Metallophthalocyanines as photocatalysts for transformation of chlorophenols and self-assembled monolayers for electrochemical detection of thiols and cyanides
- Authors: Ozoemena, Kenneth Ikechukwu
- Date: 2003
- Subjects: Electrochemistry Cyanides Thiols Chlorophenols Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4089 , http://hdl.handle.net/10962/d1007709
- Description: Photochemical properties of sulphonated phthalocyanine complexes of aluminium, zinc, tin and silicon, and octa-carboxyphthalocyanine complexes of aluminium and zinc have been investigated. These water-soluble metallophthalocyanine (MPc) complexes, especially the sulphonated aluminium and zinc phthalocyanines, were found to be good photosensitisers for the transformation of the toxic mono-, tri- and penta-chlorophenols in aqueous solutions. The efficiency of MPc sensitiser towards photo-transformation of chlorophenols depends on its effectiveness to generate singlet oxygen as well as its photostability. Octa-substituted thiol-derivatised phthalocyanine complexes of cobalt, iron and zinc were synthesized and their spectral and electrochemical properties investigated. The photochemical properties ofthe zinc phthalocyanine complexes in non-aqueous solutions were comparable to those in literature. Ultrathin films of the octasubstituted thiol-derivatised phthalocyanine complexes of cobalt, iron and zinc were, for the first time, immobilized onto gold electrodes using the self-assembling technique. Surface electrochemistry indicates that the ultrathin films are surface-confined self-assembled monolayer (SAM) species. Gold electrodes modified with the redox-active SAMs of cobalt and iron phthalocyanine complexes proved to be potential electrochemical sensors for the detection of thiols (L-cysteine, homocysteine and penicillamine) and thiocyanate in aqueous solutions (pH 4). The limits of detection for the thiols and thiocyanate were in the range of ∼ 10⁻⁷ and 10⁻⁶ mol dm⁻³, respectively. The modification process was reproducible and the modified electrodes showed good stability and, if stored in pH 4 buffer solutions, could be used for the analysis of thiols and thiocyanate for about a month without the need for recalibration. Etching of gold marred electrochemical detection of cyanide with the MPc-SAM-modified gold electrodes. Interestingly, however, kinetic and equilibria studies revealed strong interaction of octabutylthiophthalocyaninatoiron (II), FeOBTPc, with cyanide in both DMF and DMSO solutions.
- Full Text:
- Date Issued: 2003
- Authors: Ozoemena, Kenneth Ikechukwu
- Date: 2003
- Subjects: Electrochemistry Cyanides Thiols Chlorophenols Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4089 , http://hdl.handle.net/10962/d1007709
- Description: Photochemical properties of sulphonated phthalocyanine complexes of aluminium, zinc, tin and silicon, and octa-carboxyphthalocyanine complexes of aluminium and zinc have been investigated. These water-soluble metallophthalocyanine (MPc) complexes, especially the sulphonated aluminium and zinc phthalocyanines, were found to be good photosensitisers for the transformation of the toxic mono-, tri- and penta-chlorophenols in aqueous solutions. The efficiency of MPc sensitiser towards photo-transformation of chlorophenols depends on its effectiveness to generate singlet oxygen as well as its photostability. Octa-substituted thiol-derivatised phthalocyanine complexes of cobalt, iron and zinc were synthesized and their spectral and electrochemical properties investigated. The photochemical properties ofthe zinc phthalocyanine complexes in non-aqueous solutions were comparable to those in literature. Ultrathin films of the octasubstituted thiol-derivatised phthalocyanine complexes of cobalt, iron and zinc were, for the first time, immobilized onto gold electrodes using the self-assembling technique. Surface electrochemistry indicates that the ultrathin films are surface-confined self-assembled monolayer (SAM) species. Gold electrodes modified with the redox-active SAMs of cobalt and iron phthalocyanine complexes proved to be potential electrochemical sensors for the detection of thiols (L-cysteine, homocysteine and penicillamine) and thiocyanate in aqueous solutions (pH 4). The limits of detection for the thiols and thiocyanate were in the range of ∼ 10⁻⁷ and 10⁻⁶ mol dm⁻³, respectively. The modification process was reproducible and the modified electrodes showed good stability and, if stored in pH 4 buffer solutions, could be used for the analysis of thiols and thiocyanate for about a month without the need for recalibration. Etching of gold marred electrochemical detection of cyanide with the MPc-SAM-modified gold electrodes. Interestingly, however, kinetic and equilibria studies revealed strong interaction of octabutylthiophthalocyaninatoiron (II), FeOBTPc, with cyanide in both DMF and DMSO solutions.
- Full Text:
- Date Issued: 2003
Molecular characterization of the tetratricopeptide repeat-mediated interactions of murine stress-inducible protein 1 with major heat shock proteins
- Authors: Odunuga, Odutayo Odutola
- Date: 2003
- Subjects: Plants -- Effect of stress on Proteins -- Purification Electrophoresis Heat shock proteins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4091 , http://hdl.handle.net/10962/d1007724
- Description: Murine stress-inducible protein 1 (mSTI1) is a co-chaperone that is homologous with the human heat shock protein 70 (Hsp70)/heat shock protein 90 (Hsp90)-organizing protein (Hop). The two proteins are homologues of the highly conserved stress-inducible protein 1 (STI1) family of co-chaperones. The STI1 proteins interact directly and simultaneously at some stage, with Hsp70 and Hsp90 in the formation of the hetero-multi-chaperone complexes that facilitate the folding of signal transducing kinases and functional maturation of steroid hormone receptors. The interactions of mSTI1 with both Hsp70 and Hsp90 is mediated by a versatile structural protein-protein interaction motif, the tetratricopeptide repeat (TPR). The TPR motif is a degenerate 34-amino acid sequence a-helical structural motif found in a significant number of functionally unrelated proteins. This study was aimed at characterizing the structural and functional determinants in the TPR domains of mSTI1 responsible for binding to and discriminating between Hsp70 and Hsp90. Guided by data from Hop's crystal structures and amino acid sequence alignment analyses, various biochemical techniques were used to both qualitatively and quantitatively characterize the contacts necessary for the N-terminal TPR domain (TPR1) of mSTI1 to bind to the C-terminal EEVD motif of heat shock cognate protein 70 (Hsc70) and to discriminate between Hsc70 and Hsp90. Substitutions in the first TPR motif of Lys⁸ or Asn¹² did not affect binding of mSTI1 to Hsc70, while double substitution of these residues abrogated binding. A substitution in the second TPR motif of Asn⁴³ lowered but did not abrogate binding. Similarly, a deletion in the second TPR motif coupled with a substitution of Lys⁸ or Asn¹² reduced but did not abrogate binding. Steady state fluorescence and circular dichroism spectroscopies revealed that the double substitution of Lys⁸ and Asn¹² resulted in perturbations of inter-domain interactions in mSTl1. Together these results suggest that mSTI1-Hsc70 interaction requires a network of electrostatic interactions not only between charged residues in the TPR1 domain of mSTI1 and the EEVD motif of Hsc70, but also outside the TPR1 domain. It is proposed that the electrostatic interactions in the first TPR motif collectively made by Lys⁸ and Asn¹² define part of the minimum interactions required for successful mSTI1-Hsc70 interaction. In the first central TPR domain (TPR1A), single substitution of Lys³°¹ was sufficient to abrogate the mSTI1-Hsp90 interaction. Using a truncated derivative of mSTI1 incapable of binding to Hsp90, residues predicted by crystallographic data to determine Hsp70 binding specificity were substituted in the TPR1 domain. The modified protein had reduced binding to Hsc70, but showed significant binding capacity for Hsp90. In contrast, topologically equivalent substitutions on a truncated derivative of mSTI1 incapable of binding to Hsc70 did not confer Hsc70 specificity on the TPR2A domain. These data suggest that binding of Hsc70 to the TPR1 domain is more specific than binding of Hsp90 to the TPR2A domain. In addition, residues C-terminal of helix A in the second TPR motif of mSTI1 were shown to be important in determining specific binding to Hsc70. Binding assays using surface plasmon resonance spectroscopy showed that the affinities of binding of mSTI1 to Hsc70 and Hsp90 were 2 μM and 1.5 μM respectively. Preliminary in vivo studies revealed differences in the dynamics of binding of endogenous and exogenous recombinant mSTI1 with Hsc70 and Hsp90. The outcome of this study poses serious implications for the mechanisms of mSTI1 interactions with Hsc70 and Hsp90 in the cell.
- Full Text:
- Date Issued: 2003
- Authors: Odunuga, Odutayo Odutola
- Date: 2003
- Subjects: Plants -- Effect of stress on Proteins -- Purification Electrophoresis Heat shock proteins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4091 , http://hdl.handle.net/10962/d1007724
- Description: Murine stress-inducible protein 1 (mSTI1) is a co-chaperone that is homologous with the human heat shock protein 70 (Hsp70)/heat shock protein 90 (Hsp90)-organizing protein (Hop). The two proteins are homologues of the highly conserved stress-inducible protein 1 (STI1) family of co-chaperones. The STI1 proteins interact directly and simultaneously at some stage, with Hsp70 and Hsp90 in the formation of the hetero-multi-chaperone complexes that facilitate the folding of signal transducing kinases and functional maturation of steroid hormone receptors. The interactions of mSTI1 with both Hsp70 and Hsp90 is mediated by a versatile structural protein-protein interaction motif, the tetratricopeptide repeat (TPR). The TPR motif is a degenerate 34-amino acid sequence a-helical structural motif found in a significant number of functionally unrelated proteins. This study was aimed at characterizing the structural and functional determinants in the TPR domains of mSTI1 responsible for binding to and discriminating between Hsp70 and Hsp90. Guided by data from Hop's crystal structures and amino acid sequence alignment analyses, various biochemical techniques were used to both qualitatively and quantitatively characterize the contacts necessary for the N-terminal TPR domain (TPR1) of mSTI1 to bind to the C-terminal EEVD motif of heat shock cognate protein 70 (Hsc70) and to discriminate between Hsc70 and Hsp90. Substitutions in the first TPR motif of Lys⁸ or Asn¹² did not affect binding of mSTI1 to Hsc70, while double substitution of these residues abrogated binding. A substitution in the second TPR motif of Asn⁴³ lowered but did not abrogate binding. Similarly, a deletion in the second TPR motif coupled with a substitution of Lys⁸ or Asn¹² reduced but did not abrogate binding. Steady state fluorescence and circular dichroism spectroscopies revealed that the double substitution of Lys⁸ and Asn¹² resulted in perturbations of inter-domain interactions in mSTl1. Together these results suggest that mSTI1-Hsc70 interaction requires a network of electrostatic interactions not only between charged residues in the TPR1 domain of mSTI1 and the EEVD motif of Hsc70, but also outside the TPR1 domain. It is proposed that the electrostatic interactions in the first TPR motif collectively made by Lys⁸ and Asn¹² define part of the minimum interactions required for successful mSTI1-Hsc70 interaction. In the first central TPR domain (TPR1A), single substitution of Lys³°¹ was sufficient to abrogate the mSTI1-Hsp90 interaction. Using a truncated derivative of mSTI1 incapable of binding to Hsp90, residues predicted by crystallographic data to determine Hsp70 binding specificity were substituted in the TPR1 domain. The modified protein had reduced binding to Hsc70, but showed significant binding capacity for Hsp90. In contrast, topologically equivalent substitutions on a truncated derivative of mSTI1 incapable of binding to Hsc70 did not confer Hsc70 specificity on the TPR2A domain. These data suggest that binding of Hsc70 to the TPR1 domain is more specific than binding of Hsp90 to the TPR2A domain. In addition, residues C-terminal of helix A in the second TPR motif of mSTI1 were shown to be important in determining specific binding to Hsc70. Binding assays using surface plasmon resonance spectroscopy showed that the affinities of binding of mSTI1 to Hsc70 and Hsp90 were 2 μM and 1.5 μM respectively. Preliminary in vivo studies revealed differences in the dynamics of binding of endogenous and exogenous recombinant mSTI1 with Hsc70 and Hsp90. The outcome of this study poses serious implications for the mechanisms of mSTI1 interactions with Hsc70 and Hsp90 in the cell.
- Full Text:
- Date Issued: 2003
Multivariate morphometric analysis and behaviour of honeybees (Apis Mellifera L.) in the southern regions of Ethiopia
- Authors: Amssalu, Argaw Bezabeh
- Date: 2003
- Subjects: Honeybee -- Ethiopia -- Behavior Honeybee -- Ethiopia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5616 , http://hdl.handle.net/10962/d1003130
- Description: Morphometric and behavioural characteristics of honeybees, Apis mellifera were analysed using multivariate and bivariate statistical methods to characterise honeybees of southern Ethiopian region. A total of 33800 morphometric character measurements were taken from 2600 individual worker honeybees of 130 honeybee colonies collected at 26 sampling localities with an average inter-locality distance of 89km to determine the occurrence of morphoclusters. 117 experienced farmer beekeepers and beekeeping experts were interviewed on pre-tested questionnaire to investigate the behavioural characteristics of these honeybees in their respective areas. Morphometric characters associated with pigmentation and body size exhibited a higher discriminant power while forewing venation angles (B4, N23 and 026) lack discriminatory power to segregate honeybees in the southern Ethiopian region. Principal components and discriminant analyses using the most discriminatory morphological characters delineated four statistically distinct morphoclusters in the southern Ethiopian region: the smallest and yellow honeybees, A. m. woyi-gambella which are different from all African honeybees, occur in the western and southern lowlands; the small and yellowiest honeybees, Apis mellifera jemenitica in the eastern escarpment; the largest and darkest honeybees, Apis mellifera bandasii in the central and eastern highlands; and dark honeybees, Apis mellifera scutellata in the wet tropical forests. High intracolonial and intercolonial variances within and between the boundaries of the honeybee groups were detected. The former suggests areas of ecological instability, while the latter areas of transitional or natural hybridisation zones. These areas are characterised by transitional ecological zones having intermediate climate and physiography. Even though honeybees of the southern Ethiopian region are generally dark and small, they show a high tendency to reproductive swarming, migration and aggressiveness, great variation in pigmentation, size and behaviour were observed both within and between the groups. A. m. jemenitica honeybees have a high propensity to migration and less a tendency for reproductive swarming. A. m. bandasii and A. m. scutellata have a high inclination to reproductive swarming and the former has a lesser and the later intermediate propensity to migration. A. m. woyi-gambella honeybees have intermediate swarming and migration tendencies. These results revealed that reproductive swarming and migration are higher in resource-rich and resource-poor areas respectively. Honey plants of the central highlands of Ethiopia are predominantly herbaceous in nature and mainly grow on open and cultivated lands. The bulk of pollen collected came comparatively from few genera. Strong correlation was observed between the intensities of flowering and rainfall. Reproductive swarming and migration occur during high and low intensity of flowering respectively.
