each author. Piercy’s He, She and It, Le Guin’s The Telling, and Atwood’s Oryx and Crake are all scrutinised, as are Lessing’s two recent ‘Ifrik’ novels. This thesis shows, then, that speculative fiction is able to realise through fiction many of the ideals of ecological thinkers. Furthermore, the increasing dystopianism of these novels reflects the greater urgency with which the problem of Othering needs to be addressed in the light of the present global ecological crisis.
- Full Text:
- Date Issued: 2008
- Authors: Glover, Jayne Ashleigh
- Date: 2008
- Subjects: Atwood, Margaret Eleanor, 1939- -- Criticism and interpretation Le Guin, Ursula K., 1929- -- Criticism and interpretation Lessing, Doris May, 1919- -- Criticism and interpretation Piercy, Marge Piercy, Marge -- Criticism and interpretation Utopias in literature Dystopias in literature Science fiction, English -- History and criticism Fantasy fiction -- History and criticism Fantasy literature -- History and criticism Women authors -- 20th Century Women authors -- 21st Century English fiction -- 20th Century English fiction -- 21st Century
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2199 , http://hdl.handle.net/10962/d1002241
- Description: This thesis examines selected speculative novels by Margaret Atwood, Ursula K. Le Guin, Doris Lessing and Marge Piercy. It argues that a specifiable ecological ethic can be traced in their work – an ethic which is explored by them through the tensions between utopian and dystopian discourses. The first part of the thesis begins by theorising the concept of an ecological ethic of respect for the Other through current ecological philosophies, such as those developed by Val Plumwood. Thereafter, it contextualises the novels within the broader field of science fiction, and speculative fiction in particular, arguing that the shift from a critical utopian to a critical dystopian style evinces their changing treatment of this ecological ethic within their work. The remainder of the thesis is divided into two parts, each providing close readings of chosen novels in the light of this argument. Part Two provides a reading of Le Guin’s early Hainish novels, The Left Hand of Darkness, The Word for World is Forest and The Dispossessed, followed by an examination of Piercy’s Woman on the Edge of Time, Lessing’s The Marriages Between Zones Three, Four and Five, and Atwood’s The Handmaid’s Tale. The third, and final, part of the thesis consists of individual chapters analysing the later speculative novels of each author. Piercy’s He, She and It, Le Guin’s The Telling, and Atwood’s Oryx and Crake are all scrutinised, as are Lessing’s two recent ‘Ifrik’ novels. This thesis shows, then, that speculative fiction is able to realise through fiction many of the ideals of ecological thinkers. Furthermore, the increasing dystopianism of these novels reflects the greater urgency with which the problem of Othering needs to be addressed in the light of the present global ecological crisis.
- Full Text:
- Date Issued: 2008