- Full Text:
- Date Issued: 2003
- Authors: Amssalu, Argaw Bezabeh
- Date: 2003
- Subjects: Honeybee -- Ethiopia -- Behavior Honeybee -- Ethiopia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5616 , http://hdl.handle.net/10962/d1003130
- Description: Morphometric and behavioural characteristics of honeybees, Apis mellifera were analysed using multivariate and bivariate statistical methods to characterise honeybees of southern Ethiopian region. A total of 33800 morphometric character measurements were taken from 2600 individual worker honeybees of 130 honeybee colonies collected at 26 sampling localities with an average inter-locality distance of 89km to determine the occurrence of morphoclusters. 117 experienced farmer beekeepers and beekeeping experts were interviewed on pre-tested questionnaire to investigate the behavioural characteristics of these honeybees in their respective areas. Morphometric characters associated with pigmentation and body size exhibited a higher discriminant power while forewing venation angles (B4, N23 and 026) lack discriminatory power to segregate honeybees in the southern Ethiopian region. Principal components and discriminant analyses using the most discriminatory morphological characters delineated four statistically distinct morphoclusters in the southern Ethiopian region: the smallest and yellow honeybees, A. m. woyi-gambella which are different from all African honeybees, occur in the western and southern lowlands; the small and yellowiest honeybees, Apis mellifera jemenitica in the eastern escarpment; the largest and darkest honeybees, Apis mellifera bandasii in the central and eastern highlands; and dark honeybees, Apis mellifera scutellata in the wet tropical forests. High intracolonial and intercolonial variances within and between the boundaries of the honeybee groups were detected. The former suggests areas of ecological instability, while the latter areas of transitional or natural hybridisation zones. These areas are characterised by transitional ecological zones having intermediate climate and physiography. Even though honeybees of the southern Ethiopian region are generally dark and small, they show a high tendency to reproductive swarming, migration and aggressiveness, great variation in pigmentation, size and behaviour were observed both within and between the groups. A. m. jemenitica honeybees have a high propensity to migration and less a tendency for reproductive swarming. A. m. bandasii and A. m. scutellata have a high inclination to reproductive swarming and the former has a lesser and the later intermediate propensity to migration. A. m. woyi-gambella honeybees have intermediate swarming and migration tendencies. These results revealed that reproductive swarming and migration are higher in resource-rich and resource-poor areas respectively. Honey plants of the central highlands of Ethiopia are predominantly herbaceous in nature and mainly grow on open and cultivated lands. The bulk of pollen collected came comparatively from few genera. Strong correlation was observed between the intensities of flowering and rainfall. Reproductive swarming and migration occur during high and low intensity of flowering respectively.
- Full Text:
- Date Issued: 2003
On the use of metabolic rate measurements to assess the stress response in juvenile spotted grunter, Pomadasys commersonnii (Haemulidae, Pisces)
- Authors: Radull, John
- Date: 2003
- Subjects: Fishes -- Metabolism Fishes -- Physiology Pomadasys -- Physiology Grunts (Fishes) -- Physiology Stress (Psychology) Stress (Physiology)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5350 , http://hdl.handle.net/10962/d1007564
- Description: Quantitication of stress requires the use of a stress indicator that is easy to measure, and which can be readily interpreted in terms of the potential long-term effects to an organism. This study evaluates the suitability of metabolic rate as an indicator of the stress response in fish. By comparing the metabolic with the cortisol stress response, the most commonly used indicator of stress in fish, it was possible to assess the suitability of metabolic rate as a stress indicator. Changes in metabolic rate were used to predict the long-term effects of transport-related stressors. This study also detennined the baseline metabolic rates of the tish. The standard and the active metabolic rates of juvenile P. cummersonnii were 0.16 ± 0.02 (mean ± S.D, n = 6) mg O₂g⁻¹h⁻¹, and 0.56 ± 0.04 mg O₂g⁻¹h⁻¹, respectively, whereas the routine metabolic rate for the fish was 0.25 ± 0.03 mg O₂g⁻¹h¹. The relationship between metabolic rate and body weight was described by the equation ϺO₂ = 0.64 W⁻°·³⁸. 24-h oxygen consumption measurements showed that juvenile P. commersonnii exhibited diel rhythmicity in oxygen consumption rate, the higher rates occurring at night and the lower rates during the daytime. The higher nocturnal metabolic activity may have been due to increased activity induced by an endogenous rhythm related to feeding. Diel rhythmicity has direct implications for the measurement of baseline metabolic rates since it could result in overestimation or underestimation of these rates. 24-h continuous oxygen consumption measurements enabled the detection of the rhythmicity in oxygen consumption rate, and thereby ensured a greater degree of accuracy in the estimation of these parameters. The metabolic stress response in juvenile P. commersonnii was best described by the equation, y = -0.0013 x² + 0.0364 x ÷ 0.3052, where x = time after application of stressor, and y = oxygen consumption rate. Using the derivative of this equation, the metabolic stress response was estimated to peak approximately 14 min after application of a simulated capture and handling stressor. Oxygen consumption increased by about 300 % as a result of the stress. Approximately 15 min after application of a similar stressor, plasma cortisol levels in stressed fish was 200 % higher than baseline levels. However, cortisol levels in fish sampled 30 min after the disturbance was similar to the baseline cortisol levels, indicating that full recovery had occurred. Although the patterns in the metabolic and cortisol stress responses were similar, metabolic rate could be measured continuously, thereby ensuring accurate interpretation of the data. Furthermore, increases in metabolic rate during the stress response are a culmination of physiological events from the primary to the tertiary levels of biological organization and are, therefore, easier to interpret in terms of long-term effects on the fish. Different transportation procedures elicited variable degrees of stress in juvenile P. commersonnii. The cost of metabolism attributed to the effects of capture and handling was twice as much as that attributed to acute temperature elevation. Acute temperature decrease resulted in a signiticant reduction in the oxygen consumption rate (ANOVA, P < 0.05). Oxygen consumption by the fish was not affected by fish density (ANOVA: F = 2.002, P = 0.5), or by oxygen depletion at dissolved oxygen concentrations above the critical level. Below this level, however, oxygen consumption decreased linearly with further decrease in dissolved oxygen concentration. These results showed that the highest energetic cost to juvenile P. commersonnii was incurred as a result of capture and handling. The results also showed that by subjecting fish to different stressors, it was possible to categorize them according to their relative metabolic costs to the fish. At 25º C, the effective concentration of 2-phenoxyethanol to fully anaesthetize (Stage IV, McFarland 1960) juvenile P. commersonnii was 0.4 ml l⁻¹ and the most appropriate concentration for deep sedation (Stage II, McFarland 1960) of the fish for at least 24 h was 0.2 ml l⁻¹. A maximum of 3 minutes was required by the fish to recover from the effects of the anaesthetic. There was no correlation between fish weight and the rate of induction of anaesthesia (r² = 0.001, p = 0.3). At the peak of the metabolic stress response, oxygen consumption was twice as high in the un-anaesthetized fish compared to the fish anaesthetized after the application of the simulated capture and handling stressor, suggesting that anaesthetization with 2-phenoxyethanol may have reduced the effect of the disturbance on the fish. Similar oxygen consumption rates for the fish anaesthetized prior to capture and the non-stressed fish suggested that the increases in metabolic rate could be linked to the struggling associated with attempts by fish to escape from the perceived stressor. Anaesthetization of juvenile P. commersonnii with 0.3 ml l⁻¹ 2-phenoxyethanol resulted in a more than 200 % increase in plasma cortisol concentration. The elevated levels of plasma cortisol in the anaesthetized fish suggested a manifestation of 2-phenoxyethanol as a stressor. At the time of capture, cortisol levels in fish that were anaesthetized prior to capture were the same as those measured in the disturbed fish at the peak of the stress response (ANOVA, p = 0.95), suggesting that the anaesthetized fish were already experiencing considerable stress at the time they were captured. Undisturbed juvenile P. commersonnii that were anaesthetized for 1 h also had cortisol levels that were five times higher than those measured in undisturbed-unanaesthetized fish, indicating that the duration of exposure to the anaesthetic had a significant effect on plasma cortisol levels. The results presented in this study demonstrate the usefulness of metabolic rate as an indicator of acute stress in fish. This was achieved by comparing the metabolic and the cortisol stress responses. The ease and accuracy with which oxygen consumption of fish could be measured made it possible to measure the stress response more accurately than by plasma cortisol concentration. It was also possible to monitor metabolic rate continuously over a long duration using polarographic oxygen sensors, thus enabling a better evaluation of the stress response. These results, thus, suggest that metabolic rate measurements could be a more practical way to quantify the effects of acute stressors on juvenile fishes. By detailing the profile of the metabolic stress response in P. commersonnii, this study makes a contribution towards understanding the physiological effects of stress in fishes. The study also contributes towards the quantification of baseline metabolic rates of this species under captivity. This study also contributes towards understanding the effects of 2-phenoxyethanol on the stress physiology of fish. By anaesthetizing fish under different conditions of stress, it was possible to evaluate the effect of 2-phenoxyethanol on the metabolic stress response. The ability of 2-phenoxyethanol to reduce physical activity of the fish, and thereby reduce the impact of acute stress on the metabolic stress response, makes it a good agent for the mitigation of stress during the capture and handling of fish. However, the increase in plasma cortisol concentration during prolonged anaesthetization using this drug suggests that the anaesthetic might be a stressor to fish and may, therefore, not be suitable for long-term sedation.
- Full Text:
- Date Issued: 2003
- Authors: Radull, John
- Date: 2003
- Subjects: Fishes -- Metabolism Fishes -- Physiology Pomadasys -- Physiology Grunts (Fishes) -- Physiology Stress (Psychology) Stress (Physiology)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5350 , http://hdl.handle.net/10962/d1007564
- Description: Quantitication of stress requires the use of a stress indicator that is easy to measure, and which can be readily interpreted in terms of the potential long-term effects to an organism. This study evaluates the suitability of metabolic rate as an indicator of the stress response in fish. By comparing the metabolic with the cortisol stress response, the most commonly used indicator of stress in fish, it was possible to assess the suitability of metabolic rate as a stress indicator. Changes in metabolic rate were used to predict the long-term effects of transport-related stressors. This study also detennined the baseline metabolic rates of the tish. The standard and the active metabolic rates of juvenile P. cummersonnii were 0.16 ± 0.02 (mean ± S.D, n = 6) mg O₂g⁻¹h⁻¹, and 0.56 ± 0.04 mg O₂g⁻¹h⁻¹, respectively, whereas the routine metabolic rate for the fish was 0.25 ± 0.03 mg O₂g⁻¹h¹. The relationship between metabolic rate and body weight was described by the equation ϺO₂ = 0.64 W⁻°·³⁸. 24-h oxygen consumption measurements showed that juvenile P. commersonnii exhibited diel rhythmicity in oxygen consumption rate, the higher rates occurring at night and the lower rates during the daytime. The higher nocturnal metabolic activity may have been due to increased activity induced by an endogenous rhythm related to feeding. Diel rhythmicity has direct implications for the measurement of baseline metabolic rates since it could result in overestimation or underestimation of these rates. 24-h continuous oxygen consumption measurements enabled the detection of the rhythmicity in oxygen consumption rate, and thereby ensured a greater degree of accuracy in the estimation of these parameters. The metabolic stress response in juvenile P. commersonnii was best described by the equation, y = -0.0013 x² + 0.0364 x ÷ 0.3052, where x = time after application of stressor, and y = oxygen consumption rate. Using the derivative of this equation, the metabolic stress response was estimated to peak approximately 14 min after application of a simulated capture and handling stressor. Oxygen consumption increased by about 300 % as a result of the stress. Approximately 15 min after application of a similar stressor, plasma cortisol levels in stressed fish was 200 % higher than baseline levels. However, cortisol levels in fish sampled 30 min after the disturbance was similar to the baseline cortisol levels, indicating that full recovery had occurred. Although the patterns in the metabolic and cortisol stress responses were similar, metabolic rate could be measured continuously, thereby ensuring accurate interpretation of the data. Furthermore, increases in metabolic rate during the stress response are a culmination of physiological events from the primary to the tertiary levels of biological organization and are, therefore, easier to interpret in terms of long-term effects on the fish. Different transportation procedures elicited variable degrees of stress in juvenile P. commersonnii. The cost of metabolism attributed to the effects of capture and handling was twice as much as that attributed to acute temperature elevation. Acute temperature decrease resulted in a signiticant reduction in the oxygen consumption rate (ANOVA, P < 0.05). Oxygen consumption by the fish was not affected by fish density (ANOVA: F = 2.002, P = 0.5), or by oxygen depletion at dissolved oxygen concentrations above the critical level. Below this level, however, oxygen consumption decreased linearly with further decrease in dissolved oxygen concentration. These results showed that the highest energetic cost to juvenile P. commersonnii was incurred as a result of capture and handling. The results also showed that by subjecting fish to different stressors, it was possible to categorize them according to their relative metabolic costs to the fish. At 25º C, the effective concentration of 2-phenoxyethanol to fully anaesthetize (Stage IV, McFarland 1960) juvenile P. commersonnii was 0.4 ml l⁻¹ and the most appropriate concentration for deep sedation (Stage II, McFarland 1960) of the fish for at least 24 h was 0.2 ml l⁻¹. A maximum of 3 minutes was required by the fish to recover from the effects of the anaesthetic. There was no correlation between fish weight and the rate of induction of anaesthesia (r² = 0.001, p = 0.3). At the peak of the metabolic stress response, oxygen consumption was twice as high in the un-anaesthetized fish compared to the fish anaesthetized after the application of the simulated capture and handling stressor, suggesting that anaesthetization with 2-phenoxyethanol may have reduced the effect of the disturbance on the fish. Similar oxygen consumption rates for the fish anaesthetized prior to capture and the non-stressed fish suggested that the increases in metabolic rate could be linked to the struggling associated with attempts by fish to escape from the perceived stressor. Anaesthetization of juvenile P. commersonnii with 0.3 ml l⁻¹ 2-phenoxyethanol resulted in a more than 200 % increase in plasma cortisol concentration. The elevated levels of plasma cortisol in the anaesthetized fish suggested a manifestation of 2-phenoxyethanol as a stressor. At the time of capture, cortisol levels in fish that were anaesthetized prior to capture were the same as those measured in the disturbed fish at the peak of the stress response (ANOVA, p = 0.95), suggesting that the anaesthetized fish were already experiencing considerable stress at the time they were captured. Undisturbed juvenile P. commersonnii that were anaesthetized for 1 h also had cortisol levels that were five times higher than those measured in undisturbed-unanaesthetized fish, indicating that the duration of exposure to the anaesthetic had a significant effect on plasma cortisol levels. The results presented in this study demonstrate the usefulness of metabolic rate as an indicator of acute stress in fish. This was achieved by comparing the metabolic and the cortisol stress responses. The ease and accuracy with which oxygen consumption of fish could be measured made it possible to measure the stress response more accurately than by plasma cortisol concentration. It was also possible to monitor metabolic rate continuously over a long duration using polarographic oxygen sensors, thus enabling a better evaluation of the stress response. These results, thus, suggest that metabolic rate measurements could be a more practical way to quantify the effects of acute stressors on juvenile fishes. By detailing the profile of the metabolic stress response in P. commersonnii, this study makes a contribution towards understanding the physiological effects of stress in fishes. The study also contributes towards the quantification of baseline metabolic rates of this species under captivity. This study also contributes towards understanding the effects of 2-phenoxyethanol on the stress physiology of fish. By anaesthetizing fish under different conditions of stress, it was possible to evaluate the effect of 2-phenoxyethanol on the metabolic stress response. The ability of 2-phenoxyethanol to reduce physical activity of the fish, and thereby reduce the impact of acute stress on the metabolic stress response, makes it a good agent for the mitigation of stress during the capture and handling of fish. However, the increase in plasma cortisol concentration during prolonged anaesthetization using this drug suggests that the anaesthetic might be a stressor to fish and may, therefore, not be suitable for long-term sedation.
- Full Text:
- Date Issued: 2003
Predictive modelling of species' potential geographical distributions
- Authors: Robertson, Mark Peter
- Date: 2003
- Subjects: Alien plants -- South Africa -- Geographical distribution Species -- Geographical distribution -- Mathematical models Cicadas -- South Africa -- Geographical distribution Scaevola plumieri -- South Africa -- Geographical distribution
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5816 , http://hdl.handle.net/10962/d1007189
- Description: Models that are used for predicting species' potential distributions are important tools that have found applications in a number of areas of applied ecology. The majority of these models can be classified as correlative, as they rely on strong, often indirect, links between species distribution records and environmental predictor variables to make predictions. Correlative models are an alternative to more complex mechanistic models that attempt to simulate the mechanisms considered to underlie the observed correlations with environmental attributes. This study explores the influence of the type and quality of the data used to calibrate correlative models. In terms of data type, the most popular techniques in use are group discrimination techniques, those that use both presence and absence locality data to make predictions. However, for many organisms absence data are either not available or are considered to be unreliable. As the available range of profile techniques (those using presence only data) appeared to be limited, new profile techniques were investigated and evaluated. A new profile modelling technique based on fuzzy classification (the Fuzzy Envelope Model) was developed and implemented. A second profile technique based on Principal Components Analysis was implemented and evaluated. Based on quantitative model evaluation tests, both of these techniques performed well and show considerable promise. In terms of data quality, the effects on model performance of false absence records, the number of locality records (sample size) and the proportion of localities representing species presence (prevalence) in samples were investigated for logistic regression distribution models. Sample size and prevalence both had a significant effect on model performance. False absence records had a significant influence on model performance, which was affected by sample size. A quantitative comparison of the performance of selected profile models and group discrimination modelling techniques suggests that different techniques may be more successful for predicting distributions for particular species or types of organism than others. The results also suggest that several different model design! sample size combinations are capable of making predictions that will on average not differ significantly in performance for a particular species. A further quantitative comparison among modelling techniques suggests that correlative techniques can perform as well as simple mechanistic techniques for predicting potential distributions.
- Full Text:
- Date Issued: 2003
- Authors: Robertson, Mark Peter
- Date: 2003
- Subjects: Alien plants -- South Africa -- Geographical distribution Species -- Geographical distribution -- Mathematical models Cicadas -- South Africa -- Geographical distribution Scaevola plumieri -- South Africa -- Geographical distribution
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5816 , http://hdl.handle.net/10962/d1007189
- Description: Models that are used for predicting species' potential distributions are important tools that have found applications in a number of areas of applied ecology. The majority of these models can be classified as correlative, as they rely on strong, often indirect, links between species distribution records and environmental predictor variables to make predictions. Correlative models are an alternative to more complex mechanistic models that attempt to simulate the mechanisms considered to underlie the observed correlations with environmental attributes. This study explores the influence of the type and quality of the data used to calibrate correlative models. In terms of data type, the most popular techniques in use are group discrimination techniques, those that use both presence and absence locality data to make predictions. However, for many organisms absence data are either not available or are considered to be unreliable. As the available range of profile techniques (those using presence only data) appeared to be limited, new profile techniques were investigated and evaluated. A new profile modelling technique based on fuzzy classification (the Fuzzy Envelope Model) was developed and implemented. A second profile technique based on Principal Components Analysis was implemented and evaluated. Based on quantitative model evaluation tests, both of these techniques performed well and show considerable promise. In terms of data quality, the effects on model performance of false absence records, the number of locality records (sample size) and the proportion of localities representing species presence (prevalence) in samples were investigated for logistic regression distribution models. Sample size and prevalence both had a significant effect on model performance. False absence records had a significant influence on model performance, which was affected by sample size. A quantitative comparison of the performance of selected profile models and group discrimination modelling techniques suggests that different techniques may be more successful for predicting distributions for particular species or types of organism than others. The results also suggest that several different model design! sample size combinations are capable of making predictions that will on average not differ significantly in performance for a particular species. A further quantitative comparison among modelling techniques suggests that correlative techniques can perform as well as simple mechanistic techniques for predicting potential distributions.
- Full Text:
- Date Issued: 2003
Pyrroloiminoquinone metabolites from South African Latrunculid sponges
- Authors: Antunes, Edith Martins
- Date: 2003
- Subjects: Sponges -- South Africa PQQ (Biochemistry) Marine metabolites -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4340 , http://hdl.handle.net/10962/d1005001
- Description: An in depth chemical investigation of the major and minor pyrroloiminoquinone metabolites produced by four species of endemic South African Latrunculid sponges, collected from Algoa Bay and the Tsitsikamma Marine Reserve off the south eastern coast of South Africa, yielded eleven new and twelve known pyrroloiminoquinone metabolites. The structures of the new metabolites were determined using standard spectroscopic techniques. Tsitsikamma pedunculata was shown to contain 7,8-dehydro-3-dihydro-discorhabdin C (2.1), 14-bromo-7,8-dehydro-3-dihydro-discorhabdin C (2.2), discorhabdin S (2.3), 14-bromo-1-hydroxy-discorhabdin S (2.4), 1-bromo-2-hydroxy-4-debromo-discorhabdin S (2.5), and 2,4-debromo-3-dihydro-discorhabdin C (2.6), together with the known compounds 14-bromo-discorhabdin C (1.51), 14-bromo-3-dihydro-discorhabdin C (1.52) and 3-dihydro-discorhabdin C. The metabolites from T. pedunculata were characterised by the presence of a reduced C-3 carbonyl and bromination at C-14. Compounds isolated from a second Latrunculid sponge, Latrunculia lorii, ranged from a substituted bicyclic pyrrolecarboxylic acid, makaluvic acid A (1.47), to the simple tricyclic known pyrroloiminoquinones makaluvamine C (1.33) and damirone B (1.20) and the more complex discorhabdin D type metabolites, discorhabdin M (3.2), 1-amino discorhabdin D (3.3), 1-methoxy discorhabdin D (3.4) and 1-alanyl discorhabdin D (3.5). Discorhabdin G* (3.1) was also isolated and characterised. This is the first reported occurrence of the known compounds 1.20, 1.33 and 1.47 in a Latrunculia sponge. Discorhabdin and bis-pyrroloiminoquinone type compounds predominated in Tsitsikamma favus. Three known, tsitsikammamines A (1.71) and B (1.72), 1.52, and five new pyrroloiminoquinones, tsitsikammamine N-oxime (4.1), tsitsikammamine B N-oxime (4.2), 2.1, 2.4 and 2.6, were isolated from this sponge. A fourth Latrunculid sponge (Strongylodesma sp.) yielded three known compounds, discorhabdins A (1.57), D (1.61) and 1.53, and one new pyrroloiminoquinone 3.3. The dual role of these metabolites as cytotoxic agents and pigments resulted in an attempt to relate the photochemical properties of these metabolites to their cytotoxicity. The pyrroloiminoquinone metabolites studied exhibited moderate singlet oxygen quantum yields, while three compounds (1.57, 4.1 and 4.2) were shown to be capable of producing radicals at a wavelength of 532 nm. The possibility of a correlation between the electrochemical properties and anti-cancer (HCT-116) activity of selected pyrroloiminoquinones was explored. A study of the oesophageal and ovarian cytotoxicities of two pyrroloiminoquinones (1.57 and 1.72), together with an investigation into the intercalation and topoisomerase I inhibitory activity of the bis-pyrroloiminoquinones (1.71, 1.72, 4.1 and 4.2), are presented.
- Full Text:
- Date Issued: 2003
- Authors: Antunes, Edith Martins
- Date: 2003
- Subjects: Sponges -- South Africa PQQ (Biochemistry) Marine metabolites -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4340 , http://hdl.handle.net/10962/d1005001
- Description: An in depth chemical investigation of the major and minor pyrroloiminoquinone metabolites produced by four species of endemic South African Latrunculid sponges, collected from Algoa Bay and the Tsitsikamma Marine Reserve off the south eastern coast of South Africa, yielded eleven new and twelve known pyrroloiminoquinone metabolites. The structures of the new metabolites were determined using standard spectroscopic techniques. Tsitsikamma pedunculata was shown to contain 7,8-dehydro-3-dihydro-discorhabdin C (2.1), 14-bromo-7,8-dehydro-3-dihydro-discorhabdin C (2.2), discorhabdin S (2.3), 14-bromo-1-hydroxy-discorhabdin S (2.4), 1-bromo-2-hydroxy-4-debromo-discorhabdin S (2.5), and 2,4-debromo-3-dihydro-discorhabdin C (2.6), together with the known compounds 14-bromo-discorhabdin C (1.51), 14-bromo-3-dihydro-discorhabdin C (1.52) and 3-dihydro-discorhabdin C. The metabolites from T. pedunculata were characterised by the presence of a reduced C-3 carbonyl and bromination at C-14. Compounds isolated from a second Latrunculid sponge, Latrunculia lorii, ranged from a substituted bicyclic pyrrolecarboxylic acid, makaluvic acid A (1.47), to the simple tricyclic known pyrroloiminoquinones makaluvamine C (1.33) and damirone B (1.20) and the more complex discorhabdin D type metabolites, discorhabdin M (3.2), 1-amino discorhabdin D (3.3), 1-methoxy discorhabdin D (3.4) and 1-alanyl discorhabdin D (3.5). Discorhabdin G* (3.1) was also isolated and characterised. This is the first reported occurrence of the known compounds 1.20, 1.33 and 1.47 in a Latrunculia sponge. Discorhabdin and bis-pyrroloiminoquinone type compounds predominated in Tsitsikamma favus. Three known, tsitsikammamines A (1.71) and B (1.72), 1.52, and five new pyrroloiminoquinones, tsitsikammamine N-oxime (4.1), tsitsikammamine B N-oxime (4.2), 2.1, 2.4 and 2.6, were isolated from this sponge. A fourth Latrunculid sponge (Strongylodesma sp.) yielded three known compounds, discorhabdins A (1.57), D (1.61) and 1.53, and one new pyrroloiminoquinone 3.3. The dual role of these metabolites as cytotoxic agents and pigments resulted in an attempt to relate the photochemical properties of these metabolites to their cytotoxicity. The pyrroloiminoquinone metabolites studied exhibited moderate singlet oxygen quantum yields, while three compounds (1.57, 4.1 and 4.2) were shown to be capable of producing radicals at a wavelength of 532 nm. The possibility of a correlation between the electrochemical properties and anti-cancer (HCT-116) activity of selected pyrroloiminoquinones was explored. A study of the oesophageal and ovarian cytotoxicities of two pyrroloiminoquinones (1.57 and 1.72), together with an investigation into the intercalation and topoisomerase I inhibitory activity of the bis-pyrroloiminoquinones (1.71, 1.72, 4.1 and 4.2), are presented.
- Full Text:
- Date Issued: 2003
Stability studies on some substituted aminobenzoic acids
- Authors: Rotich, Moses Kipngeno
- Date: 2003
- Subjects: Aminobenzoic acids Aminobenzoic acids -- Stability Salicylic acid
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4347 , http://hdl.handle.net/10962/d1005012
- Description: he thermal behaviour in the solid state of various substituted aminobenzoic acids (3-aminobenzoic acid (3-ABA), 4-aminobenzoic acid (4-ABA), 3-aminosalicylic acid (3-ASA), 4-aminosalicylic acid (4-ASA), and 5-aminosalicylic acid (5-ASA), as well as the "parent" benzoic acid (BA) and salicylic acid (SA) as reference substances, and possible decomposition products: 2-aminophenol (2-AP), 3-aminophenol (3-AP) and 4-aminophenol (4-AP), has been examined. The various sets of isomers studied showed considerable and interesting differences. Most sublimed well before melting, generally with an increasing rate of mass loss beyond their very different melting points. The existence of ranges of isomers allows for the comparison of their behaviour, including such aspects as melting, vaporisation, and the influence of products on the course of decomposition of initially-solid reactants. The differences in behaviour of 4-ASA and 5-ASA were the most remarkable, with 5-ASA being far more stable and apparently not decarboxylating readily, while 4-ASA sublimed at temperatures below the melting point, becoming less stable and decarboxylating in the liquid form. There is also a marked difference in the thermal behaviour of 3-ASA, as compared with 4-ASA and 5-ASA. It decarboxylated at higher temperatures (260°C) than 4-ASA (150°C). The addition of the possible decomposition products to these compounds showed faster decomposition for 4-ASA mixed with 3-AP. The sodium salts of 3-ASA and 4-ASA decarboxylate while that of 5-ASA did not. Binary mixtures of the substances listed above with beta-cyclodextrin (BCD), hydroxypropylbeta-cyclodextrin (HPBCD) and gamma-cyclodextrin (GCD) were prepared (by simple physical mixing or by kneading with a solvent) and were then examined for possible interactions using DSC, TG-FTIR, HSM, XRD and NMR. Generally, kneaded mixtures showed greater changes in thermal behaviour from that of the individual components than the physical mixtures, but changes in the physical mixtures were also significant. Comparison of the effects of the different CDs on the thermal behaviour of individual ASA isomers showed that HPBCD has the greatest interaction with 3-ASA and 5-ASA, followed by GCD, while BCD generally showed the least interactions. For 4-ASA, the effect of GCD is more marked than for 3-ASA and 5-ASA. GCD has the largest molecular cavity.
- Full Text:
- Date Issued: 2003
- Authors: Rotich, Moses Kipngeno
- Date: 2003
- Subjects: Aminobenzoic acids Aminobenzoic acids -- Stability Salicylic acid
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4347 , http://hdl.handle.net/10962/d1005012
- Description: he thermal behaviour in the solid state of various substituted aminobenzoic acids (3-aminobenzoic acid (3-ABA), 4-aminobenzoic acid (4-ABA), 3-aminosalicylic acid (3-ASA), 4-aminosalicylic acid (4-ASA), and 5-aminosalicylic acid (5-ASA), as well as the "parent" benzoic acid (BA) and salicylic acid (SA) as reference substances, and possible decomposition products: 2-aminophenol (2-AP), 3-aminophenol (3-AP) and 4-aminophenol (4-AP), has been examined. The various sets of isomers studied showed considerable and interesting differences. Most sublimed well before melting, generally with an increasing rate of mass loss beyond their very different melting points. The existence of ranges of isomers allows for the comparison of their behaviour, including such aspects as melting, vaporisation, and the influence of products on the course of decomposition of initially-solid reactants. The differences in behaviour of 4-ASA and 5-ASA were the most remarkable, with 5-ASA being far more stable and apparently not decarboxylating readily, while 4-ASA sublimed at temperatures below the melting point, becoming less stable and decarboxylating in the liquid form. There is also a marked difference in the thermal behaviour of 3-ASA, as compared with 4-ASA and 5-ASA. It decarboxylated at higher temperatures (260°C) than 4-ASA (150°C). The addition of the possible decomposition products to these compounds showed faster decomposition for 4-ASA mixed with 3-AP. The sodium salts of 3-ASA and 4-ASA decarboxylate while that of 5-ASA did not. Binary mixtures of the substances listed above with beta-cyclodextrin (BCD), hydroxypropylbeta-cyclodextrin (HPBCD) and gamma-cyclodextrin (GCD) were prepared (by simple physical mixing or by kneading with a solvent) and were then examined for possible interactions using DSC, TG-FTIR, HSM, XRD and NMR. Generally, kneaded mixtures showed greater changes in thermal behaviour from that of the individual components than the physical mixtures, but changes in the physical mixtures were also significant. Comparison of the effects of the different CDs on the thermal behaviour of individual ASA isomers showed that HPBCD has the greatest interaction with 3-ASA and 5-ASA, followed by GCD, while BCD generally showed the least interactions. For 4-ASA, the effect of GCD is more marked than for 3-ASA and 5-ASA. GCD has the largest molecular cavity.
- Full Text:
- Date Issued: 2003
Structural and synthetic investigations of diterpenoid natural products from southern African marine invertebrates
- Authors: Gray, Christopher Anthony
- Date: 2003
- Subjects: Ethyl acetoacetate Diterpenes Limpets -- South Africa Natural products -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4349 , http://hdl.handle.net/10962/d1005014
- Description: This thesis is divided into two parts. The first part (Chapter Two) documents a bioassay guided investigation of the ethyl acetate extracts of four marine invertebrates from Mozambique (an Irciniid sponge, a Haliclona sp. sponge, an ascidian tentatively identified as Diplosoma sp., and the soft coral Cladiella kashmani). Eight known compounds [ilimaquinone (2.1), renierone (2.7), N-formyl-1,2-dihydrorenierone (2.8), 1,6-dimethyl-7-methoxy-5,8-dihydroisoquinoline-5,8-dione (2.9), mimosamycin (2.10) 7Z-allylidene-5-hydroxy-7,7a-dihydro-2H-cyclopenta[b]pyran-6-one (2.11), flaccidoxide (2.18) and 11S,12S-epoxycembra-1Z,3E,7E-trien-14S-ol (2.19)] and a new diterpene [13S,14R-diacetoxy-11S,12R-epoxycembra-1Z,3E,7E-triene (2.20)] were isolated and identified using standard spectroscopic techniques. Anomalies in the published spectral data of 2.1 and 2.8 were exposed and corrected, and the absolute stereochemistry of the cembrane diterpenes 2.18 and 2.20 established using the modified Mosher’s method. The comparative activities of the nine natural products against four cancer cell lines (A549, LOX, OVCAR3, SNB19) are reported. The second part of the thesis (Chapter Three – Chapter Six) is concerned with an ecological, structural and synthetic study of diterpenes from the endemic South African pulmonate limpet Trimusculus costatus. Two new labdane diterpenes [6b,7a-diacetoxylabda-8,13E-dien-15-ol (3.10) and 2a,6b,7a-triacetoxylabda-8,13E-dien-15-ol (3.11)] were isolated from T. costatus and evaluated for anti-feeding activity against the common predatory fish Pomadasys commersonnii. A strategy for the semi-synthesis of 3.10 from rhinocerotinoic acid (4.14), a diterpene reportedly present in the ubiquitous South African shrub Elytropappus rhinocerotis, was devised in order to allow further bioactivity tests to be performed and unequivocally assign the unknown absolute stereochemistry of the T. costatus metabolites. Attempts to isolate rhinocerotinoic acid from local specimens of Elytropappus rhinocerotis were unsuccessful, and as the repetition of a published synthesis of 4.14 from (-)-sclareol (4.15) gave rhinocerotinoic acid in unacceptably low yields with poor stereoselectivity, an improved synthesis of 4.14 is presented. Comprehensive studies using hispanone (5.1) as a model compound showed that 6,7-dioxygenated labda-8-enes could be prepared from compounds possessing a 7-oxo-labda-8-ene skeleton with some degree of stereocontrol. In the process, fourteen new hispanone analogues were prepared and most of these were tested for activity in a suite of ten agro-chemical assays. The novel compound 7b-hydroxy-9a-carbonitrile-15,16-epoxylabda-13(16),14-dien-6-one (5.34) exhibited significant activity against the crop fungus Phytophthora infestans and is currently being subjected to further agro-chemical tests. Unfortunately, the results from the oxygenation study performed on the model compound 5.1 could not be directly extrapolated to rhinocerotinoic acid. Attempts to prepare the naturally occurring 3.10 from 4.14 via an alternative route were unsuccessful but yielded an analogue of 3.10 in which the substituents at C-6 and C-7 are in a diequatorial rather than a diaxial configuration.
- Full Text:
- Date Issued: 2003
- Authors: Gray, Christopher Anthony
- Date: 2003
- Subjects: Ethyl acetoacetate Diterpenes Limpets -- South Africa Natural products -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4349 , http://hdl.handle.net/10962/d1005014
- Description: This thesis is divided into two parts. The first part (Chapter Two) documents a bioassay guided investigation of the ethyl acetate extracts of four marine invertebrates from Mozambique (an Irciniid sponge, a Haliclona sp. sponge, an ascidian tentatively identified as Diplosoma sp., and the soft coral Cladiella kashmani). Eight known compounds [ilimaquinone (2.1), renierone (2.7), N-formyl-1,2-dihydrorenierone (2.8), 1,6-dimethyl-7-methoxy-5,8-dihydroisoquinoline-5,8-dione (2.9), mimosamycin (2.10) 7Z-allylidene-5-hydroxy-7,7a-dihydro-2H-cyclopenta[b]pyran-6-one (2.11), flaccidoxide (2.18) and 11S,12S-epoxycembra-1Z,3E,7E-trien-14S-ol (2.19)] and a new diterpene [13S,14R-diacetoxy-11S,12R-epoxycembra-1Z,3E,7E-triene (2.20)] were isolated and identified using standard spectroscopic techniques. Anomalies in the published spectral data of 2.1 and 2.8 were exposed and corrected, and the absolute stereochemistry of the cembrane diterpenes 2.18 and 2.20 established using the modified Mosher’s method. The comparative activities of the nine natural products against four cancer cell lines (A549, LOX, OVCAR3, SNB19) are reported. The second part of the thesis (Chapter Three – Chapter Six) is concerned with an ecological, structural and synthetic study of diterpenes from the endemic South African pulmonate limpet Trimusculus costatus. Two new labdane diterpenes [6b,7a-diacetoxylabda-8,13E-dien-15-ol (3.10) and 2a,6b,7a-triacetoxylabda-8,13E-dien-15-ol (3.11)] were isolated from T. costatus and evaluated for anti-feeding activity against the common predatory fish Pomadasys commersonnii. A strategy for the semi-synthesis of 3.10 from rhinocerotinoic acid (4.14), a diterpene reportedly present in the ubiquitous South African shrub Elytropappus rhinocerotis, was devised in order to allow further bioactivity tests to be performed and unequivocally assign the unknown absolute stereochemistry of the T. costatus metabolites. Attempts to isolate rhinocerotinoic acid from local specimens of Elytropappus rhinocerotis were unsuccessful, and as the repetition of a published synthesis of 4.14 from (-)-sclareol (4.15) gave rhinocerotinoic acid in unacceptably low yields with poor stereoselectivity, an improved synthesis of 4.14 is presented. Comprehensive studies using hispanone (5.1) as a model compound showed that 6,7-dioxygenated labda-8-enes could be prepared from compounds possessing a 7-oxo-labda-8-ene skeleton with some degree of stereocontrol. In the process, fourteen new hispanone analogues were prepared and most of these were tested for activity in a suite of ten agro-chemical assays. The novel compound 7b-hydroxy-9a-carbonitrile-15,16-epoxylabda-13(16),14-dien-6-one (5.34) exhibited significant activity against the crop fungus Phytophthora infestans and is currently being subjected to further agro-chemical tests. Unfortunately, the results from the oxygenation study performed on the model compound 5.1 could not be directly extrapolated to rhinocerotinoic acid. Attempts to prepare the naturally occurring 3.10 from 4.14 via an alternative route were unsuccessful but yielded an analogue of 3.10 in which the substituents at C-6 and C-7 are in a diequatorial rather than a diaxial configuration.
- Full Text:
- Date Issued: 2003
Structures and struggles of rural local government in South Africa: the case of traditional authorities in the Eastern Cape
- Authors: Ntsebeza, Lungisile
- Date: 2003
- Subjects: Local government -- South Africa -- Eastern Cape Tribal government -- South Africa -- Eastern Cape Political leadership -- South Africa -- Eastern Cape Tribal government -- South Africa -- History South Africa -- Politics and government
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3304 , http://hdl.handle.net/10962/d1003092
- Description: This thesis is about the political implications of the constitutional recognition of the hereditary institution of traditional leadership in post-1994 South Africa for the democratization process in the rural areas of the former Bantustans. The thesis is organized around three related conceptual, historical and political questions. The conceptual question deals with the meaning of democracy in rural areas under the jurisdiction of traditional authorities. The historical question traces how the institution and traditional authorities have survived to the present post-colonial period. Lastly, this study investigates the political issue of why an ANC-led government came to recognize the institution. The focus of the thesis is the sphere of rural local government in the Xhalanga district, where these issues are best illustrated. The thesis argues that the institution of traditional leadership and its officials survived precisely because they were incorporated into the colonial and apartheid administrative structures in the project of indirect rule. Traditional authorities were central to the apartheid policy of retribalisation, which was essentially a form of control of Africans in the Bantustans. Rural residents engaged in fierce struggles against the imposition of rural local government structures such as the District Council and Tribal Authorities. In so far as traditional authorities were part of government structures, they could not avoid being targets in these struggles. In explaining the recognition of the institution of traditional leadership, the thesis focuses on the policies of the ANC, the majority party in the Government of National Unity, towards traditional authorities. Organisationally weak on the rural grounds, the ANC operated through what they considered to be “good/progressive/comrade chiefs”. The ANC had hoped that these traditional authorities would accept a non-political ceremonial role. However, traditional authorities have rejected this ceremonial role. Their refusal, coupled with the ANC’s ambivalence in resolving the tension imply, the study concludes, that the (political) citizenship rights of rural people are partial: they are neither citizens nor subjects.
- Full Text:
- Date Issued: 2003
- Authors: Ntsebeza, Lungisile
- Date: 2003
- Subjects: Local government -- South Africa -- Eastern Cape Tribal government -- South Africa -- Eastern Cape Political leadership -- South Africa -- Eastern Cape Tribal government -- South Africa -- History South Africa -- Politics and government
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3304 , http://hdl.handle.net/10962/d1003092
- Description: This thesis is about the political implications of the constitutional recognition of the hereditary institution of traditional leadership in post-1994 South Africa for the democratization process in the rural areas of the former Bantustans. The thesis is organized around three related conceptual, historical and political questions. The conceptual question deals with the meaning of democracy in rural areas under the jurisdiction of traditional authorities. The historical question traces how the institution and traditional authorities have survived to the present post-colonial period. Lastly, this study investigates the political issue of why an ANC-led government came to recognize the institution. The focus of the thesis is the sphere of rural local government in the Xhalanga district, where these issues are best illustrated. The thesis argues that the institution of traditional leadership and its officials survived precisely because they were incorporated into the colonial and apartheid administrative structures in the project of indirect rule. Traditional authorities were central to the apartheid policy of retribalisation, which was essentially a form of control of Africans in the Bantustans. Rural residents engaged in fierce struggles against the imposition of rural local government structures such as the District Council and Tribal Authorities. In so far as traditional authorities were part of government structures, they could not avoid being targets in these struggles. In explaining the recognition of the institution of traditional leadership, the thesis focuses on the policies of the ANC, the majority party in the Government of National Unity, towards traditional authorities. Organisationally weak on the rural grounds, the ANC operated through what they considered to be “good/progressive/comrade chiefs”. The ANC had hoped that these traditional authorities would accept a non-political ceremonial role. However, traditional authorities have rejected this ceremonial role. Their refusal, coupled with the ANC’s ambivalence in resolving the tension imply, the study concludes, that the (political) citizenship rights of rural people are partial: they are neither citizens nor subjects.
- Full Text:
- Date Issued: 2003
Studies of the environmental and endocrine control of reproduction in the four striped field mouse, Rhabdomys pumilio
- Authors: Jackson, Claire
- Date: 2003
- Subjects: Microtus Microtus -- South Africa -- Reproduction Mice -- Reproduction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5777 , http://hdl.handle.net/10962/d1005465
- Description: Previous studies of the control of reproduction in Rhabdomys pumilio have shown that day length alone does not inhibit spermatogenesis, that a reduction in food availability and ambient temperature results in an inhibition of gametogenesis, that females are more susceptible to inhibition than are males, and that mice that are able to maintain a body fat store in the face of an energetic challenge, are less likely to show reproductive inhibition than those that lose their fat store. In the present study, field and laboratory experiments were conducted to examine the effects of winter food supplementation on reproduction and population dynamics, and the effects of exogenous GnRH, leptin and mercaptoacetate (MA) on reproductive activity of Rhabdomys pumilio exposed to an energetic challenge. In the field food supplementation experiments in Thomas Baines Nature Reserve (2000, 2001), there was no winter inhibition of reproduction and provision of supplementary food had little effect. While at Mountain Zebra National Park (2002) winter was harsher, females became reproductively inactive, spermatogenesis continued and the provision of extra food resulted in higher rates of individual growth and larger reproductive organs. Treatment of mice that had been exposed to a prolonged energetic challenge, with exogenous GnRH (1µg/mouse/treatment) resulted in an increase in the masses of the testes and epididymides, and in the activity of the reproductive organs. Treatment with exogenous leptin (40µg/mouse/treatment), concurrently with an energetic challenge, countered the negative effects of the energetic challenge, and treated males had larger reproductive organs. MA (600µmol/kg body mass), given concurrently with an energetic challenge, did not inhibit fat metabolism, although the high-fat diet countered the effects of the energetic challenge. Results suggest that the first response of male Rhabdomys pumilio to an energetic challenge is a reduction in the size of the reproductive organs, without an inhibition of spermatogenesis. It is likely that this effect is mediated via white fat and leptin, and leptin’s influence on the hypothalamic-pituitary-gonad axis. Results of the study support the suggestion that females are more sensitive to reproductive inhibition than males and that reproduction in Rhabdomys pumilio is truly opportunistic.
- Full Text:
- Date Issued: 2003
- Authors: Jackson, Claire
- Date: 2003
- Subjects: Microtus Microtus -- South Africa -- Reproduction Mice -- Reproduction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5777 , http://hdl.handle.net/10962/d1005465
- Description: Previous studies of the control of reproduction in Rhabdomys pumilio have shown that day length alone does not inhibit spermatogenesis, that a reduction in food availability and ambient temperature results in an inhibition of gametogenesis, that females are more susceptible to inhibition than are males, and that mice that are able to maintain a body fat store in the face of an energetic challenge, are less likely to show reproductive inhibition than those that lose their fat store. In the present study, field and laboratory experiments were conducted to examine the effects of winter food supplementation on reproduction and population dynamics, and the effects of exogenous GnRH, leptin and mercaptoacetate (MA) on reproductive activity of Rhabdomys pumilio exposed to an energetic challenge. In the field food supplementation experiments in Thomas Baines Nature Reserve (2000, 2001), there was no winter inhibition of reproduction and provision of supplementary food had little effect. While at Mountain Zebra National Park (2002) winter was harsher, females became reproductively inactive, spermatogenesis continued and the provision of extra food resulted in higher rates of individual growth and larger reproductive organs. Treatment of mice that had been exposed to a prolonged energetic challenge, with exogenous GnRH (1µg/mouse/treatment) resulted in an increase in the masses of the testes and epididymides, and in the activity of the reproductive organs. Treatment with exogenous leptin (40µg/mouse/treatment), concurrently with an energetic challenge, countered the negative effects of the energetic challenge, and treated males had larger reproductive organs. MA (600µmol/kg body mass), given concurrently with an energetic challenge, did not inhibit fat metabolism, although the high-fat diet countered the effects of the energetic challenge. Results suggest that the first response of male Rhabdomys pumilio to an energetic challenge is a reduction in the size of the reproductive organs, without an inhibition of spermatogenesis. It is likely that this effect is mediated via white fat and leptin, and leptin’s influence on the hypothalamic-pituitary-gonad axis. Results of the study support the suggestion that females are more sensitive to reproductive inhibition than males and that reproduction in Rhabdomys pumilio is truly opportunistic.
- Full Text:
- Date Issued: 2003
The development and evaluation of Cryptophlebia Leucotreta granulovirus (CrleGV) as a biological control agent for the management of false codling moth, Cryptophlebia Leucotreta, on citrus
- Authors: Moore, Sean Douglas
- Date: 2003
- Subjects: Cryptophlebia leucotreta Cryptophlebia leucotreta -- Control Pests -- Biological control Citrus -- Diseases and pests
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3942 , http://hdl.handle.net/10962/d1004001
- Description: A granulovirus isolated from Cryptophlebia leucotreta larvae was shown through restriction endonuclease analysis to be a novel strain (CrleGV-SA). No more than one isolate could be identified from a laboratory culture of C. leucotreta. However, a preliminary examination of restricted DNA profiles of isolates from different geographical regions indicated some minor differences. In surface dose bioassays on artificial diet, LC50 and LC90 values with neonate larvae were estimated to be 4.095 x 103 OBs/ml and 1.185 x 105 OBs/ml respectively. LT50 and LT90 values with neonate larvae were estimated to be 4 days 22 h and 7 days 8 h, respectively. Detached fruit (navel orange) bioassays with neonate larvae indicated that virus concentrations that are likely to be effective in the field range from 1.08 x 107 to 3.819 x 1010 OBs/ml. In surface dose bioassays with fifth instar larvae LC50 and LC90 values were estimated to be 2.678 x 107 OBs/ml and 9.118 x 109 OBs/ml respectively. LT50 and LT90 values were estimated to be 7 days 17 h and 9 days 8 h, respectively. A new artificial diet for mass rearing the host was developed. Microbial contamination of diet was significantly reduced by adding nipagin and sorbic acid to the diet and by surface sterilising C. leucotreta eggs with Sporekill. Almost 20 % more eggs were produced from moths reared on the new diet compared to moths reared on the old diet. A further 9 % improvement in egg production and a reduction in the labour required to produce eggs, was made with the development of a new oviposition cage attached to the moth eclosion box. Virus was mass produced in fifth instar C. leucotreta larvae by surface inoculating diet with the LC90. When 300 individuals were placed onto inoculated diet, 56 % of them were recovered six to 11 days later as infected larvae. Mean larval equivalents was 1.158 x 1011 OBs/larva. When larvae and diet were harvested together, highest yields of virus were achieved at eight days after inoculation. Microbial contamination in semi-purified preparations of CrleGV ranged from 176211 to 433594 (OB:CFU ratio). Half-life of CrleGV in the field was estimated to be less than 1 day on the northern aspect of trees and between 3 - 6 days on the southern aspect. Original activity remaining (OAR) of the virus dropped below 50 % after 5 days on the northern aspect of trees and was still at 69 % on the southern aspect of trees after 3 weeks. In field trials, CrleGV reduced C. leucotreta infestation of navel oranges by up to 60 % for a period of 39 days. CrleGV in combination with augmentation of the C. leucotreta egg parasitoid, Trichogrammatoidea cryptophlebiae, reduced infestation by 70 %. The integration of CrleGV into an integrated pest management (IPM) system for the management of C. leucotreta on citrus is proposed.
- Full Text:
- Date Issued: 2003
- Authors: Moore, Sean Douglas
- Date: 2003
- Subjects: Cryptophlebia leucotreta Cryptophlebia leucotreta -- Control Pests -- Biological control Citrus -- Diseases and pests
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3942 , http://hdl.handle.net/10962/d1004001
- Description: A granulovirus isolated from Cryptophlebia leucotreta larvae was shown through restriction endonuclease analysis to be a novel strain (CrleGV-SA). No more than one isolate could be identified from a laboratory culture of C. leucotreta. However, a preliminary examination of restricted DNA profiles of isolates from different geographical regions indicated some minor differences. In surface dose bioassays on artificial diet, LC50 and LC90 values with neonate larvae were estimated to be 4.095 x 103 OBs/ml and 1.185 x 105 OBs/ml respectively. LT50 and LT90 values with neonate larvae were estimated to be 4 days 22 h and 7 days 8 h, respectively. Detached fruit (navel orange) bioassays with neonate larvae indicated that virus concentrations that are likely to be effective in the field range from 1.08 x 107 to 3.819 x 1010 OBs/ml. In surface dose bioassays with fifth instar larvae LC50 and LC90 values were estimated to be 2.678 x 107 OBs/ml and 9.118 x 109 OBs/ml respectively. LT50 and LT90 values were estimated to be 7 days 17 h and 9 days 8 h, respectively. A new artificial diet for mass rearing the host was developed. Microbial contamination of diet was significantly reduced by adding nipagin and sorbic acid to the diet and by surface sterilising C. leucotreta eggs with Sporekill. Almost 20 % more eggs were produced from moths reared on the new diet compared to moths reared on the old diet. A further 9 % improvement in egg production and a reduction in the labour required to produce eggs, was made with the development of a new oviposition cage attached to the moth eclosion box. Virus was mass produced in fifth instar C. leucotreta larvae by surface inoculating diet with the LC90. When 300 individuals were placed onto inoculated diet, 56 % of them were recovered six to 11 days later as infected larvae. Mean larval equivalents was 1.158 x 1011 OBs/larva. When larvae and diet were harvested together, highest yields of virus were achieved at eight days after inoculation. Microbial contamination in semi-purified preparations of CrleGV ranged from 176211 to 433594 (OB:CFU ratio). Half-life of CrleGV in the field was estimated to be less than 1 day on the northern aspect of trees and between 3 - 6 days on the southern aspect. Original activity remaining (OAR) of the virus dropped below 50 % after 5 days on the northern aspect of trees and was still at 69 % on the southern aspect of trees after 3 weeks. In field trials, CrleGV reduced C. leucotreta infestation of navel oranges by up to 60 % for a period of 39 days. CrleGV in combination with augmentation of the C. leucotreta egg parasitoid, Trichogrammatoidea cryptophlebiae, reduced infestation by 70 %. The integration of CrleGV into an integrated pest management (IPM) system for the management of C. leucotreta on citrus is proposed.
- Full Text:
- Date Issued: 2003
The diamondback moth, Plutella xylostella (L.), (Lepidoptera: Plutellidae) and its biological control in the Eastern Cape Province, South Africa
- Authors: Smith, Tamara Jane
- Date: 2003
- Subjects: Plutellidae Plutellidae -- South Africa -- Eastern Cape Insect pests -- Biological control -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5626 , http://hdl.handle.net/10962/d1004742
- Description: The diamondback moth, Plutella xylostella (L.), is a pest on crucifer crops worldwide, damaging the leaves, florets and seed pods of many crucifers including cabbage, cauliflower, broccoli and canola. It has been controlled using broad-spectrum insecticides, but this has led to a rapid build-up of insecticide resistance. In the Grahamstown area of the Eastern Cape Province, South Africa, diamondback moth showed resistance to cypermethrin (a pyrethroid) on commercially grown cabbages. Therefore it is imperative that other methods of control be adopted, including both cultural control and biological control using parasitoids, and that these are incorporated into an Integrated Pest Management (IPM) programme. The diamondback moth and its parasitoids were monitored weekly from April 1997 to November 1999 at three sites near Grahamstown. One site was a commercial farm with an active insecticide spraying program; the others were unsprayed. Infestation levels were highest during spring (September to November) and autumn (March to May). Nine species of parasitoids were associated with the diamondback moth, with abundances being highest over spring and early summer (September to December). Cotesia plutellae (Kurdjumov) dominated the sprayed site, while the unsprayed sites yielded a complex of parasitoids, including C. plutellae, Diadegma mollipla (Holmgren), Diadromus collaris Gravenhorst and Oomyzus sokolowsldi (Kurdjumov). Parasitism levels ranged between 10 and 90%. There was a large amount of site-to-site and year-to-year variation. Parasitoids were an effective mortality factor against the diamondback moth. The effects of temperature on development and mortality, and of field size and non-crop plants on the distribution of diamondback moth and its parasitoids, were investigated. The results show that high temperatures can depress pest populations, and that the size and surroundings of fields can be manipulated to improve cultural control of the diamondback moth. Suggestions for effective rPM in the Eastern Cape Province include a reduction in insecticide applications, the use of bioinsecticides, for example Bacillus thuringiensis Berliner (Bt) and the encouragement of indigenous parasitoids by planting suitable nectar sources. Cultural control methods are also important and involve removal of cabbage refuse after harvest, management of wild crucifers around cabbage fields, scouting and monitoring the moth population and determining the optimal field size to assist with control by parasitoids.
- Full Text:
- Date Issued: 2003
- Authors: Smith, Tamara Jane
- Date: 2003
- Subjects: Plutellidae Plutellidae -- South Africa -- Eastern Cape Insect pests -- Biological control -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5626 , http://hdl.handle.net/10962/d1004742
- Description: The diamondback moth, Plutella xylostella (L.), is a pest on crucifer crops worldwide, damaging the leaves, florets and seed pods of many crucifers including cabbage, cauliflower, broccoli and canola. It has been controlled using broad-spectrum insecticides, but this has led to a rapid build-up of insecticide resistance. In the Grahamstown area of the Eastern Cape Province, South Africa, diamondback moth showed resistance to cypermethrin (a pyrethroid) on commercially grown cabbages. Therefore it is imperative that other methods of control be adopted, including both cultural control and biological control using parasitoids, and that these are incorporated into an Integrated Pest Management (IPM) programme. The diamondback moth and its parasitoids were monitored weekly from April 1997 to November 1999 at three sites near Grahamstown. One site was a commercial farm with an active insecticide spraying program; the others were unsprayed. Infestation levels were highest during spring (September to November) and autumn (March to May). Nine species of parasitoids were associated with the diamondback moth, with abundances being highest over spring and early summer (September to December). Cotesia plutellae (Kurdjumov) dominated the sprayed site, while the unsprayed sites yielded a complex of parasitoids, including C. plutellae, Diadegma mollipla (Holmgren), Diadromus collaris Gravenhorst and Oomyzus sokolowsldi (Kurdjumov). Parasitism levels ranged between 10 and 90%. There was a large amount of site-to-site and year-to-year variation. Parasitoids were an effective mortality factor against the diamondback moth. The effects of temperature on development and mortality, and of field size and non-crop plants on the distribution of diamondback moth and its parasitoids, were investigated. The results show that high temperatures can depress pest populations, and that the size and surroundings of fields can be manipulated to improve cultural control of the diamondback moth. Suggestions for effective rPM in the Eastern Cape Province include a reduction in insecticide applications, the use of bioinsecticides, for example Bacillus thuringiensis Berliner (Bt) and the encouragement of indigenous parasitoids by planting suitable nectar sources. Cultural control methods are also important and involve removal of cabbage refuse after harvest, management of wild crucifers around cabbage fields, scouting and monitoring the moth population and determining the optimal field size to assist with control by parasitoids.
- Full Text:
- Date Issued: 2003
The fundamental right to just administrative action: judicial review of administrative action in the democratic South Africa
- Authors: Plasket, Clive
- Date: 2003
- Subjects: Judicial review of administrative acts -- South Africa Administrative acts -- South Africa Administrative law -- South Africa Public administration -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3693 , http://hdl.handle.net/10962/d1003208
- Description: For most of its existence South African administrative law has been shaped by the doctrine of parliamentary sovereignty – the heart of the constitutional order from 1910 to 1994 – and a racist political system that favoured the white minority at the expense of the black majority. In these circumstances, the rules of administrative law were of limited use in protecting the individual from exercises of administrative power that infringed fundamental human rights, often on a grand scale. On 27 April 1994, however, a new political and constitutional order came into existence that swept away the very foundations of the old order: parliamentary sovereignty was replaced by constitutional supremacy and the racial exclusivity of the old order was replaced by a commitment to equality, freedom and dignity in a democratic state. A justiciable Bill of Rights was at centre stage in this new order. That Bill of Rights includes a fundamental right to just administrative action. It is both the new constitutional order and this rather unusual fundamental right that have changed the nature of South African administrative law. This thesis examines the effect of the fundamental right to just administrative action on the law and practice of the judicial review of administrative action. It does so principally by examining the legal position before and after 27 April 1994 with particular reference to: what is meant by administrative action; the exercise of administrative power by private bodies regulated by the rules of administrative law, on the one hand, and exercises of private power regulated by rules of private law, on the other; the rules of standing, the notion of justiciability and the constitutionality of rules that seek to limit the right of the individual to approach a court to review administrative action; the meaning and scope of the right to lawful, reasonable and procedurally fair administrative action, in terms of the common law, the Constitution and the Promotion of Administrative Justice Act 3 of 2000; the meaning, scope and efficacy of the rights to reasons for administrative actions and of access to information; the procedure of judicial review and remedies that may be granted for the infringement of a person’s right to just administrative action; and conclusions and recommendations with regard to progress made in the construction of South Africa’s new, democratically based, administrative law.
- Full Text:
- Date Issued: 2003
- Authors: Plasket, Clive
- Date: 2003
- Subjects: Judicial review of administrative acts -- South Africa Administrative acts -- South Africa Administrative law -- South Africa Public administration -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3693 , http://hdl.handle.net/10962/d1003208
- Description: For most of its existence South African administrative law has been shaped by the doctrine of parliamentary sovereignty – the heart of the constitutional order from 1910 to 1994 – and a racist political system that favoured the white minority at the expense of the black majority. In these circumstances, the rules of administrative law were of limited use in protecting the individual from exercises of administrative power that infringed fundamental human rights, often on a grand scale. On 27 April 1994, however, a new political and constitutional order came into existence that swept away the very foundations of the old order: parliamentary sovereignty was replaced by constitutional supremacy and the racial exclusivity of the old order was replaced by a commitment to equality, freedom and dignity in a democratic state. A justiciable Bill of Rights was at centre stage in this new order. That Bill of Rights includes a fundamental right to just administrative action. It is both the new constitutional order and this rather unusual fundamental right that have changed the nature of South African administrative law. This thesis examines the effect of the fundamental right to just administrative action on the law and practice of the judicial review of administrative action. It does so principally by examining the legal position before and after 27 April 1994 with particular reference to: what is meant by administrative action; the exercise of administrative power by private bodies regulated by the rules of administrative law, on the one hand, and exercises of private power regulated by rules of private law, on the other; the rules of standing, the notion of justiciability and the constitutionality of rules that seek to limit the right of the individual to approach a court to review administrative action; the meaning and scope of the right to lawful, reasonable and procedurally fair administrative action, in terms of the common law, the Constitution and the Promotion of Administrative Justice Act 3 of 2000; the meaning, scope and efficacy of the rights to reasons for administrative actions and of access to information; the procedure of judicial review and remedies that may be granted for the infringement of a person’s right to just administrative action; and conclusions and recommendations with regard to progress made in the construction of South Africa’s new, democratically based, administrative law.
- Full Text:
- Date Issued: 2003
The geochemistry of ore fluids and control of gold mineralization in banded iron-formation at the Kalahari Goldridge deposit, Kraaipan greenstone belt, South Africa
- Authors: Hammond, Napoleon Quaye
- Date: 2003
- Subjects: Gold ores -- Geology -- South Africa -- North-West Greenstone belts -- South Africa -- North-West Ore deposits -- South Africa -- North-West Geochemistry -- South Africa -- North-West
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5048 , http://hdl.handle.net/10962/d1008370
- Description: The Kalahari Goldridge mine is located within the Archaean Kraaipan Greenstone Belt about 60 km SW of Mafikeng in the Northwestern Province, South Africa. Several gold deposits are located within approximately north - south-striking banded iron-formation (BIF). Current opencast mining operations are focused on the largest of these (D Zone). The orebody is stratabound and hosted primarily in the BIF, which consists of alternating chert and magnetite-chloritestilpnomelane-sulphide-carbonate bands ranging from mm to cm scale. The ore body varies in thickness from 15 to 45 m along a strike length of about 1.5 km. The BlF is sandwiched between a sericite-carbonate-chlorite schist at the immediate footwall and carbonaceous meta-pelites in the hanging-wall. Further west in the footwall, the schists are underlain by mafic meta-volcanic amphibolite. Overlying the hanging-wall carbonaceous metapeiites are schist units and meta-greywackes that become increasingly conglomeratic up the stratigraphy. Stilpnomelane-, chlorite- and minnesotaite-bearing assemblages in the BlFs indicate metamorphic temperatures of 300 - 450°C and pressures of less than 5 kbars. The BIF generally strikes approximately 3400 and dips from 60 to 75°E. Brittle-ductile deformation is evidenced by small-scale isoclinal folds, brecciation, extension fractures and boudinaging of cherty BIF units. Fold axial planes are sub-parallel to the foliation orientation with sub-vertical plunges parallel to prominent rodding and mineral lineation in the footwall. Gold mineralization at the Kalahari Goldridge deposit is associated with two generations of subhorizontal quartz-carbonate veins dips approximately 20 to 40°W. The first generation consists of ladder vein sets (Group lIA) preferentially developed in Fe-rich meso bands, whilst the second generation consists of large quartz-carbonate veins (Group lIB), which crosscut the entire ore body extending into the footwall and hanging-wall in places. Major structures that control the ore body are related to meso-scale isoclinal folds with fold axes subparallel to mineral elongation lineations, which plunge approximately 067°E. These linear structures form orthogonal orientation with the plane of the mineralized shallowdipping veins indicating stretching and development of fluid - focusing conduits. A second-order controlling feature corresponds to the intersection of the mineralized veins and foliation planes of host rock, plunging approximately 008°N and trending 341°. G0ld is closely associated with sulphides, mainly pyrite and pyrrhotite and to a lesser extent with bismuth tellurides, and carbonate gangue. The ore fluid responsible for the gold deposition is in the C-O-H system with increased CH₄ contents attributed to localized hydrolysis reaction between interbedded carbonaceous sediment and ore fluid. The fluid is characterized by significant C0₂ contents and low salinities below 7.0 wt % NaCl equivalent (averages of 3.5 and 3.0 wt % NaCl equivalent for the first and second episodes of the mineralization respectively) . Calculated values of f0₂. ranging from 10⁻²⁹·⁹⁸ to 10⁻³²·⁹⁶ bars, bracket the C0₂-CH₄ and pyrite-pyrrhotite-magnetite buffer boundaries and reveal the reducing nature of the ore fluid at deposition. Calculated total sulphur content in the ore fluid (mΣs), ranges from 0.011 to 0.018M and is consistent with the range (10⁻³·⁵ to 10⁻¹M) reported for subamphibolite facies ore fluids. The close association of sulphides with the Au and nature of the fluid also give credence that the Au was carried in solution by the Au(HS)₂ - complex. Extensive epigenetic replacement of magnetite and chlorite in BIF and other meta-pelitic sediments in the deposit by sulphides and carbonates, both on meso scopic and microscopic scales gives evidence of an interaction by a CO₂- and H₂S-bearing fluid with the Fe-rich host rocks in the deposit. This facilitated Au precipitation due to changes in the physico-chemical conditions of the ore fluid such as a decrease in the mΣs and pH leading to the destabilization of the reduced sulphur complexes. Local gradients in f0₂ may account for gold precipitation in places within carbonaceous sediments. The fineness of the gold grams (1000*Au/(Au + Ag) ranges from 823 to 921. This compares favourably with the fineness reported for some Archaean BIFhosced deposits (851 - 970). Mass balance transfer calculations indicate that major chemical changes associated with the hydrothermal alteration of BIF include enrichment of Au, Ag, Bi, Te, volatiles (S and CO₂), MgO, Ba, K and Rb but significant depletion of SiO₂ and minor losses of Fe₂O₃. In addition, anomalous enrichment of Sc (average, 1247%) suggests its possible use as an exploration tool in the ferruginous sediments in the Kraaipan greenstone terrane. Evidence from light stable isotopes and fluid inclusions suggests that the mineralized veins crystallized from a single homogeneous fluid source during the two episodes of mineralization under the similar physicochemical conditions. Deposition occurred at temperatures rangmg from 350 to 400°C and fluid pressures ranging from 0.7 to 2.0kbars. Stable isotope constraints indicate the following range for the hydrothermal fluid; θ¹⁸H₂O = 6.65 to 10.48%0, 8¹³CΣc = -6.0 to -8.0 %0 and 8³⁴SΣs = + 1.69 to + 4.0%0 . These data do not offer conclusive evidence for the source of fluid associated with the mineralization at the Kalahari Goldridge deposit as they overlap the range prescribed for fluid derived from devolatization of deep-seated volcano-sedimentary piles near the brittle-ductile transition in greenstone belts during prograde metamorphism, and magmatic hydrothermal fluids. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2003
- Authors: Hammond, Napoleon Quaye
- Date: 2003
- Subjects: Gold ores -- Geology -- South Africa -- North-West Greenstone belts -- South Africa -- North-West Ore deposits -- South Africa -- North-West Geochemistry -- South Africa -- North-West
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5048 , http://hdl.handle.net/10962/d1008370
- Description: The Kalahari Goldridge mine is located within the Archaean Kraaipan Greenstone Belt about 60 km SW of Mafikeng in the Northwestern Province, South Africa. Several gold deposits are located within approximately north - south-striking banded iron-formation (BIF). Current opencast mining operations are focused on the largest of these (D Zone). The orebody is stratabound and hosted primarily in the BIF, which consists of alternating chert and magnetite-chloritestilpnomelane-sulphide-carbonate bands ranging from mm to cm scale. The ore body varies in thickness from 15 to 45 m along a strike length of about 1.5 km. The BlF is sandwiched between a sericite-carbonate-chlorite schist at the immediate footwall and carbonaceous meta-pelites in the hanging-wall. Further west in the footwall, the schists are underlain by mafic meta-volcanic amphibolite. Overlying the hanging-wall carbonaceous metapeiites are schist units and meta-greywackes that become increasingly conglomeratic up the stratigraphy. Stilpnomelane-, chlorite- and minnesotaite-bearing assemblages in the BlFs indicate metamorphic temperatures of 300 - 450°C and pressures of less than 5 kbars. The BIF generally strikes approximately 3400 and dips from 60 to 75°E. Brittle-ductile deformation is evidenced by small-scale isoclinal folds, brecciation, extension fractures and boudinaging of cherty BIF units. Fold axial planes are sub-parallel to the foliation orientation with sub-vertical plunges parallel to prominent rodding and mineral lineation in the footwall. Gold mineralization at the Kalahari Goldridge deposit is associated with two generations of subhorizontal quartz-carbonate veins dips approximately 20 to 40°W. The first generation consists of ladder vein sets (Group lIA) preferentially developed in Fe-rich meso bands, whilst the second generation consists of large quartz-carbonate veins (Group lIB), which crosscut the entire ore body extending into the footwall and hanging-wall in places. Major structures that control the ore body are related to meso-scale isoclinal folds with fold axes subparallel to mineral elongation lineations, which plunge approximately 067°E. These linear structures form orthogonal orientation with the plane of the mineralized shallowdipping veins indicating stretching and development of fluid - focusing conduits. A second-order controlling feature corresponds to the intersection of the mineralized veins and foliation planes of host rock, plunging approximately 008°N and trending 341°. G0ld is closely associated with sulphides, mainly pyrite and pyrrhotite and to a lesser extent with bismuth tellurides, and carbonate gangue. The ore fluid responsible for the gold deposition is in the C-O-H system with increased CH₄ contents attributed to localized hydrolysis reaction between interbedded carbonaceous sediment and ore fluid. The fluid is characterized by significant C0₂ contents and low salinities below 7.0 wt % NaCl equivalent (averages of 3.5 and 3.0 wt % NaCl equivalent for the first and second episodes of the mineralization respectively) . Calculated values of f0₂. ranging from 10⁻²⁹·⁹⁸ to 10⁻³²·⁹⁶ bars, bracket the C0₂-CH₄ and pyrite-pyrrhotite-magnetite buffer boundaries and reveal the reducing nature of the ore fluid at deposition. Calculated total sulphur content in the ore fluid (mΣs), ranges from 0.011 to 0.018M and is consistent with the range (10⁻³·⁵ to 10⁻¹M) reported for subamphibolite facies ore fluids. The close association of sulphides with the Au and nature of the fluid also give credence that the Au was carried in solution by the Au(HS)₂ - complex. Extensive epigenetic replacement of magnetite and chlorite in BIF and other meta-pelitic sediments in the deposit by sulphides and carbonates, both on meso scopic and microscopic scales gives evidence of an interaction by a CO₂- and H₂S-bearing fluid with the Fe-rich host rocks in the deposit. This facilitated Au precipitation due to changes in the physico-chemical conditions of the ore fluid such as a decrease in the mΣs and pH leading to the destabilization of the reduced sulphur complexes. Local gradients in f0₂ may account for gold precipitation in places within carbonaceous sediments. The fineness of the gold grams (1000*Au/(Au + Ag) ranges from 823 to 921. This compares favourably with the fineness reported for some Archaean BIFhosced deposits (851 - 970). Mass balance transfer calculations indicate that major chemical changes associated with the hydrothermal alteration of BIF include enrichment of Au, Ag, Bi, Te, volatiles (S and CO₂), MgO, Ba, K and Rb but significant depletion of SiO₂ and minor losses of Fe₂O₃. In addition, anomalous enrichment of Sc (average, 1247%) suggests its possible use as an exploration tool in the ferruginous sediments in the Kraaipan greenstone terrane. Evidence from light stable isotopes and fluid inclusions suggests that the mineralized veins crystallized from a single homogeneous fluid source during the two episodes of mineralization under the similar physicochemical conditions. Deposition occurred at temperatures rangmg from 350 to 400°C and fluid pressures ranging from 0.7 to 2.0kbars. Stable isotope constraints indicate the following range for the hydrothermal fluid; θ¹⁸H₂O = 6.65 to 10.48%0, 8¹³CΣc = -6.0 to -8.0 %0 and 8³⁴SΣs = + 1.69 to + 4.0%0 . These data do not offer conclusive evidence for the source of fluid associated with the mineralization at the Kalahari Goldridge deposit as they overlap the range prescribed for fluid derived from devolatization of deep-seated volcano-sedimentary piles near the brittle-ductile transition in greenstone belts during prograde metamorphism, and magmatic hydrothermal fluids. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2003
The phosphorylation and nuclear localization of the co-chaperone murine stress-inducible protein 1
- Authors: Longshaw, Victoria Mary
- Date: 2003
- Subjects: Phosphorylation Proteins Heat shock proteins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3979 , http://hdl.handle.net/10962/d1004038
- Description: The co-chaperone murine stress-inducible protein 1 (mSTI1), a heat shock protein 70 (Hsp70)/ heat shock protein 90 (Hsp90) organizing protein (Hop) homologue, mediates the assembly of the Hsp70/Hsp90 chaperone heterocomplex. mSTI1 is phosphorylated in vitro by cell cycle kinases, proximal to a putative nuclear localization signal (NLS), substantiating a predicted CKII-cdc2-NLS (CcN) motif at position 189-239. Stable transfectants of NIH 3T3 fibroblasts that expressed mSTI1-EGFP, NLSmSTI1-EGFP and EGFP, were prepared. Fluorescence microscopy revealed mSTI1 was cytoplasmically localized, and that this localization was not affected by the fusion of mSTI1 with the EGFP moiety. NLSmSTI1-EGFP was targeted to the nucleus compared to EGFP, suggesting that the NLSmSTI1 was a functional NLS. The localization of mSTI1 was determined under normal and heat shock conditions, inhibition of nuclear export (leptomycin B), inhibition of CKII 5,6-dichlorobenzimidazole riboside, DRB), inhibition of cdc2 kinase (olomoucine), and G1/S phase arrest (hydroxyurea). mSTI1-EGFP and mSTI1 were excluded from the nucleus in the majority of resting cells, but accumulated in the nucleus following leptomycin B treatment, implying that mSTI1 possibly undergoes a functional import process, and export via the chromosomal region maintenance 1 (CRM-1)-mediated export pathway. Hydroxyurea and olomoucine (but not DRB or heat shock) treatment increased the proportion of cells in which mSTI1-EGFP exhibited cytoplasmic and nuclear localization. 2D gel electrophoresis detected three endogenous mSTI1 isoforms, which changed following hydroxyurea treatment. Furthermore, point inactivation and mimicking of phosphorylatable residues in mSTI1 altered the translocation of the protein and the isoform composition. Modification of mSTI1 at S189 and T198 decreased the number of isoforms of mSTI1-EGFP, suggesting that the protein is modified at these sites in vivo. The removal of the in vitro cdc2 kinase site at T198 promoted a nuclear localization during G1/S phase arrest. Therefore active cdc2 kinase, but not CKII, may be required for cytoplasmic localization of mSTI1. The CKII site appears to have no regulatory role under heat shock conditions or during the cell cycle. In vitro phosphorylation studies on untagged mSTI1 further supported the prediction that S189 is the only site recognised by CKII. The cdc2 kinase site at T198, however, although the major site, was not the only site phosphorylated in vitro. However, mSTI1 and cdc2 kinase did not interact in a detectable stable complex. Bioinformatic analysis of mSTI1 revealed NLS residues were conserved in STI1 proteins, and the NLS and TPR2A motifs were in close proximity. This may have mechanistic implications for the formation of the Hsp90-mSTI1 heterocomplex. The cytoplasmic or nuclear localization of mSTI1 is predicted to be the result of a dynamic equilibrium between nuclear import and nuclear export, the fulcrum of which may be shifted under different cell cycle conditions. These data provide the first evidence of regulated nuclear import/export of a major Hsp70/Hsp90 co-chaperone, and the regulation of this nuclear import by cell cycle status and cell cycle kinases.
- Full Text:
- Date Issued: 2003
- Authors: Longshaw, Victoria Mary
- Date: 2003
- Subjects: Phosphorylation Proteins Heat shock proteins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3979 , http://hdl.handle.net/10962/d1004038
- Description: The co-chaperone murine stress-inducible protein 1 (mSTI1), a heat shock protein 70 (Hsp70)/ heat shock protein 90 (Hsp90) organizing protein (Hop) homologue, mediates the assembly of the Hsp70/Hsp90 chaperone heterocomplex. mSTI1 is phosphorylated in vitro by cell cycle kinases, proximal to a putative nuclear localization signal (NLS), substantiating a predicted CKII-cdc2-NLS (CcN) motif at position 189-239. Stable transfectants of NIH 3T3 fibroblasts that expressed mSTI1-EGFP, NLSmSTI1-EGFP and EGFP, were prepared. Fluorescence microscopy revealed mSTI1 was cytoplasmically localized, and that this localization was not affected by the fusion of mSTI1 with the EGFP moiety. NLSmSTI1-EGFP was targeted to the nucleus compared to EGFP, suggesting that the NLSmSTI1 was a functional NLS. The localization of mSTI1 was determined under normal and heat shock conditions, inhibition of nuclear export (leptomycin B), inhibition of CKII 5,6-dichlorobenzimidazole riboside, DRB), inhibition of cdc2 kinase (olomoucine), and G1/S phase arrest (hydroxyurea). mSTI1-EGFP and mSTI1 were excluded from the nucleus in the majority of resting cells, but accumulated in the nucleus following leptomycin B treatment, implying that mSTI1 possibly undergoes a functional import process, and export via the chromosomal region maintenance 1 (CRM-1)-mediated export pathway. Hydroxyurea and olomoucine (but not DRB or heat shock) treatment increased the proportion of cells in which mSTI1-EGFP exhibited cytoplasmic and nuclear localization. 2D gel electrophoresis detected three endogenous mSTI1 isoforms, which changed following hydroxyurea treatment. Furthermore, point inactivation and mimicking of phosphorylatable residues in mSTI1 altered the translocation of the protein and the isoform composition. Modification of mSTI1 at S189 and T198 decreased the number of isoforms of mSTI1-EGFP, suggesting that the protein is modified at these sites in vivo. The removal of the in vitro cdc2 kinase site at T198 promoted a nuclear localization during G1/S phase arrest. Therefore active cdc2 kinase, but not CKII, may be required for cytoplasmic localization of mSTI1. The CKII site appears to have no regulatory role under heat shock conditions or during the cell cycle. In vitro phosphorylation studies on untagged mSTI1 further supported the prediction that S189 is the only site recognised by CKII. The cdc2 kinase site at T198, however, although the major site, was not the only site phosphorylated in vitro. However, mSTI1 and cdc2 kinase did not interact in a detectable stable complex. Bioinformatic analysis of mSTI1 revealed NLS residues were conserved in STI1 proteins, and the NLS and TPR2A motifs were in close proximity. This may have mechanistic implications for the formation of the Hsp90-mSTI1 heterocomplex. The cytoplasmic or nuclear localization of mSTI1 is predicted to be the result of a dynamic equilibrium between nuclear import and nuclear export, the fulcrum of which may be shifted under different cell cycle conditions. These data provide the first evidence of regulated nuclear import/export of a major Hsp70/Hsp90 co-chaperone, and the regulation of this nuclear import by cell cycle status and cell cycle kinases.
- Full Text:
- Date Issued: 2003
Versions of confinement: Melville's bodies and the psychology of conquest
- Authors: Goddard, Kevin Graham
- Date: 2003
- Subjects: Melville, Herman, 1819-1891 -- Criticism and interpretation Human body in literature
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2216 , http://hdl.handle.net/10962/d1002259
- Description: This thesis explores aspects of Melville’s presentation of both the whale and the human bodies in Moby-Dick and human bodies in other important novels. It argues that Melville uses his presentation of bodies to explore some of the versions of confinement those bodies experience, and by doing so, analyses the psychology which subtends that confinement. Throughout Melville’s works bodies are confined, both within literal spatial limits and by the psychology which creates and/or accepts these spatial limits. The thesis argues that perhaps the most important version of bodily confinement Melville addresses is the impulse to conquer bodies, both that of the other and one’s own. It adopts a largely psychoanalytic approach to interpreting bodies and their impulse to conquer, so that the body is seen to figure both in its actions and its external appearance the operations of the inner psyche. The figure of the body is equally prevalent in Melville’s exploration of nationalist conquest, where, as with Manifest Destiny and antebellum expansionism, the psychological and physical lack experienced by characters can be read as motivating factors in the ideology of conquest. A final important strand of the thesis is its argument in favour of a gradual shift in Melville’s interpretation of the value and possibility of genuine communion between human beings and between humans and the whale. One may read Typee as an attempt by Melville to explore the possibility of a this-worldly utopia in which human beings can return to a version of primitive interconnectedness. This exploration may be seen to be extended in Moby-Dick, particularly in Ishmael’s attempts to find communion with others and in some moments of encounter with the whales. The thesis uses phenomenology as a theory to interpret what Melville is trying to suggest in these moments of encounter. However, it argues, finally, that such encounter, or ‘intersubjectivity’ is eventually jettisoned, especially in the works after Moby-Dick. By the end of Melville’s life and work, any hope of an intersubjective utopia he may have harboured as a younger man have been removed in favour of a refusal actually to assert any final ‘truth’ about social, political or even religious experience. Billy Budd, his last body, is hanged, and his final word is silence.
- Full Text:
- Date Issued: 2003
- Authors: Goddard, Kevin Graham
- Date: 2003
- Subjects: Melville, Herman, 1819-1891 -- Criticism and interpretation Human body in literature
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2216 , http://hdl.handle.net/10962/d1002259
- Description: This thesis explores aspects of Melville’s presentation of both the whale and the human bodies in Moby-Dick and human bodies in other important novels. It argues that Melville uses his presentation of bodies to explore some of the versions of confinement those bodies experience, and by doing so, analyses the psychology which subtends that confinement. Throughout Melville’s works bodies are confined, both within literal spatial limits and by the psychology which creates and/or accepts these spatial limits. The thesis argues that perhaps the most important version of bodily confinement Melville addresses is the impulse to conquer bodies, both that of the other and one’s own. It adopts a largely psychoanalytic approach to interpreting bodies and their impulse to conquer, so that the body is seen to figure both in its actions and its external appearance the operations of the inner psyche. The figure of the body is equally prevalent in Melville’s exploration of nationalist conquest, where, as with Manifest Destiny and antebellum expansionism, the psychological and physical lack experienced by characters can be read as motivating factors in the ideology of conquest. A final important strand of the thesis is its argument in favour of a gradual shift in Melville’s interpretation of the value and possibility of genuine communion between human beings and between humans and the whale. One may read Typee as an attempt by Melville to explore the possibility of a this-worldly utopia in which human beings can return to a version of primitive interconnectedness. This exploration may be seen to be extended in Moby-Dick, particularly in Ishmael’s attempts to find communion with others and in some moments of encounter with the whales. The thesis uses phenomenology as a theory to interpret what Melville is trying to suggest in these moments of encounter. However, it argues, finally, that such encounter, or ‘intersubjectivity’ is eventually jettisoned, especially in the works after Moby-Dick. By the end of Melville’s life and work, any hope of an intersubjective utopia he may have harboured as a younger man have been removed in favour of a refusal actually to assert any final ‘truth’ about social, political or even religious experience. Billy Budd, his last body, is hanged, and his final word is silence.
- Full Text:
- Date Issued: 2003
Where the global meets the local : South African youth and their experience of global media
- Authors: Strelitz, Larry Nathan
- Date: 2003
- Subjects: Mass media and youth -- South Africa Mass media -- Sociological aspects Mass media and culture -- South Africa Youth -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3290 , http://hdl.handle.net/10962/d1003078
- Description: Within the context of debates concerning the impact of global media on local youth, this study explores how a sample of South African youth responds to texts which were produced internationally, but distributed locally. Recognising the profound rootedness of media consumption in everyday life, the research examines the way these youth, differentially embedded in the South African economic and ideological formation, use these texts as part of their ongoing attempts to make sense of their lives. The study rejects the 'either/or' formulations that often accompany competing structuralist and culturalist approaches to text/audience relationships. Instead, using a combination of quantitative and qualitative research methods, it seeks to highlight the interplay between agency and structure, between individual choice and the structuring of experience by wider social and historical factors. The findings of the study point to the complex individual and social reasons that lie behind media consumption choices, and the diverse (and socially patterned) reasons why local audiences are either attracted to, or reject, global media. These and other findings, the study argues, highlight the deficiencies of the media imperialism thesis with its definitive claims for cultural homogenisation, seen as the primary, or most politically significant, effect of the globalisation of media. As such, this study should be read as a dialogue with those schools of thought that take a more unequivocal point of view on the impact of globalised media culture.
- Full Text:
- Date Issued: 2003
- Authors: Strelitz, Larry Nathan
- Date: 2003
- Subjects: Mass media and youth -- South Africa Mass media -- Sociological aspects Mass media and culture -- South Africa Youth -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3290 , http://hdl.handle.net/10962/d1003078
- Description: Within the context of debates concerning the impact of global media on local youth, this study explores how a sample of South African youth responds to texts which were produced internationally, but distributed locally. Recognising the profound rootedness of media consumption in everyday life, the research examines the way these youth, differentially embedded in the South African economic and ideological formation, use these texts as part of their ongoing attempts to make sense of their lives. The study rejects the 'either/or' formulations that often accompany competing structuralist and culturalist approaches to text/audience relationships. Instead, using a combination of quantitative and qualitative research methods, it seeks to highlight the interplay between agency and structure, between individual choice and the structuring of experience by wider social and historical factors. The findings of the study point to the complex individual and social reasons that lie behind media consumption choices, and the diverse (and socially patterned) reasons why local audiences are either attracted to, or reject, global media. These and other findings, the study argues, highlight the deficiencies of the media imperialism thesis with its definitive claims for cultural homogenisation, seen as the primary, or most politically significant, effect of the globalisation of media. As such, this study should be read as a dialogue with those schools of thought that take a more unequivocal point of view on the impact of globalised media culture.
- Full Text:
- Date Issued: 2003
An analysis of the impact of democratization on debt-led growth : the Nigerian experience, 1970-2000
- Authors: Dinneya, Godson Eze
- Date: 2013-05-22
- Subjects: Debts, External -- Nigeria Nigeria -- Politics and government -- 1960- Nigeria -- Economic policy Nigeria -- Economic conditions -- 1960-
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1074 , http://hdl.handle.net/10962/d1007807
- Description: The debt-for democracy hypothesis is that undemocratic governments were largely responsible for not only the accumulation but also poor management of externally sourced capital resources. External borrowing had therefore failed to lead to growth of the economies of debtor countries under undemocratic political leadership. Despite this explanation of the debt problem conventional empirical analyses of the debt-growth relationship did not include political institutional variables. This study investigates the relationship between democratization and debt-led growth, using Nigeria, a typical debtor country whose politics was dominated by 'undemocratic ' governance, as a case study. Two broad research questions are investigated namely, whether available data support a negative or positive contribution of debt to the growth of the Nigeria economy during the period 1970-2000; and ifso was there any link between the levels of democratization in Nigeria and debt-led growth. Using a census of major political events in Nigeria around four dimensions of democratization, four primary indices of democratization and one composite index were constructed for the period. Using the Taylor (1983) marginal conditions to gauge the contribution of external debt to the growth of the Nigerian economy, the study found that external debt is capable of playing a double edged sword on the performance of the economy. Positive contributions coincided with the periods when Nigeria's oil dominated foreign exchange revenues were robust, and/ or when debt management strategies were better articulated and vice versa. The analyses of the link between democratization and debt-led growth using both correlation and regression techniques, yielded different results in two definitional contexts of debt-led growth. When defined purely in terms of the Taylor marginal conditions for a positive contribution of debt to the economy of a borrowing nation, the results support the pessimist view that democratization impeded growth. On the contrary, when debt-led growth was defined in a broader sense to incorporate variables such as domestic savings and investment, foreign direct investments, public and private consumption and debt burden, there was strong evidence that debt-led growth performed beller at higher levels of democratization than other wise. The result using the narrow definition was found to be a direct consequence of the overriding influence of export performance in the Taylor conditions. With Nigeria's exports almost entirely dominated by extractive industry the result derived using the narrow definition confirmed the theoretical links between natural resource endowment and regime type on the one hand, and external capital and the nature of the host country 's industry on the other. In the first resource dependence allowed the political leadership to be more detached and less accountable to the electorate since they did not need to levy taxes. Secondly foreign investors concerned with security of their sunk investments in the extractive oil induslly in particular favoured continuity of powerfol regimes with less democratic content. In both findings one thing was common: democratization was associated more with those factors whose decreases affect growth positively than with those whose increases improve growth. The conclusion from this is that the impact of democratization is stronger with negative than with positive growth factors. In other words, while democratization may be supportive of growth its greater impact appears to be in limiting the factors that themselves limit growth. To benefit from the favourable impact of democratisation on debt-led growth therefore the study suggests that improvements in the democratisation process in Nigeria is needed It identifies political education as central to this improvement. A model is developed to show how improvements in the political institutional framework may trickle down, through an enabling environment that is capable of engendering growth-enhancing domestic and international responses to lead in the direction of debt-led growth.
- Full Text:
An analysis of the impact of democratization on debt-led growth : the Nigerian experience, 1970-2000
- Authors: Dinneya, Godson Eze
- Date: 2013-05-22
- Subjects: Debts, External -- Nigeria Nigeria -- Politics and government -- 1960- Nigeria -- Economic policy Nigeria -- Economic conditions -- 1960-
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1074 , http://hdl.handle.net/10962/d1007807
- Description: The debt-for democracy hypothesis is that undemocratic governments were largely responsible for not only the accumulation but also poor management of externally sourced capital resources. External borrowing had therefore failed to lead to growth of the economies of debtor countries under undemocratic political leadership. Despite this explanation of the debt problem conventional empirical analyses of the debt-growth relationship did not include political institutional variables. This study investigates the relationship between democratization and debt-led growth, using Nigeria, a typical debtor country whose politics was dominated by 'undemocratic ' governance, as a case study. Two broad research questions are investigated namely, whether available data support a negative or positive contribution of debt to the growth of the Nigeria economy during the period 1970-2000; and ifso was there any link between the levels of democratization in Nigeria and debt-led growth. Using a census of major political events in Nigeria around four dimensions of democratization, four primary indices of democratization and one composite index were constructed for the period. Using the Taylor (1983) marginal conditions to gauge the contribution of external debt to the growth of the Nigerian economy, the study found that external debt is capable of playing a double edged sword on the performance of the economy. Positive contributions coincided with the periods when Nigeria's oil dominated foreign exchange revenues were robust, and/ or when debt management strategies were better articulated and vice versa. The analyses of the link between democratization and debt-led growth using both correlation and regression techniques, yielded different results in two definitional contexts of debt-led growth. When defined purely in terms of the Taylor marginal conditions for a positive contribution of debt to the economy of a borrowing nation, the results support the pessimist view that democratization impeded growth. On the contrary, when debt-led growth was defined in a broader sense to incorporate variables such as domestic savings and investment, foreign direct investments, public and private consumption and debt burden, there was strong evidence that debt-led growth performed beller at higher levels of democratization than other wise. The result using the narrow definition was found to be a direct consequence of the overriding influence of export performance in the Taylor conditions. With Nigeria's exports almost entirely dominated by extractive industry the result derived using the narrow definition confirmed the theoretical links between natural resource endowment and regime type on the one hand, and external capital and the nature of the host country 's industry on the other. In the first resource dependence allowed the political leadership to be more detached and less accountable to the electorate since they did not need to levy taxes. Secondly foreign investors concerned with security of their sunk investments in the extractive oil induslly in particular favoured continuity of powerfol regimes with less democratic content. In both findings one thing was common: democratization was associated more with those factors whose decreases affect growth positively than with those whose increases improve growth. The conclusion from this is that the impact of democratization is stronger with negative than with positive growth factors. In other words, while democratization may be supportive of growth its greater impact appears to be in limiting the factors that themselves limit growth. To benefit from the favourable impact of democratisation on debt-led growth therefore the study suggests that improvements in the democratisation process in Nigeria is needed It identifies political education as central to this improvement. A model is developed to show how improvements in the political institutional framework may trickle down, through an enabling environment that is capable of engendering growth-enhancing domestic and international responses to lead in the direction of debt-led growth.
- Full Text:
An analysis of selected World Trade Organisation agreements to determine whether they discriminate unfairly against developing economices
- Authors: Grimett, Leticia Anthea
- Date: 2013-07-29
- Subjects: World Trade Organization Foreign trade regulation General Agreement on Tariffs and Trade (Organization) Free trade -- Developing countries Foreign trade regulation -- Developing countries Competition, Unfair -- Developing countries
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3718 , http://hdl.handle.net/10962/d1008368
- Description: The focus of this thesis is the question whether or not the WTO discriminates unfairly against developing economies. In the absence of a test of guidelines for detennining unfairness or fairness of WTO provisions or Agreements has been drawn up using welfare economic and constitutional law principles as a foundation. Unfairness is therefore determined by asking whether the provisions of each Agreement are rational, proportional, efficient and whether they prevent the abuse of power amongst states. In addition, the economic effects of the provisions of the selected Agreements have been analysed to determine whether the relevant provisions are welfare enhancing and conclusive to promoting growth and development within developing economies. The Agreements chosed for analysis are the Agreements on Trade-related Investment Measures (TRIMS), Trade-related Intellectual Property (TRIPS), Agriculture and Services (GATS). The dispute settlement and negotiating process, labour standards and the impact of decreasing most-favoured nation rates on developing economy competitiveness is also discussed. Application of the test has shown that the WTO provisions do not reflect the interests of all members. Even though most member states are developing economies, the3 Agreements constantly cater foe developed country concerns and interests. Where provision is made for developing country interests, it is the LDC's who are favoured, with nonnal developing economies being bound by the same provisions as the developed economies. A fonnal, as opposed to a substantive, defmition has been adopted by the WTO, with a result that the process of equality is placed above the outcomes. While concessions have been made to development, members have not gone for enough. A main reason for the imbalance can be attributed to the negotiating process, which is based upon concessionary bargaining and trade-off. Those states with greater economic power are therefore at an advantage as they have the leverage needed to influence the outcomes of negotiations and hence the provisions of the various Agreements. Even with the LDC's, the WTO has been found to discriminate unfairly against developing economies because it does not adequately address developing country concerns. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Authors: Grimett, Leticia Anthea
- Date: 2013-07-29
- Subjects: World Trade Organization Foreign trade regulation General Agreement on Tariffs and Trade (Organization) Free trade -- Developing countries Foreign trade regulation -- Developing countries Competition, Unfair -- Developing countries
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3718 , http://hdl.handle.net/10962/d1008368
- Description: The focus of this thesis is the question whether or not the WTO discriminates unfairly against developing economies. In the absence of a test of guidelines for detennining unfairness or fairness of WTO provisions or Agreements has been drawn up using welfare economic and constitutional law principles as a foundation. Unfairness is therefore determined by asking whether the provisions of each Agreement are rational, proportional, efficient and whether they prevent the abuse of power amongst states. In addition, the economic effects of the provisions of the selected Agreements have been analysed to determine whether the relevant provisions are welfare enhancing and conclusive to promoting growth and development within developing economies. The Agreements chosed for analysis are the Agreements on Trade-related Investment Measures (TRIMS), Trade-related Intellectual Property (TRIPS), Agriculture and Services (GATS). The dispute settlement and negotiating process, labour standards and the impact of decreasing most-favoured nation rates on developing economy competitiveness is also discussed. Application of the test has shown that the WTO provisions do not reflect the interests of all members. Even though most member states are developing economies, the3 Agreements constantly cater foe developed country concerns and interests. Where provision is made for developing country interests, it is the LDC's who are favoured, with nonnal developing economies being bound by the same provisions as the developed economies. A fonnal, as opposed to a substantive, defmition has been adopted by the WTO, with a result that the process of equality is placed above the outcomes. While concessions have been made to development, members have not gone for enough. A main reason for the imbalance can be attributed to the negotiating process, which is based upon concessionary bargaining and trade-off. Those states with greater economic power are therefore at an advantage as they have the leverage needed to influence the outcomes of negotiations and hence the provisions of the various Agreements. Even with the LDC's, the WTO has been found to discriminate unfairly against developing economies because it does not adequately address developing country concerns. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
Democracy and party dominance in Kenya and South Africa : a comparative study of the Kenya African National Union and the African National Congres
- Authors: Mwangi, Oscar Gakuo
- Date: 2013-08-15
- Subjects: Kenya African National Union African National Congress Political parties -- South Africa Political parties -- Kenya Democracy -- South Africa Democracy -- Kenya South Africa -- Politics and government Kenya -- Politics and government
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2876 , http://hdl.handle.net/10962/d1008431
- Description: Kenya and South Africa can be described as dominant party systems, under the dominance of the Kenya African National Union CKANU) and the African National Congress CANC) respectively. A dominant party system is in essence a democracy. The spirit of democracy may, however, apparently be contradicted by the weight of party dominance, thus questioning the content of and prospects for democracy under party dominance in both Kenya and South Africa. The study is a comparative analysis of party dominance in Kenya and South Africa. The main objective is to exan1ine the relationship between party dominance and democracy in both countries. It seeks to find out how party dominance is reproducing itself and surviving the post 1990 transition processes in Kenya and South Africa. More importantly, the study also seeks to find out how party dominance impacts upon institutions that support or uphold democratization and subsequently democracy. The findings of the study demonstrate that party dominance has reproduced itself and survived the post-1990 period, and is also impacting upon democratization and democracy. The dominant parties take a similar trajectory in pursuit of dominance over the state and its apparatuses. However, they differ when it comes to their relationship with the civil society. That between KANU and civil society is antagonistic, as the ruling party seeks to augment political power through authoritarian dominance of the latter to, while that of the ANC and civil society is responsive, as the former seeks to enhance political stability in the country. The impact of party dominance upon institutions that support democracy takes similar and different trajectories in both countries. Similarities arise with respect to the detrimental impact upon institutions of the Executive that ensure accountability and transparency, evident in the increasing cases of corruption, nepotism and political patronage appointments. Similarly, there has been a detrimental impact upon the Legislature regarding parliamentary proceedings. Parliamentary committees and opposition parties are being rendered ineffective as organs of ensuring transparency and accountability, and are often subject to delegitimation. The impact of party dominance on the Judiciary, however, differs in both countries. In Kenya, the judiciary continues to suffer from excessive interference from the Executive and the ruling party, whereas in South Africa the judicial system remains largely independent with regard to the application of justice, despite constant criticisms from the dominant party. The study concludes that South Africa is, gradually, going the Kenyan way. If this condition is left unchecked there is the possibility that South Africa could eventually end up a psuedo-democracy like Kenya, where formal democratic political institutions such as multiparty elections, exist to mask the reality of authoritarian dominance. The thesis recommends that strengthening civil society organizations, opposition political parties, and state institutions in both countries to ensure greater accountability and transparency, will reverse this detrimental effect of party dominance. It also recommends meaningful constitutional reforms that will guarantee greater independence of these institutions, and the decentralization of governmental and political power to check and limit the powers of the dominant party. Also recommended are areas for further research. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Authors: Mwangi, Oscar Gakuo
- Date: 2013-08-15
- Subjects: Kenya African National Union African National Congress Political parties -- South Africa Political parties -- Kenya Democracy -- South Africa Democracy -- Kenya South Africa -- Politics and government Kenya -- Politics and government
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2876 , http://hdl.handle.net/10962/d1008431
- Description: Kenya and South Africa can be described as dominant party systems, under the dominance of the Kenya African National Union CKANU) and the African National Congress CANC) respectively. A dominant party system is in essence a democracy. The spirit of democracy may, however, apparently be contradicted by the weight of party dominance, thus questioning the content of and prospects for democracy under party dominance in both Kenya and South Africa. The study is a comparative analysis of party dominance in Kenya and South Africa. The main objective is to exan1ine the relationship between party dominance and democracy in both countries. It seeks to find out how party dominance is reproducing itself and surviving the post 1990 transition processes in Kenya and South Africa. More importantly, the study also seeks to find out how party dominance impacts upon institutions that support or uphold democratization and subsequently democracy. The findings of the study demonstrate that party dominance has reproduced itself and survived the post-1990 period, and is also impacting upon democratization and democracy. The dominant parties take a similar trajectory in pursuit of dominance over the state and its apparatuses. However, they differ when it comes to their relationship with the civil society. That between KANU and civil society is antagonistic, as the ruling party seeks to augment political power through authoritarian dominance of the latter to, while that of the ANC and civil society is responsive, as the former seeks to enhance political stability in the country. The impact of party dominance upon institutions that support democracy takes similar and different trajectories in both countries. Similarities arise with respect to the detrimental impact upon institutions of the Executive that ensure accountability and transparency, evident in the increasing cases of corruption, nepotism and political patronage appointments. Similarly, there has been a detrimental impact upon the Legislature regarding parliamentary proceedings. Parliamentary committees and opposition parties are being rendered ineffective as organs of ensuring transparency and accountability, and are often subject to delegitimation. The impact of party dominance on the Judiciary, however, differs in both countries. In Kenya, the judiciary continues to suffer from excessive interference from the Executive and the ruling party, whereas in South Africa the judicial system remains largely independent with regard to the application of justice, despite constant criticisms from the dominant party. The study concludes that South Africa is, gradually, going the Kenyan way. If this condition is left unchecked there is the possibility that South Africa could eventually end up a psuedo-democracy like Kenya, where formal democratic political institutions such as multiparty elections, exist to mask the reality of authoritarian dominance. The thesis recommends that strengthening civil society organizations, opposition political parties, and state institutions in both countries to ensure greater accountability and transparency, will reverse this detrimental effect of party dominance. It also recommends meaningful constitutional reforms that will guarantee greater independence of these institutions, and the decentralization of governmental and political power to check and limit the powers of the dominant party. Also recommended are areas for further research. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text: