A comparative study of atmospheric dynamics in the mesosphere and lower thermosphere (MLT) near Grahamstown (South Africa) and Adelaide (Australia)
- Authors: Malinga, Sandile Bethuel
- Date: 2002
- Subjects: Atmospheric physics Atmospheric physics -- South Africa -- Eastern Cape Atmospheric physics -- Australia Dynamic meteorology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5506 , http://hdl.handle.net/10962/d1007307
- Description: The observations made near Grahamstown (33 .3°S, 26.5°E), South Africa and Adelaide (34.5°S, 138.5°E), Australia over the years 1987 to 1994 are used to study the dynamics of the mesosphere and lower thermosphere (ML T) region with a focus on ∼ 90 km altitude. In particular this thesis deals with on the atmospheric mean flow and the solar diurnal and semi diurnal oscillations with a view to (i) deducing their patterns at the two sites, (ii) comparing the dynamic structures observed at the two sites with special emphases on longitudinal variations, and (iii) putting these observations in a global context by comparing with other ground-based observations, satellite observations and numerical simulations. The main findings are summarised below. The mean flow and the tides at Grahamstown and Adelaide are characteristically variable at planetary time scales. Wavelet spectral and multiresolution analyses reveal that the dominant planetary oscillation is the quasi-16-day oscillation. However, no apparent correlation in the 16-day waves of the mean flow, the diurnal tide and the semidiurnal tide was found. The short-term fluctuations were also investigated using complex demodulation and bispectral techniques and it was found that some of the observed variations in tides could be due to non-linear wave-wave interactions. The long-term trends of the mean flow and tides show patterns that are in broad agreement with theory, results from elsewhere (ground-based and satellite) and the results of the Global-Scale Wave Model and various models by Portnyagin and others. In general the mean flow, the amplitudes and phases of both tides were found to exhibit seasonal and interannual variations which are thought to be related to various factors including (i) changes in the atmospheric mean environment, (ii) thermotidal forcing (iii) gravity wave effects, (iv) planetary scale influence, (v) long-term (e.g. quasi-biennial oscillation) modulation, and (vi) solar activity. There are significant longitudinal differences in the dynamic structure between Grahamstown and Adelaide. More especially, Grahamstown tends to have stronger mean flow and tidal activity than Adelaide. For tides, these differences are thought to be partly due to nonmigrating tidal modes but, in general, migrating modes were found to be dominant.
- Full Text:
- Date Issued: 2002
- Authors: Malinga, Sandile Bethuel
- Date: 2002
- Subjects: Atmospheric physics Atmospheric physics -- South Africa -- Eastern Cape Atmospheric physics -- Australia Dynamic meteorology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5506 , http://hdl.handle.net/10962/d1007307
- Description: The observations made near Grahamstown (33 .3°S, 26.5°E), South Africa and Adelaide (34.5°S, 138.5°E), Australia over the years 1987 to 1994 are used to study the dynamics of the mesosphere and lower thermosphere (ML T) region with a focus on ∼ 90 km altitude. In particular this thesis deals with on the atmospheric mean flow and the solar diurnal and semi diurnal oscillations with a view to (i) deducing their patterns at the two sites, (ii) comparing the dynamic structures observed at the two sites with special emphases on longitudinal variations, and (iii) putting these observations in a global context by comparing with other ground-based observations, satellite observations and numerical simulations. The main findings are summarised below. The mean flow and the tides at Grahamstown and Adelaide are characteristically variable at planetary time scales. Wavelet spectral and multiresolution analyses reveal that the dominant planetary oscillation is the quasi-16-day oscillation. However, no apparent correlation in the 16-day waves of the mean flow, the diurnal tide and the semidiurnal tide was found. The short-term fluctuations were also investigated using complex demodulation and bispectral techniques and it was found that some of the observed variations in tides could be due to non-linear wave-wave interactions. The long-term trends of the mean flow and tides show patterns that are in broad agreement with theory, results from elsewhere (ground-based and satellite) and the results of the Global-Scale Wave Model and various models by Portnyagin and others. In general the mean flow, the amplitudes and phases of both tides were found to exhibit seasonal and interannual variations which are thought to be related to various factors including (i) changes in the atmospheric mean environment, (ii) thermotidal forcing (iii) gravity wave effects, (iv) planetary scale influence, (v) long-term (e.g. quasi-biennial oscillation) modulation, and (vi) solar activity. There are significant longitudinal differences in the dynamic structure between Grahamstown and Adelaide. More especially, Grahamstown tends to have stronger mean flow and tidal activity than Adelaide. For tides, these differences are thought to be partly due to nonmigrating tidal modes but, in general, migrating modes were found to be dominant.
- Full Text:
- Date Issued: 2002
A historical study of John Graham Lake and South African/United States pentecostalism
- Authors: Burpeau, Kemp Pendleton
- Date: 2002
- Subjects: Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2587 , http://hdl.handle.net/10962/d1006484 , Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Description: American minister John Graham Lake (1870-1935) was a pivotal participant in an era of profound religious and political transition. Surprisingly, Lake's often provocative life had previously been largely neglected as a field of academic inquiry. In the U.S. Lake associated with key Holiness, Wesleyan and Apostolic Faith charismatics like John Alexander Dowie of the Zion City, Illinois Utopia, Charles Parham of the Topeka Revival and William Seymour of the Azusa Street Revival. Lake served as an important intermediary between Parham's often reactionary, white orientation that was unreceptive to an enthusiastic black liturgy and Seymour's expansive African-American egalitarianism expressed through exuberant spirit manifestations. Lake's South African ministry was shaped by his middle class white business background, Azusa Street message and American perspectives. He brought together the faith healing movement inspired by Dutch Reformed minister Andrew Murray, P. Ie Roux's black and white Zion charismatic adherents affiliated with Dowie and the new U.S. Pentecostalism of Parham and Seymour. Lake's African-American influenced Pentecostalism was compatible with indigenous African worship. His emphasis on the spiritual needs of the disempowered found a receptive audience in talented black evangelists Elias Letwaba and Edward Lion. Even though acquainted with Mohandas Gandhi, Lake did not undertake a South African social gospel-type civil protest against societal injustice. In fact, Lake's participation with Afrikaner politicians like Louis Botha in fashioning a segregationist land use law was most troubling. Lake was ambivalent about racial integration. His belief in an egalitarian status for all Christians, his Populist/Progressive ethics and his enthusiastic promotion of women's rights were complicated by his advocacy, or at least tolerance, of some disparate racial treatment in his Apostolic Faith Mission and South African society at large. Lake's paternalism and notion of Westem cultural superiority conflicted with his love of all persons. Lake's otherworldly prioritization of individual spiritualism over a socioeconomic agenda usually stymied activism. His uncharacteristic use of nonviolent protest to protect faith healing formed a remarkable contrast with his reluctance to actively campaign against unequal racial treatment in Africa and America. Historiographical perspectives on Lake range from the saintly pioneer charismatic missionary to the Elmer Gantry type charlatan acting only for personal benefit. Lake was a unique personality with his flamboyant rhetoric, strong convictions and feelings of personal worth. His distinctive Jesus as healing and suffering God theology evidenced both consistency with precedent as well as creative anticipation. Shortcomings resulting from his preference to address social concerns on an individual spiritual rather than societal level, his liberties with truth and his bad business judgments resulting in litigation. Nevertheless, Lake's life demonstrated that a gifted but imperfect instrument could accomplish a meaningful ministry. , Adobe Acrobat Pro 9.5.4 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
- Authors: Burpeau, Kemp Pendleton
- Date: 2002
- Subjects: Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2587 , http://hdl.handle.net/10962/d1006484 , Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Description: American minister John Graham Lake (1870-1935) was a pivotal participant in an era of profound religious and political transition. Surprisingly, Lake's often provocative life had previously been largely neglected as a field of academic inquiry. In the U.S. Lake associated with key Holiness, Wesleyan and Apostolic Faith charismatics like John Alexander Dowie of the Zion City, Illinois Utopia, Charles Parham of the Topeka Revival and William Seymour of the Azusa Street Revival. Lake served as an important intermediary between Parham's often reactionary, white orientation that was unreceptive to an enthusiastic black liturgy and Seymour's expansive African-American egalitarianism expressed through exuberant spirit manifestations. Lake's South African ministry was shaped by his middle class white business background, Azusa Street message and American perspectives. He brought together the faith healing movement inspired by Dutch Reformed minister Andrew Murray, P. Ie Roux's black and white Zion charismatic adherents affiliated with Dowie and the new U.S. Pentecostalism of Parham and Seymour. Lake's African-American influenced Pentecostalism was compatible with indigenous African worship. His emphasis on the spiritual needs of the disempowered found a receptive audience in talented black evangelists Elias Letwaba and Edward Lion. Even though acquainted with Mohandas Gandhi, Lake did not undertake a South African social gospel-type civil protest against societal injustice. In fact, Lake's participation with Afrikaner politicians like Louis Botha in fashioning a segregationist land use law was most troubling. Lake was ambivalent about racial integration. His belief in an egalitarian status for all Christians, his Populist/Progressive ethics and his enthusiastic promotion of women's rights were complicated by his advocacy, or at least tolerance, of some disparate racial treatment in his Apostolic Faith Mission and South African society at large. Lake's paternalism and notion of Westem cultural superiority conflicted with his love of all persons. Lake's otherworldly prioritization of individual spiritualism over a socioeconomic agenda usually stymied activism. His uncharacteristic use of nonviolent protest to protect faith healing formed a remarkable contrast with his reluctance to actively campaign against unequal racial treatment in Africa and America. Historiographical perspectives on Lake range from the saintly pioneer charismatic missionary to the Elmer Gantry type charlatan acting only for personal benefit. Lake was a unique personality with his flamboyant rhetoric, strong convictions and feelings of personal worth. His distinctive Jesus as healing and suffering God theology evidenced both consistency with precedent as well as creative anticipation. Shortcomings resulting from his preference to address social concerns on an individual spiritual rather than societal level, his liberties with truth and his bad business judgments resulting in litigation. Nevertheless, Lake's life demonstrated that a gifted but imperfect instrument could accomplish a meaningful ministry. , Adobe Acrobat Pro 9.5.4 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
Biological generation of reactive alkaline species and their application in a sustainable bioprocess for the remediation of acid and metal contaminated wastewaters
- Authors: Van Hille, Robert Paul
- Date: 2002
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:21049 , http://hdl.handle.net/10962/6129
- Description: This project focused on the development of an integrated biological system for the treatment of acidic and metal-laden effluents, based on the sustainable biological generation of reactive alkaline species. Initial studies concentrated on the binding and accumulation of heavy metals by biomass of the cyanobacteria, Spirulina sp. Metal binding was rapid, with saturation reached in 30 minutes, and followed an affinity series of Pb > Cu > Zn >>Fe. The binding capacity of the Spirulina for each of the metals was relatively low when compared to a range of other biosorbents. The toxicity thresholds of the algae was determined for copper and zinc. These were low (10umoles/g) and as such, the algae were not suitable for application in a treatment system in which they came into direct contact with the toxic metals. The algae were able to increase the pH of the surrounding medium. This occurred as a result of the accumulation of inorganic carbon, from bicarbonate, as a response to low concentrations of carbon dioxide in the medium. The resulting release of a hydroxide ion into solution led to the increase in pH. The increase in pH was shown to be due to a reduction in acidity, rather than an increase in alkalinity. The enzyme carbonic anhydrase was shown to be pivotal in this system. Attempts to determine the enzyme activity directly were unsuccessful, due to the inherent inaccuracy of the assay system. An indirect method of determining enzyme activity, by measuring changes in the carbonate species equilibrium, was developed. Under optimal conditions Spirulina was able to reduce the acidity by an amount equivalent to the addition of 3670umoles NaOH g·' h·'. Predictive modelling showed that this enhanced the potential of the medium to effect metal precipitation. For the algal system to be sustainable, a readily available source of bicarbonate was needed. This was achieved by the oxidation of organic carbon, under sulphidogenic conditions, by a bacterial consortium isolated from the anaerobic component of a facultative pond. The consortium was shown to consist of sulphate reducing (most likely Desulvovibrio and Desulfotomaculum)and acetogenic bacteria. Sulphate removal rates of 500mg 1·' day·' and 135mg 1·' day·' were achieved in a 21 agitated and 281 upflow reactor respectively. The bicarbonate generation rate in the 281 reactor was calculated as 4033umoles 1·' day·', which proved sufficient to act as a feed for the algal system. Sparging the anaerobic digester overflow with air and nitrogen resulted in a reduction in the aqueous sulphide concentration. Using nitrogen, a 70% recovery of sulphide, as H2S gas, was achieved in 60 minutes, while with air, this dropped to 40%, due to the oxidation of the aqueous sulphide. The stripping ofH2S resulted in an increase in pH. The H2S gas was used for the selective precipitation of copper and lead in the integrated system. The dynamics of metal precipitation was investigated. For simple reactions, between individual IV metal and base species, it was possible to generate an accurate predictive model and confirm the precipitating species using wavelength dispersive X-ray spectroscopy (WDS). In more complex systems, where precipitation of the artificial acid mine drainage was examined, the predictive modelling and WDS could not accurately describe the system. The addition of aqueous sulphide to copper and iron resulted in the formation of metastable, amorphous precipitates, which remained in suspension. Ageing of the copper precipitate resulted in the evolution of a stable crystalline structure (covellite) and the aggregation and settling of the precipitate. In the case of iron, the amorphous precipitate underwent oxidation before a stable iron sulphide could evolve and the settled precipitate was an iron oxide or oxyhydroxide. The artificial acid mine drainage was treated with sulphide, hydroxide, anaerobic digester overflow and algal overflow. The best metal removal was achieved with the sulphide and hydroxide, while the algal overflow outperformed the anaerobic digester overflow. The precipitate generated by the addition of sulphide was the most compact, followed by the algal overflow, the anaerobic digester overflow and the hydroxide. Efficient precipitation of all the heavy metals, except manganese, was achieved using the algal overflow at an acidity to alkalinity ratio of 1 :2. This ratio was selected for use in the pilot system. The Spirulina based pilot system was effectively used to treat an effluent from the Black Mountain base metal mine. The necessity to maintain the algae in suspension and avoid biomass washout were practical considerations which counted against this system. The replacement of the Spirulina by Oscillatoria, which adhered to a solid support, overcame these problems. The integrated biological system was able to effectively treat an artificial acid mine drainage for 90 days, reducing the concentration of all metals, except manganese, to below the acceptable environmental risk levels. The treatment of the final effluent in a second anaerobic digester reduced the manganese concentration to 4.5uM and proved that the sulphate reducing bacteria could be cultivated on enriched, partially treated acid mine drainage. The integrated biological treatment system performed well, effectively treating an effluent modelled closely on the quality of the water being discharged from the East Rand Basin. The cost of such a system would be considerably less than a "high tech" physico-chemical system. This, coupled with the potential long term sustainability of a biological system, would make it a potentially attractive option for the treatment of future acid mine drainage discharges.
- Full Text:
- Date Issued: 2002
- Authors: Van Hille, Robert Paul
- Date: 2002
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:21049 , http://hdl.handle.net/10962/6129
- Description: This project focused on the development of an integrated biological system for the treatment of acidic and metal-laden effluents, based on the sustainable biological generation of reactive alkaline species. Initial studies concentrated on the binding and accumulation of heavy metals by biomass of the cyanobacteria, Spirulina sp. Metal binding was rapid, with saturation reached in 30 minutes, and followed an affinity series of Pb > Cu > Zn >>Fe. The binding capacity of the Spirulina for each of the metals was relatively low when compared to a range of other biosorbents. The toxicity thresholds of the algae was determined for copper and zinc. These were low (10umoles/g) and as such, the algae were not suitable for application in a treatment system in which they came into direct contact with the toxic metals. The algae were able to increase the pH of the surrounding medium. This occurred as a result of the accumulation of inorganic carbon, from bicarbonate, as a response to low concentrations of carbon dioxide in the medium. The resulting release of a hydroxide ion into solution led to the increase in pH. The increase in pH was shown to be due to a reduction in acidity, rather than an increase in alkalinity. The enzyme carbonic anhydrase was shown to be pivotal in this system. Attempts to determine the enzyme activity directly were unsuccessful, due to the inherent inaccuracy of the assay system. An indirect method of determining enzyme activity, by measuring changes in the carbonate species equilibrium, was developed. Under optimal conditions Spirulina was able to reduce the acidity by an amount equivalent to the addition of 3670umoles NaOH g·' h·'. Predictive modelling showed that this enhanced the potential of the medium to effect metal precipitation. For the algal system to be sustainable, a readily available source of bicarbonate was needed. This was achieved by the oxidation of organic carbon, under sulphidogenic conditions, by a bacterial consortium isolated from the anaerobic component of a facultative pond. The consortium was shown to consist of sulphate reducing (most likely Desulvovibrio and Desulfotomaculum)and acetogenic bacteria. Sulphate removal rates of 500mg 1·' day·' and 135mg 1·' day·' were achieved in a 21 agitated and 281 upflow reactor respectively. The bicarbonate generation rate in the 281 reactor was calculated as 4033umoles 1·' day·', which proved sufficient to act as a feed for the algal system. Sparging the anaerobic digester overflow with air and nitrogen resulted in a reduction in the aqueous sulphide concentration. Using nitrogen, a 70% recovery of sulphide, as H2S gas, was achieved in 60 minutes, while with air, this dropped to 40%, due to the oxidation of the aqueous sulphide. The stripping ofH2S resulted in an increase in pH. The H2S gas was used for the selective precipitation of copper and lead in the integrated system. The dynamics of metal precipitation was investigated. For simple reactions, between individual IV metal and base species, it was possible to generate an accurate predictive model and confirm the precipitating species using wavelength dispersive X-ray spectroscopy (WDS). In more complex systems, where precipitation of the artificial acid mine drainage was examined, the predictive modelling and WDS could not accurately describe the system. The addition of aqueous sulphide to copper and iron resulted in the formation of metastable, amorphous precipitates, which remained in suspension. Ageing of the copper precipitate resulted in the evolution of a stable crystalline structure (covellite) and the aggregation and settling of the precipitate. In the case of iron, the amorphous precipitate underwent oxidation before a stable iron sulphide could evolve and the settled precipitate was an iron oxide or oxyhydroxide. The artificial acid mine drainage was treated with sulphide, hydroxide, anaerobic digester overflow and algal overflow. The best metal removal was achieved with the sulphide and hydroxide, while the algal overflow outperformed the anaerobic digester overflow. The precipitate generated by the addition of sulphide was the most compact, followed by the algal overflow, the anaerobic digester overflow and the hydroxide. Efficient precipitation of all the heavy metals, except manganese, was achieved using the algal overflow at an acidity to alkalinity ratio of 1 :2. This ratio was selected for use in the pilot system. The Spirulina based pilot system was effectively used to treat an effluent from the Black Mountain base metal mine. The necessity to maintain the algae in suspension and avoid biomass washout were practical considerations which counted against this system. The replacement of the Spirulina by Oscillatoria, which adhered to a solid support, overcame these problems. The integrated biological system was able to effectively treat an artificial acid mine drainage for 90 days, reducing the concentration of all metals, except manganese, to below the acceptable environmental risk levels. The treatment of the final effluent in a second anaerobic digester reduced the manganese concentration to 4.5uM and proved that the sulphate reducing bacteria could be cultivated on enriched, partially treated acid mine drainage. The integrated biological treatment system performed well, effectively treating an effluent modelled closely on the quality of the water being discharged from the East Rand Basin. The cost of such a system would be considerably less than a "high tech" physico-chemical system. This, coupled with the potential long term sustainability of a biological system, would make it a potentially attractive option for the treatment of future acid mine drainage discharges.
- Full Text:
- Date Issued: 2002
Biosulphidogenic hydrolysis of lignin and lignin model compounds
- Authors: Madikane, Mzekelo
- Date: 2002
- Subjects: Lignin Lignin -- Biodegradation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3917 , http://hdl.handle.net/10962/d1003976
- Description: Lignin degradation under biosulphidogenic conditions has not been extensively reported in the literature. Although aerobic degradation of lignin is well documented, anaerobic biodegradation has focused mainly on methanogenic systems with biosulphidogenic systems receiving less attention. Sulphate reducing bacteria are known to generate moderately high levels of both sulphide and alkalinity at room temperatures, and these conditions draw some comparison with the Kraft pulping process. In the Kraft pulping process, lignin is degraded chemically at ±170°C under high sulphide and alkaline conditions and may provide a model for understanding biosulphidogenic lignin degrading activity. The aim of this study was to investigate the biosulphidogenic hydrolysis of lignin within the context of the chemical and biological conditions generated by a mixed sulphate reducing bacteria consortia. Bioreactor studies with a mixed sulphate reducing consortia and pine wood powder (both untreated and depectinated) resulted in the generation of comparable levels of sulphide and alkalinity used in the chemical hydrolysis studies. Aromatic compound yields were between 20 to 50% of the chemical hydrolysis studies. This fluctuation may have been due to the utilization of these aromatic compounds as electron donors by the sulphate reducing consortia as evidenced by the high rate of sulphate reduction in both the untreated and depectinated wood bioreactors. Biodegradation of lignin model compounds was investigated in order to elucidate lignin degradation mechanisms. Both mono-aromatic and dimeric lignin model compounds were used as electron donors and carbon sources for the mixed sulphate reducing consortia. Biodegradation and mass spectrometer analysis of mono-aromatic compounds, ferulic acid and ferulic acid ethyl ester resulted in the production of intermediates such as catechol, cyclohexane carboxylic acid and adipic acid. These intermediates were also observed in the degradation of dimeric ferulic acid. Biodegradation of salicin resulted in the production of salicyl alcohol, ortho-cresol and acetate. Biodegradation of benzylic ether resulted in the production of vanillin and acetate as end products. The results of these studies provide evidence for a biosulphidogenic hydrolysis of lignin, and also the utilisation of lignin-derived aromatic compounds as electron donor sources, by a mixed sulphate reducing consortia.
- Full Text:
- Date Issued: 2002
- Authors: Madikane, Mzekelo
- Date: 2002
- Subjects: Lignin Lignin -- Biodegradation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3917 , http://hdl.handle.net/10962/d1003976
- Description: Lignin degradation under biosulphidogenic conditions has not been extensively reported in the literature. Although aerobic degradation of lignin is well documented, anaerobic biodegradation has focused mainly on methanogenic systems with biosulphidogenic systems receiving less attention. Sulphate reducing bacteria are known to generate moderately high levels of both sulphide and alkalinity at room temperatures, and these conditions draw some comparison with the Kraft pulping process. In the Kraft pulping process, lignin is degraded chemically at ±170°C under high sulphide and alkaline conditions and may provide a model for understanding biosulphidogenic lignin degrading activity. The aim of this study was to investigate the biosulphidogenic hydrolysis of lignin within the context of the chemical and biological conditions generated by a mixed sulphate reducing bacteria consortia. Bioreactor studies with a mixed sulphate reducing consortia and pine wood powder (both untreated and depectinated) resulted in the generation of comparable levels of sulphide and alkalinity used in the chemical hydrolysis studies. Aromatic compound yields were between 20 to 50% of the chemical hydrolysis studies. This fluctuation may have been due to the utilization of these aromatic compounds as electron donors by the sulphate reducing consortia as evidenced by the high rate of sulphate reduction in both the untreated and depectinated wood bioreactors. Biodegradation of lignin model compounds was investigated in order to elucidate lignin degradation mechanisms. Both mono-aromatic and dimeric lignin model compounds were used as electron donors and carbon sources for the mixed sulphate reducing consortia. Biodegradation and mass spectrometer analysis of mono-aromatic compounds, ferulic acid and ferulic acid ethyl ester resulted in the production of intermediates such as catechol, cyclohexane carboxylic acid and adipic acid. These intermediates were also observed in the degradation of dimeric ferulic acid. Biodegradation of salicin resulted in the production of salicyl alcohol, ortho-cresol and acetate. Biodegradation of benzylic ether resulted in the production of vanillin and acetate as end products. The results of these studies provide evidence for a biosulphidogenic hydrolysis of lignin, and also the utilisation of lignin-derived aromatic compounds as electron donor sources, by a mixed sulphate reducing consortia.
- Full Text:
- Date Issued: 2002
Catalytic behaviour of metallophthalocyanines towards the detection of nitric oxide
- Authors: Vilakazi, Lea Sibulelo
- Date: 2002
- Subjects: Electrochemistry Nitric oxide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4418 , http://hdl.handle.net/10962/d1006852
- Description: Electrocatalytic reduction and oxidation of nitric oxide (NO) using cobalt phthalocyanine complexes have been studied and compared to vitamin B₁₂ and other metallophthalocyanine (MPc) complexes. Modifying a glassy carbon electrode with these complexes resulted in improved sensitivity of the electrode allowing detection of NO to 10⁻⁹ mol dm⁻³. The mechanisms of catalysis were studied. Electrocatalysis of NO involves coordination of NO to the MPc complex. Hence catalytic activity is affected by the nature of the metal center. However coordination of NO to the MPc complex has to be reversible to eliminate poisoning of the electrode. Though FePc gave the best sensitivity and lowered the reduction potential more than CoPc, the strong Fe-NO bond resulted in the poisoning of the electrode hence, rendering the electrode unstable. Rate constants for NO coordination to the MPc complexes were studied. These rates were smaller than the studied NO porphyrin coordination rates. Electrocatalytic reduction of NO using MPc complexes involves a transfer of an electron from the metal center to the NO ligand. Hence, substitution of electron-donating grohps on the cobalt pthalocyanine complex resulted in improved sensitivity and catalytic activity. A CoPc modified microelectrode (11μm) was used to monitor NO in human blood components and to detect NO in a rat brain. Detections of NO were also done in aqueous solutions in the presence of interfering species such as dopamine and serotonin. An interaction between NO and serotonin was observed.
- Full Text:
- Date Issued: 2002
- Authors: Vilakazi, Lea Sibulelo
- Date: 2002
- Subjects: Electrochemistry Nitric oxide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4418 , http://hdl.handle.net/10962/d1006852
- Description: Electrocatalytic reduction and oxidation of nitric oxide (NO) using cobalt phthalocyanine complexes have been studied and compared to vitamin B₁₂ and other metallophthalocyanine (MPc) complexes. Modifying a glassy carbon electrode with these complexes resulted in improved sensitivity of the electrode allowing detection of NO to 10⁻⁹ mol dm⁻³. The mechanisms of catalysis were studied. Electrocatalysis of NO involves coordination of NO to the MPc complex. Hence catalytic activity is affected by the nature of the metal center. However coordination of NO to the MPc complex has to be reversible to eliminate poisoning of the electrode. Though FePc gave the best sensitivity and lowered the reduction potential more than CoPc, the strong Fe-NO bond resulted in the poisoning of the electrode hence, rendering the electrode unstable. Rate constants for NO coordination to the MPc complexes were studied. These rates were smaller than the studied NO porphyrin coordination rates. Electrocatalytic reduction of NO using MPc complexes involves a transfer of an electron from the metal center to the NO ligand. Hence, substitution of electron-donating grohps on the cobalt pthalocyanine complex resulted in improved sensitivity and catalytic activity. A CoPc modified microelectrode (11μm) was used to monitor NO in human blood components and to detect NO in a rat brain. Detections of NO were also done in aqueous solutions in the presence of interfering species such as dopamine and serotonin. An interaction between NO and serotonin was observed.
- Full Text:
- Date Issued: 2002
Chemical studies of selected chromone derivatives
- Authors: Nchinda, Aloysius Tchangwe
- Date: 2002
- Subjects: Heterocyclic compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4434 , http://hdl.handle.net/10962/d1007442
- Description: This investigation has been geared towards several aspects of chromone chemistry. Selected 2-(N,N-dimethylarnino)chromones have been synthesized via 2-hydroxyacetophenone boron difluoride complex intermediates, and potentiometric analysis of these compounds in ethanolwater has been used to determine the influence of substituents on their basicity. The pKa values have been found to lie within a narrow range (1.92 - 2.52), and the observed substituent effects have been rationalized with the aid of semi-empirical and ab initio molecular orbital calculations. An efficient route has been developed for the synthesis of the naturally-occurring chromone, "granulosin" [7,8-(methylenedioxy)-2-propylchromone], and several C-2 side chain analogues in good yields, by condensing 2'-hydroxy-3',4'-(methylenedioxy)acetophenone with a range of ethyl carboxylate esters. These compounds show significant cytotoxic activity against the brine shrimp, Artemia salina, and two of them, the 2-ethyl and 2-benzyl derivatives also show 100% activity as pesticides on Beet army worms (BAW). Another naturally-occurring chromone derivative, 5-hydroxy-2-isopropyl-7-methoxychromone, and four C-2 side chain analogues have been prepared in moderate yields. These compounds also show significant cytotoxic activity against the brine shrimp, Artemia salina, and it is apparent that the presence of the hydroxyl group at C-5 is critical for such activity. The electronimpact mass spectra of both series of chromone derivatives have been investigated, permitting the elucidation of characteristic fragmentation patterns. In work directed towards the synthesis of potential HIV -1 protease inhibitors, five novel chromone-containing analogues of the clinically useful drug, ritonavir, have been synthesized. The design strategy has involved the coupling of substituted chromone-2- carboxylic acids with a specially prepared, hydroxyethylene dipeptide isostere to afford ritonavir analogues containing chromone termini. An interactive docking procedure has been used to explore the docking of ritonavir and the novel chromone-containing analogues into ' the active site of the enzyme, and has indicated the capacity of the ritonavir analogues to form hydrogen-bonds with the HJV-l enzyme receptor. Various substituted cbromone-3-carbaldehydes, which have been synthesized from the corresponding o-hyclroxyacetophenones using Vilsmeier-Haack methodology, have been examined as substrates for Morita-Baylis-Hillman reactions, using 3-hyclroxyquinuclidine as the catalyst and arcylonitrile and methyl acrylate as the activated alkenes. Optimization of the reaction conditions has permitted efficient conversion of the cbromone-3-carbaldehydes to the Morita-Baylis-Hillman products and, in some cases, dimeric products, within 24 h. Heating of the Morita-Baylis-Hillman products, arising from reactions with methyl acrylate, at 80 ºC for 3 h in the presence of DABCO as catalyst, has been shown to effect transformation to the corresponding dimers in good yield.
- Full Text:
- Date Issued: 2002
- Authors: Nchinda, Aloysius Tchangwe
- Date: 2002
- Subjects: Heterocyclic compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4434 , http://hdl.handle.net/10962/d1007442
- Description: This investigation has been geared towards several aspects of chromone chemistry. Selected 2-(N,N-dimethylarnino)chromones have been synthesized via 2-hydroxyacetophenone boron difluoride complex intermediates, and potentiometric analysis of these compounds in ethanolwater has been used to determine the influence of substituents on their basicity. The pKa values have been found to lie within a narrow range (1.92 - 2.52), and the observed substituent effects have been rationalized with the aid of semi-empirical and ab initio molecular orbital calculations. An efficient route has been developed for the synthesis of the naturally-occurring chromone, "granulosin" [7,8-(methylenedioxy)-2-propylchromone], and several C-2 side chain analogues in good yields, by condensing 2'-hydroxy-3',4'-(methylenedioxy)acetophenone with a range of ethyl carboxylate esters. These compounds show significant cytotoxic activity against the brine shrimp, Artemia salina, and two of them, the 2-ethyl and 2-benzyl derivatives also show 100% activity as pesticides on Beet army worms (BAW). Another naturally-occurring chromone derivative, 5-hydroxy-2-isopropyl-7-methoxychromone, and four C-2 side chain analogues have been prepared in moderate yields. These compounds also show significant cytotoxic activity against the brine shrimp, Artemia salina, and it is apparent that the presence of the hydroxyl group at C-5 is critical for such activity. The electronimpact mass spectra of both series of chromone derivatives have been investigated, permitting the elucidation of characteristic fragmentation patterns. In work directed towards the synthesis of potential HIV -1 protease inhibitors, five novel chromone-containing analogues of the clinically useful drug, ritonavir, have been synthesized. The design strategy has involved the coupling of substituted chromone-2- carboxylic acids with a specially prepared, hydroxyethylene dipeptide isostere to afford ritonavir analogues containing chromone termini. An interactive docking procedure has been used to explore the docking of ritonavir and the novel chromone-containing analogues into ' the active site of the enzyme, and has indicated the capacity of the ritonavir analogues to form hydrogen-bonds with the HJV-l enzyme receptor. Various substituted cbromone-3-carbaldehydes, which have been synthesized from the corresponding o-hyclroxyacetophenones using Vilsmeier-Haack methodology, have been examined as substrates for Morita-Baylis-Hillman reactions, using 3-hyclroxyquinuclidine as the catalyst and arcylonitrile and methyl acrylate as the activated alkenes. Optimization of the reaction conditions has permitted efficient conversion of the cbromone-3-carbaldehydes to the Morita-Baylis-Hillman products and, in some cases, dimeric products, within 24 h. Heating of the Morita-Baylis-Hillman products, arising from reactions with methyl acrylate, at 80 ºC for 3 h in the presence of DABCO as catalyst, has been shown to effect transformation to the corresponding dimers in good yield.
- Full Text:
- Date Issued: 2002
Continuity and generalized continuity in dynamics and other applications
- Authors: Mimna, Roy Allan
- Date: 2002
- Subjects: Topological dynamics -- Research Dynamics -- Mathematical models -- Research Perturbation (Mathematics) Attractors (Mathematics) Baire classes Mathematics -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5404 , http://hdl.handle.net/10962/d1005218
- Description: The topological dynamics of continuous and noncontinuous dynamical systems are investigated. Various definitions of chaos are studied, as well as notions of stability. Results are obtained on asymptotically stable sets and the perturbation stability of such sets. The primary focus is on the traditional point sets of topological dynamics, including the chain recurrent set, omega-limit sets and attractors. The basic setting is that of a continuous function on a compact metric space, sometimes with additional properties on the space. The investigation includes results on the dynamical properties of typical continuous functions in the sense of Baire category. Results are also developed concerning dynamical systems involving quasi-continuous functions. An invariance property for the omega-limit sets of such functions is given. Omega-limit sets are characterized for Riemann integrable derivatives and derivatiyes which are continuous almost everywhere. Techniques used in the investigation and formulation of results include finding theorems which relate the rather disparate notions of dynamical properties and generalized continuity. In addition to dynamical systems, numerous other applications of generalized continuity are imoestigated. Techniques used include application of the Baire Category Theorem and the notion of semi-closure. For example, results are formulated concerning functions determined by dense sets, including separately continuous functions, thus generalizing the classical result for continuous functions on dense subsets of the domain. The uniform boundedness theorem is extended to functions which are not necessarily continuous, including various derivatives. The closed graph theorem is strictly generalized in two separate ways, and applications are presented using these generalizations. An invariance property of separately continuous functions is given. Cluster sets are studied in connection with separate continuity, and various results are presented concerning locally bounded functions.
- Full Text:
- Date Issued: 2002
- Authors: Mimna, Roy Allan
- Date: 2002
- Subjects: Topological dynamics -- Research Dynamics -- Mathematical models -- Research Perturbation (Mathematics) Attractors (Mathematics) Baire classes Mathematics -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5404 , http://hdl.handle.net/10962/d1005218
- Description: The topological dynamics of continuous and noncontinuous dynamical systems are investigated. Various definitions of chaos are studied, as well as notions of stability. Results are obtained on asymptotically stable sets and the perturbation stability of such sets. The primary focus is on the traditional point sets of topological dynamics, including the chain recurrent set, omega-limit sets and attractors. The basic setting is that of a continuous function on a compact metric space, sometimes with additional properties on the space. The investigation includes results on the dynamical properties of typical continuous functions in the sense of Baire category. Results are also developed concerning dynamical systems involving quasi-continuous functions. An invariance property for the omega-limit sets of such functions is given. Omega-limit sets are characterized for Riemann integrable derivatives and derivatiyes which are continuous almost everywhere. Techniques used in the investigation and formulation of results include finding theorems which relate the rather disparate notions of dynamical properties and generalized continuity. In addition to dynamical systems, numerous other applications of generalized continuity are imoestigated. Techniques used include application of the Baire Category Theorem and the notion of semi-closure. For example, results are formulated concerning functions determined by dense sets, including separately continuous functions, thus generalizing the classical result for continuous functions on dense subsets of the domain. The uniform boundedness theorem is extended to functions which are not necessarily continuous, including various derivatives. The closed graph theorem is strictly generalized in two separate ways, and applications are presented using these generalizations. An invariance property of separately continuous functions is given. Cluster sets are studied in connection with separate continuity, and various results are presented concerning locally bounded functions.
- Full Text:
- Date Issued: 2002
Detection of neurotransmitters using metallophthalocyanines as electrocatalysts
- Authors: Oni, Joshua Idowu
- Date: 2002
- Subjects: Neurotransmitters Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4435 , http://hdl.handle.net/10962/d1007470
- Description: Some metallophthalocyanine complexes were synthesized and their catalytic activities towards the detection and quantification of the neurotransmitters dopamine, serotonin and histamine were investigated. The study of the possible interaction between these transmitter substances and the metallophthalocyanine complexes was undertaken. Dopamine, serotonin and histamine formed complexes with Iron (II) tetrasulfophthalocyanine. The rate and equilibrium constants obtained for the coordination are in the range of values reported in the literature for ligand coordination to iron phthalocyanine complexes. Carbon paste electrodes of millimetric diameters modified with Iron (II) tetrasulfophthalocyanine exhibited good electro catalytic activity towards the detection and analysis of dopamine and serotonin while at the same time eliminated the problem of interference posed by ascorbic acid in the electrochemical analysis of neurotransmitters. A detection limit of the order of 10-6 mol dm-3 was obtained for both dopamine and serotonin at the modified electrodes. Carbon paste ultra micro electrodes modified with iron (II) tetrasulfophthalocyanine were also used for the detection of dopamine and serotonin as well as the simultaneous determination of dopamine and ascorbic acid in a mixture. The detection limit obtained for dopamine at the ultra microelectrode was 4.2xlO-7 mol dm-3 The electrode kinetics of vitamin BI as well as the stability of the electrode towards its determination was improved upon by modifying carbon paste electrodes with manganese phthalocyanine. The modified electrodes were used for the analysis of vitamin BI in tablets.
- Full Text:
- Date Issued: 2002
- Authors: Oni, Joshua Idowu
- Date: 2002
- Subjects: Neurotransmitters Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4435 , http://hdl.handle.net/10962/d1007470
- Description: Some metallophthalocyanine complexes were synthesized and their catalytic activities towards the detection and quantification of the neurotransmitters dopamine, serotonin and histamine were investigated. The study of the possible interaction between these transmitter substances and the metallophthalocyanine complexes was undertaken. Dopamine, serotonin and histamine formed complexes with Iron (II) tetrasulfophthalocyanine. The rate and equilibrium constants obtained for the coordination are in the range of values reported in the literature for ligand coordination to iron phthalocyanine complexes. Carbon paste electrodes of millimetric diameters modified with Iron (II) tetrasulfophthalocyanine exhibited good electro catalytic activity towards the detection and analysis of dopamine and serotonin while at the same time eliminated the problem of interference posed by ascorbic acid in the electrochemical analysis of neurotransmitters. A detection limit of the order of 10-6 mol dm-3 was obtained for both dopamine and serotonin at the modified electrodes. Carbon paste ultra micro electrodes modified with iron (II) tetrasulfophthalocyanine were also used for the detection of dopamine and serotonin as well as the simultaneous determination of dopamine and ascorbic acid in a mixture. The detection limit obtained for dopamine at the ultra microelectrode was 4.2xlO-7 mol dm-3 The electrode kinetics of vitamin BI as well as the stability of the electrode towards its determination was improved upon by modifying carbon paste electrodes with manganese phthalocyanine. The modified electrodes were used for the analysis of vitamin BI in tablets.
- Full Text:
- Date Issued: 2002
Dynamics of early stage fishes associated with selected warm temperate estuaries in South Africa
- Authors: Strydom, Nadine Amelia
- Date: 2002
- Subjects: Estuarine fishes -- South Africa Fishes -- Infancy -- South Africa Estuarine ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5262 , http://hdl.handle.net/10962/d1005106
- Description: Early stage fishes, namely larvae and early juveniles, were collected from 12 estuaries and associated habitats in the warm temperate region of South Africa between July 1998 and December 2000. This study served to provide new information and expand on existing knowledge of early stage fish assemblages associated with various types of Eastern Cape estuaries. A total of 65 536 predominantly postflexion fish larvae were collected. Together with early juveniles, taxa comprised 72 species from 25 teleost fish families. Surf zones associated with two intermittently open estuaries showed that estuary-dependent marine species predominated in this zone. Early stage fishes responded positively during natural estuary opening events and concentrated along the estuary outflow plume, suggesting that cueing from estuary and/or river water may be taking place. A habitat study in the Swartkops Estuary, using light traps, showed that newly recruited larval fishes concentrated along the margins of the estuary and unlike their older juvenile counterparts, were poorly represented in eelgrass beds. A multi-estuary comparison, including seven permanently open and five intermittently open estuaries, indicated that early stage fish assemblages were more diverse than indicated by past investigations. Early stage fishes were also shown to concentrate in the mesohaline regions of these estuaries. Studies of estuaries with altered freshwater flow regimes were also included in the research. A regulated release of dam water in the euhaline Kromme Estuary failed to induce a cueing response from estuary-dependent marine fish larvae. This project showed that large amounts of freshwater are required to reverse the negative effects of river impoundments. The release study did show that estuary-resident fishes were sensitive to small natural pulses of freshwater and responded by spawning. However, excessive river supply through an inter-basin water transfer scheme was shown to have a flushing effect on the larvae and early juveniles of the estuary-resident Gilchristella aestuaria in the upper reaches of the Great Fish Estuary. This effect was evident in comparisons with the freshwater starved Kariega Estuary where concentrations of G. aestuaria, a species usually more abundant in freshwater rich estuaries, were considerably higher. This finding suggests that freshwater minima and maxima be considered when assessing and managing estuarine systems.
- Full Text:
- Date Issued: 2002
- Authors: Strydom, Nadine Amelia
- Date: 2002
- Subjects: Estuarine fishes -- South Africa Fishes -- Infancy -- South Africa Estuarine ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5262 , http://hdl.handle.net/10962/d1005106
- Description: Early stage fishes, namely larvae and early juveniles, were collected from 12 estuaries and associated habitats in the warm temperate region of South Africa between July 1998 and December 2000. This study served to provide new information and expand on existing knowledge of early stage fish assemblages associated with various types of Eastern Cape estuaries. A total of 65 536 predominantly postflexion fish larvae were collected. Together with early juveniles, taxa comprised 72 species from 25 teleost fish families. Surf zones associated with two intermittently open estuaries showed that estuary-dependent marine species predominated in this zone. Early stage fishes responded positively during natural estuary opening events and concentrated along the estuary outflow plume, suggesting that cueing from estuary and/or river water may be taking place. A habitat study in the Swartkops Estuary, using light traps, showed that newly recruited larval fishes concentrated along the margins of the estuary and unlike their older juvenile counterparts, were poorly represented in eelgrass beds. A multi-estuary comparison, including seven permanently open and five intermittently open estuaries, indicated that early stage fish assemblages were more diverse than indicated by past investigations. Early stage fishes were also shown to concentrate in the mesohaline regions of these estuaries. Studies of estuaries with altered freshwater flow regimes were also included in the research. A regulated release of dam water in the euhaline Kromme Estuary failed to induce a cueing response from estuary-dependent marine fish larvae. This project showed that large amounts of freshwater are required to reverse the negative effects of river impoundments. The release study did show that estuary-resident fishes were sensitive to small natural pulses of freshwater and responded by spawning. However, excessive river supply through an inter-basin water transfer scheme was shown to have a flushing effect on the larvae and early juveniles of the estuary-resident Gilchristella aestuaria in the upper reaches of the Great Fish Estuary. This effect was evident in comparisons with the freshwater starved Kariega Estuary where concentrations of G. aestuaria, a species usually more abundant in freshwater rich estuaries, were considerably higher. This finding suggests that freshwater minima and maxima be considered when assessing and managing estuarine systems.
- Full Text:
- Date Issued: 2002
Effects of Axial Ligands on the Photosensitising Properties of Silicon Octaphenoxyphthalocyanines
- Authors: Maree, Machiel David
- Date: 2002
- Subjects: Ligands , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4553 , http://hdl.handle.net/10962/d1018246
- Description: Various axially substituted Silicon octaphenoxyphthalocyanines were synthesised as potential photosensitisers in the photodynamic therapy of cancer. Conventional reflux reactions were used for synthesis as well as new microwave irradiation reactions, wherein the reaction times were decreased tenfold with a marginal increase in reaction yield and product purity. An interesting series of oligomeric (dimer to a nonamer) silicon octaphenoxyphthalocyanines were also successfully synthesised in a reaction similar to polymerisation reactions. These compounds were found to undergo an axial ligand transformation upon irradiation with red light (> 600 nm) in dimethylsulphoxide solution. All the ligands were transformed into the dihydroxy silicon octaphenoxyphthalocyanine with varying degrees of phototransformation quantum yields ranging in order from 10⁻³ to 10⁻⁵ depending on the axial ligand involved. During and after axial ligand transformations a photodegredation of the dihydroxy silicon octaphenoxy phthalocyanine was observed upon continued irradiation. The oligomers were found to undergo the same axial ligand transformation process with a phototransformation quantum yield of 10⁻⁵ The singlet oxygen quantum yields of the unaggregated monomeric silicon octaphenoxy phthalocyanines were all found to be approximately 0.2 with the exception of a compound with two (trihexyl)siloxy axial substituents that had a singlet oxygen quantum yield of approximately 0.4 in dimethylsulphoxide solutions. The oligomers showed a surprising trend of an increase in singlet oxygen quantum yield with an increase in phthalocyanine ring number up to the pentamer and then a dramatic decrease to the nonamer. The triplet quantum yield and triplet lifetime were determined by laser flash photolysis for selected compounds and no correlation was observed with any of these properties and the singlet oxygen quantum yields. These selected compounds all fluoresce and a very good correlation was found between the fluorescence lifetimes determined experimentally by laser photolysis and the Strickler-Berg equation for the non-aggregated compounds. Electrochemical measurements also indicate the importance of the axial ligands upon the behaviour of the phthalocyanines as cyclic voltammetric behaviour was determined by the nature of the axial ligand.
- Full Text:
- Date Issued: 2002
- Authors: Maree, Machiel David
- Date: 2002
- Subjects: Ligands , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4553 , http://hdl.handle.net/10962/d1018246
- Description: Various axially substituted Silicon octaphenoxyphthalocyanines were synthesised as potential photosensitisers in the photodynamic therapy of cancer. Conventional reflux reactions were used for synthesis as well as new microwave irradiation reactions, wherein the reaction times were decreased tenfold with a marginal increase in reaction yield and product purity. An interesting series of oligomeric (dimer to a nonamer) silicon octaphenoxyphthalocyanines were also successfully synthesised in a reaction similar to polymerisation reactions. These compounds were found to undergo an axial ligand transformation upon irradiation with red light (> 600 nm) in dimethylsulphoxide solution. All the ligands were transformed into the dihydroxy silicon octaphenoxyphthalocyanine with varying degrees of phototransformation quantum yields ranging in order from 10⁻³ to 10⁻⁵ depending on the axial ligand involved. During and after axial ligand transformations a photodegredation of the dihydroxy silicon octaphenoxy phthalocyanine was observed upon continued irradiation. The oligomers were found to undergo the same axial ligand transformation process with a phototransformation quantum yield of 10⁻⁵ The singlet oxygen quantum yields of the unaggregated monomeric silicon octaphenoxy phthalocyanines were all found to be approximately 0.2 with the exception of a compound with two (trihexyl)siloxy axial substituents that had a singlet oxygen quantum yield of approximately 0.4 in dimethylsulphoxide solutions. The oligomers showed a surprising trend of an increase in singlet oxygen quantum yield with an increase in phthalocyanine ring number up to the pentamer and then a dramatic decrease to the nonamer. The triplet quantum yield and triplet lifetime were determined by laser flash photolysis for selected compounds and no correlation was observed with any of these properties and the singlet oxygen quantum yields. These selected compounds all fluoresce and a very good correlation was found between the fluorescence lifetimes determined experimentally by laser photolysis and the Strickler-Berg equation for the non-aggregated compounds. Electrochemical measurements also indicate the importance of the axial ligands upon the behaviour of the phthalocyanines as cyclic voltammetric behaviour was determined by the nature of the axial ligand.
- Full Text:
- Date Issued: 2002
Effects of substituents on the photosensitizing and electrocatalytic properties of phthalocyanines
- Authors: Maree, Suzanne Elizabeth
- Date: 2002
- Subjects: Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4554 , http://hdl.handle.net/10962/d1018247
- Description: In this work a selection of octasubstituted phthalocyaninato Zinc, Ge(IV) and Sn(IV) complexes were synthesized for possible use in photodynamic therapy and their photochemistry, photophysics and electrochemistry studied. Third-generation complexes containing steroids, e.g. cholesterol and estrone, were synthesized to improve tumour selectivity. The zinc phthalocyanine complexes (ZnPc) showed that complexes containing electron-donating groups have higher photostability. Germanium phthalocyanine complexes (GePc) undergo phototransformation rather than direct photobleaching and the tin phthalocyanine complexes (SnPc) undergo photobleaching mediated by photoreduction of the phthalocyanine ring. Singlet oxygen production showed increased in the following order: GePc>SnPc>ZnPc. Triplet lifetimes of the GePc (168-340μs) are very similar to that of the ZnPc (197 - 366μs), but the triplet lifetimes of the SnPc are ten fold shorter (10 - 32μs ). Triplet quantum yields are higher for the GePc (0.20 - 0.50) and SnPc (0.08 - 0.45) than for the ZnPc (0.02 - 0.25). Fluorescence lifetimes of GePc ( 4.0 - 5.1 ns) are significantly longer than that of ZnPc (1.9 - 3.0 ns) and SnPc (0.2 - 0.4 ns). Fluorescence quantum yields decrease in the following order: GePc(0.21-0.31)>ZnPc(0.02-0.21)>SnPc(0.02- 0.06). Ring-substituted cobalt phthalocyanine complexes of the form CoPc(R)4 (R= NH2, N02, C(CH3)3, S03H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the Com/Co11 couple of the CoPc(R)4 complexes in acidic media and to the Con/Co1 couple in basic media. The catalytic current and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive and the currents increasing with increase in pH.
- Full Text:
- Date Issued: 2002
- Authors: Maree, Suzanne Elizabeth
- Date: 2002
- Subjects: Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4554 , http://hdl.handle.net/10962/d1018247
- Description: In this work a selection of octasubstituted phthalocyaninato Zinc, Ge(IV) and Sn(IV) complexes were synthesized for possible use in photodynamic therapy and their photochemistry, photophysics and electrochemistry studied. Third-generation complexes containing steroids, e.g. cholesterol and estrone, were synthesized to improve tumour selectivity. The zinc phthalocyanine complexes (ZnPc) showed that complexes containing electron-donating groups have higher photostability. Germanium phthalocyanine complexes (GePc) undergo phototransformation rather than direct photobleaching and the tin phthalocyanine complexes (SnPc) undergo photobleaching mediated by photoreduction of the phthalocyanine ring. Singlet oxygen production showed increased in the following order: GePc>SnPc>ZnPc. Triplet lifetimes of the GePc (168-340μs) are very similar to that of the ZnPc (197 - 366μs), but the triplet lifetimes of the SnPc are ten fold shorter (10 - 32μs ). Triplet quantum yields are higher for the GePc (0.20 - 0.50) and SnPc (0.08 - 0.45) than for the ZnPc (0.02 - 0.25). Fluorescence lifetimes of GePc ( 4.0 - 5.1 ns) are significantly longer than that of ZnPc (1.9 - 3.0 ns) and SnPc (0.2 - 0.4 ns). Fluorescence quantum yields decrease in the following order: GePc(0.21-0.31)>ZnPc(0.02-0.21)>SnPc(0.02- 0.06). Ring-substituted cobalt phthalocyanine complexes of the form CoPc(R)4 (R= NH2, N02, C(CH3)3, S03H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the Com/Co11 couple of the CoPc(R)4 complexes in acidic media and to the Con/Co1 couple in basic media. The catalytic current and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive and the currents increasing with increase in pH.
- Full Text:
- Date Issued: 2002
Elucidation and manipulation of the Hydantoin-Hydrolysing Enzyme System of Agrobacterium tumefaciens RU-OR for the Biocatalytic production of D-amino acids
- Authors: Hartley, Carol Janet
- Date: 2002
- Subjects: Amino acids Agrobacterium tumefaciens
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3916 , http://hdl.handle.net/10962/d1003975
- Description: There is widespread interest in the biocatalytic production of enantiomerically pure D-amino acids for use in the synthesis of antibiotics, insecticides, herbicides, drug carriers and many other pharmaceuticals. Hydantoin-hydrolysing enzyme systems can be successfully utilised to stereoselectively convert racemic hydantoins into enantiomerically pure amino acid products. In fact, the use of microbial D-hydantoinase and D-stereoselective N-carbamoyl amino acid amidohydrolase activity to produce D-p-hydroxyphenylglycine from D,L-5-phydroxyphenylhydantoin has been described as one of the most successful biotechnological applications of enzyme technology developed to date. A need to utilise the novel biodiversity of South African microorganisms for the development of an indigenous process to produce enantiomerically pure amino acids was identified in 1995. Subsequently, the Rhodes Hydantoinase Group was established and several local hydantoin-hydrolysing microorganisms were isolated. The research in this study describes the isolation and selection of Agrobacterium tumefaciens RU-OR, which produced D-stereoselective hydantoinhydrolysing activity. Characterisation of the hydantoin-hydrolysing enzyme system of RU-OR revealed novel biocatalytic properties, and potential for the application of this strain for the biocatalytic production of D-amino acids. A fundamental understanding of the regulation of hydantoin-hydrolysing enzyme activity in A. tumefaciens RU-OR was established, and utilised to produce mutant strains with altered regulation of hydantoin-hydrolysing activity. These strains were used to further elucidate the mechanisms regulating the production of hydantoins-hydrolysing activity in A. tumefaciens RU-OR cells. Overproduction of hydantoinase and N-carbamoyl-D-amino acid amidohydrolase activity in selected mutant strains resulted in efficient conversion of D,L-5-p-hydroxyphenylhydantoin to D-p-hydroxyphenylglycine. Thus the establishment of a primary understanding of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR could be used to manipulate the hydantoin-hydrolysing activity in RU-OR cells to produce an improved biocatalyst. The isolation of A. tumfecaiens RU-OR genes encoding for hydantoin-hydrolysing activity revealed two separate N-carbamoyl-D-amino acid amidohydrolaseencoding genes (ncaR1 and ncaR2) in this bacterium with distinct chromosomal locations, nucleotide coding sequence and predicted primary amino acid sequence. The novel biocatalytic properties of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR and mutant derivatives present fascinating opportunities for further elucidation of the natural function, regulation and biocatalytic potential of hydantoin-hydrolysing enzymes.
- Full Text:
- Date Issued: 2002
- Authors: Hartley, Carol Janet
- Date: 2002
- Subjects: Amino acids Agrobacterium tumefaciens
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3916 , http://hdl.handle.net/10962/d1003975
- Description: There is widespread interest in the biocatalytic production of enantiomerically pure D-amino acids for use in the synthesis of antibiotics, insecticides, herbicides, drug carriers and many other pharmaceuticals. Hydantoin-hydrolysing enzyme systems can be successfully utilised to stereoselectively convert racemic hydantoins into enantiomerically pure amino acid products. In fact, the use of microbial D-hydantoinase and D-stereoselective N-carbamoyl amino acid amidohydrolase activity to produce D-p-hydroxyphenylglycine from D,L-5-phydroxyphenylhydantoin has been described as one of the most successful biotechnological applications of enzyme technology developed to date. A need to utilise the novel biodiversity of South African microorganisms for the development of an indigenous process to produce enantiomerically pure amino acids was identified in 1995. Subsequently, the Rhodes Hydantoinase Group was established and several local hydantoin-hydrolysing microorganisms were isolated. The research in this study describes the isolation and selection of Agrobacterium tumefaciens RU-OR, which produced D-stereoselective hydantoinhydrolysing activity. Characterisation of the hydantoin-hydrolysing enzyme system of RU-OR revealed novel biocatalytic properties, and potential for the application of this strain for the biocatalytic production of D-amino acids. A fundamental understanding of the regulation of hydantoin-hydrolysing enzyme activity in A. tumefaciens RU-OR was established, and utilised to produce mutant strains with altered regulation of hydantoin-hydrolysing activity. These strains were used to further elucidate the mechanisms regulating the production of hydantoins-hydrolysing activity in A. tumefaciens RU-OR cells. Overproduction of hydantoinase and N-carbamoyl-D-amino acid amidohydrolase activity in selected mutant strains resulted in efficient conversion of D,L-5-p-hydroxyphenylhydantoin to D-p-hydroxyphenylglycine. Thus the establishment of a primary understanding of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR could be used to manipulate the hydantoin-hydrolysing activity in RU-OR cells to produce an improved biocatalyst. The isolation of A. tumfecaiens RU-OR genes encoding for hydantoin-hydrolysing activity revealed two separate N-carbamoyl-D-amino acid amidohydrolaseencoding genes (ncaR1 and ncaR2) in this bacterium with distinct chromosomal locations, nucleotide coding sequence and predicted primary amino acid sequence. The novel biocatalytic properties of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR and mutant derivatives present fascinating opportunities for further elucidation of the natural function, regulation and biocatalytic potential of hydantoin-hydrolysing enzymes.
- Full Text:
- Date Issued: 2002
Genetic characterization of conspecific populations of Tilapia Sparrmanii (A.Smith 1840) in the dolomitic sinkholes and springs of the North-West Province (South Africa), and their comparison to Tilapia Guinasana (Trewavas 1936)
- Authors: Nxomani, Clifford David
- Date: 2002
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4079 , http://hdl.handle.net/10962/d1007452
- Description: This study was undertaken to investigate the genetic relationships of allopatric populations of the cichlid fish, Tilapia sparrmanii (A. Smith 1840) inhabiting the sinkholes and springs of the North West Province, South Africa. It also examined the genetic relationships of T sparrmanii to its polychromatic sister species, Tilapia guinasana (Trewavas 1936) which is endemic to the Guinas sinkhole in Namibia. Finally, the study investigated whether there is a genetic basis for T guinasana's colour polymorphism. The research was prompted by the concern of conservation authorities about the possible loss of unique fauna given the high demand for use of the subterranean waters for agricultural, domestic and industrial purposes. Such demands have the potential to drain these habitats. Further concerns related to habitat destruction and the introduction of alien species in the ecosystems inhabited by both fish species. Three approaches were adopted in attempting to answer the above questions. First was the investigation of Sodium dodecylsulphate (SDS)-Polyacrylamide Gel Electrophoresis (PAGE) of total cellular proteins as a fast and relatively inexpensive indicator of genetic relatedness between the fish populations. Secondly, genetic differentiation between the T sparrmanii populations and its relationship to T guinasana were assayed using restriction endonuclease analysis of Polymerase Chain Reaction (PCR)-amplified regions of the cytochrome b gene and the d-Ioop of mitochondrial DNA, coupled with Temperature Gradient Gel Electrophoresis (TGGE) analysis of the same regions. The third approach involved the use of Random Amplified Polymorphic DNA (RAPD) fingerprinting of the populations ofT sparrmanii as an indicator of genetic differentiation between them. RAPD fingerprinting was further used to investigate the genetic relationships between T sparrmanii and T guinasana and to probe the genetic basis of the polychromatism of the latter. SDS-PAGE did not reveal any genetic differentiation between the T sparrmanii populations, nor could the analysis detect variation within them. It however clearly distinguished at a species level between T sparrmanii and T guinasana as well as between these and other fish species, thus indicating its possible utility as an indicator of genetic relatedness at a species level. Mitochondrial studies employing the Restriction Fragment Length Polymorphism (RFLP) of Polymerase Chain Reaction (PCR)-amplified cytochrome b (1.1 kb) and d-Ioop regions (0.9 kb) with six and five restriction enzymes respectively, failed to reveal genetic differences within and between the allopatric populations. TGGE of500 bp of the d-Ioop and 400 bp of the 12sRNA PCR-amplified fragments did not reveal any differences between the populations of T. sparrmanii, nor did the analysis reveal any differences between T. sparrmanii and T. guinasana. The lack of differentiation between the T. sparrmanii populations by these mitochondrial Dna analysis techniques, despite habitat fragmentation, indicated a recent origin of the populations from a common ancestral population. Failure to distinguish between T. sparrmanii and T. guinasana may be related to the sensitivity of the techniques utilized. RAPD fingerprinting analysis indicated that the populations are genetically differentiated from each other. Using a measure of coefficient of variation, the population with the highest variation was the Wondergat population (13.99%), followed by the Klerkskraal popUlation (8.29%), the Malmani and Marico Oog populations (each with 5.88%) and the least variation (4.95 and 4.83%) was with the Amalinda and Molopo Oog populations respectively. This high degree of intra population similarity points to the fact that this differentiation is still confined within the limits of con specificity. The genetic distances between all of the T. sparrmanii populations across all primers ranged from 0.09 to 0.234 and averaged 0.146, a value that falls in the upper end of conspecific population differentiation. Such results indicate populational sub-division below the species level. RAPD fingerprinting therefore proved more sensitive than protein or mitochondrial studies. The differentiation it detected between the populations is a reflection of their adaptation to local conditions of the unique ecosystems they inhabit. A comparison with a subset of primers between T. guinasana and T. sparrmanii confirmed the separate species status of the former from the latter. The mean genetic distance between the T. sparrmanii populations was 0.136, compared to that between T. sparrmanii and T. guinasana which was found to be 0.374. Statistical analysis of the difference between the mean genetic distances indicated significance with 95% confidence. The polychromatism of T guinasana was investigated to determine whether there were significant differences between its five colour morphs. RAPD fingerprinting indicated with 95% confidence that there were significant differences between the colour forms based on the genetic distances computed between them. These genetic differences appeared to correlate with the observed assortative mating between the colour forms of the species. The manifestation of the polychromatism at sexual maturity in T guinasana probably indicates that colouration plays an important role in the breeding process. The genetic uniqueness shown here between the populations of T sparrmanii and the colour forms of T guinasana indicate for protective measures to be put in place if the genetic resources of the isolated fish populations are to be preserved. These must be coupled with a thorough assessment of the temporal and spatial distribution of genetic variability of the populations as a guide to a long-term management strategy for the fish populations and the ecosystems they inhabit. This study therefore has shown that the allopatric populations of T sparrmanii in the sinkholes and springs of the North-West Province are genetically unique, as well as show that the colour forms of T guinasana are genetically distinct.
- Full Text:
- Date Issued: 2002
- Authors: Nxomani, Clifford David
- Date: 2002
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4079 , http://hdl.handle.net/10962/d1007452
- Description: This study was undertaken to investigate the genetic relationships of allopatric populations of the cichlid fish, Tilapia sparrmanii (A. Smith 1840) inhabiting the sinkholes and springs of the North West Province, South Africa. It also examined the genetic relationships of T sparrmanii to its polychromatic sister species, Tilapia guinasana (Trewavas 1936) which is endemic to the Guinas sinkhole in Namibia. Finally, the study investigated whether there is a genetic basis for T guinasana's colour polymorphism. The research was prompted by the concern of conservation authorities about the possible loss of unique fauna given the high demand for use of the subterranean waters for agricultural, domestic and industrial purposes. Such demands have the potential to drain these habitats. Further concerns related to habitat destruction and the introduction of alien species in the ecosystems inhabited by both fish species. Three approaches were adopted in attempting to answer the above questions. First was the investigation of Sodium dodecylsulphate (SDS)-Polyacrylamide Gel Electrophoresis (PAGE) of total cellular proteins as a fast and relatively inexpensive indicator of genetic relatedness between the fish populations. Secondly, genetic differentiation between the T sparrmanii populations and its relationship to T guinasana were assayed using restriction endonuclease analysis of Polymerase Chain Reaction (PCR)-amplified regions of the cytochrome b gene and the d-Ioop of mitochondrial DNA, coupled with Temperature Gradient Gel Electrophoresis (TGGE) analysis of the same regions. The third approach involved the use of Random Amplified Polymorphic DNA (RAPD) fingerprinting of the populations ofT sparrmanii as an indicator of genetic differentiation between them. RAPD fingerprinting was further used to investigate the genetic relationships between T sparrmanii and T guinasana and to probe the genetic basis of the polychromatism of the latter. SDS-PAGE did not reveal any genetic differentiation between the T sparrmanii populations, nor could the analysis detect variation within them. It however clearly distinguished at a species level between T sparrmanii and T guinasana as well as between these and other fish species, thus indicating its possible utility as an indicator of genetic relatedness at a species level. Mitochondrial studies employing the Restriction Fragment Length Polymorphism (RFLP) of Polymerase Chain Reaction (PCR)-amplified cytochrome b (1.1 kb) and d-Ioop regions (0.9 kb) with six and five restriction enzymes respectively, failed to reveal genetic differences within and between the allopatric populations. TGGE of500 bp of the d-Ioop and 400 bp of the 12sRNA PCR-amplified fragments did not reveal any differences between the populations of T. sparrmanii, nor did the analysis reveal any differences between T. sparrmanii and T. guinasana. The lack of differentiation between the T. sparrmanii populations by these mitochondrial Dna analysis techniques, despite habitat fragmentation, indicated a recent origin of the populations from a common ancestral population. Failure to distinguish between T. sparrmanii and T. guinasana may be related to the sensitivity of the techniques utilized. RAPD fingerprinting analysis indicated that the populations are genetically differentiated from each other. Using a measure of coefficient of variation, the population with the highest variation was the Wondergat population (13.99%), followed by the Klerkskraal popUlation (8.29%), the Malmani and Marico Oog populations (each with 5.88%) and the least variation (4.95 and 4.83%) was with the Amalinda and Molopo Oog populations respectively. This high degree of intra population similarity points to the fact that this differentiation is still confined within the limits of con specificity. The genetic distances between all of the T. sparrmanii populations across all primers ranged from 0.09 to 0.234 and averaged 0.146, a value that falls in the upper end of conspecific population differentiation. Such results indicate populational sub-division below the species level. RAPD fingerprinting therefore proved more sensitive than protein or mitochondrial studies. The differentiation it detected between the populations is a reflection of their adaptation to local conditions of the unique ecosystems they inhabit. A comparison with a subset of primers between T. guinasana and T. sparrmanii confirmed the separate species status of the former from the latter. The mean genetic distance between the T. sparrmanii populations was 0.136, compared to that between T. sparrmanii and T. guinasana which was found to be 0.374. Statistical analysis of the difference between the mean genetic distances indicated significance with 95% confidence. The polychromatism of T guinasana was investigated to determine whether there were significant differences between its five colour morphs. RAPD fingerprinting indicated with 95% confidence that there were significant differences between the colour forms based on the genetic distances computed between them. These genetic differences appeared to correlate with the observed assortative mating between the colour forms of the species. The manifestation of the polychromatism at sexual maturity in T guinasana probably indicates that colouration plays an important role in the breeding process. The genetic uniqueness shown here between the populations of T sparrmanii and the colour forms of T guinasana indicate for protective measures to be put in place if the genetic resources of the isolated fish populations are to be preserved. These must be coupled with a thorough assessment of the temporal and spatial distribution of genetic variability of the populations as a guide to a long-term management strategy for the fish populations and the ecosystems they inhabit. This study therefore has shown that the allopatric populations of T sparrmanii in the sinkholes and springs of the North-West Province are genetically unique, as well as show that the colour forms of T guinasana are genetically distinct.
- Full Text:
- Date Issued: 2002
Heterologous expression of the helicoverpa armigera stunt virus in Saccharomyces cerevisiae
- Authors: Venter, Philip Arno
- Date: 2002
- Subjects: Helicoverpa armigera Saccharomyces cerevisiae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3895 , http://hdl.handle.net/10962/d1003811
- Description: Lepidopteran insects like Helicoverpa armigera, more commonly known as the cotton bollworm, are economically important pests of a wide variety of crops throughout the world. The Helicoverpa armigera stunt virus (HaSV), a tetravirus with a bipartite single-stranded positive-sense RNA genome, has great potential as a biological pesticide against H. armigera. The larger genomic strand of this virus (RNA1) encodes the viral replicase, while the other (RNA2) encodes the 71 kDa capsid protein precursor (p71). 240 copies of p71 assemble into a procapsid with the concomitant encapsidation of the viral RNA. This is followed by a complex maturation event that is characterized by the autoproteolytic cleavage of p71 into the 64 kDa capsid protein (P64) and a 7 kDa peptide (p7). The rearrangements that occur during maturation results in the formation of mature HaSV capsids that can thereupon deliver RNA to other susceptible host cells. The principal objective of the research described in this study was to demonstrate that this virus could be assembled in Saccharomyces cerevisiae. S. cerevisiae expression vectors were constructed for the production of p71. This protein was detected in cell lysates from two different strains of S. cerevisiae, both containing either chromosomal or episomal copies of an expression cassette for P71. A number of factors relating to the expression of P71 (e.g. strains used, expression loci and expression rate) and the preparation of protein extracts from S. cerevisiae (e.g. the presence of various protease inhibitors and salt concentrations) were examined to attain optimal levels of soluble p71. A small fraction of the optimized soluble p71 was shown to be in the form of virus-like particles (VLPs), with a yield of ≤10⁷ VLPs from a 1.5l culture of P71⁺ cells. These particles were exclusively in the procapsid form, had a similar buoyant density to that of wild-type HaSV and could undergo maturation when the pH was reduced to 5. S. cerevisiae vectors were constructed for the episomal expression of the HaSV genomic RNAs. These vectors directed the transcription of RNA1 and RNA2 transcripts, which had similar sizes to those of the HaSV genomic RNAs. Mature HaSV particles were purified from cells, transgenic for P71, RNA1 and RNA2, by way of two different virus purification protocols that were developed during this study. RT-PCR analyses on RNA-extracts from these particles demonstrated that RNA transcripts, which were produced in trans with p71, could be encapsidated by HaSV capsids in S. cerevisiae. A droplet-feed bioassay on H. armigera larvae demonstrated that the S. cerevisiae-derived HaSV particles caused impaired larval development. This response was correlated with the detection of HaSV RNA2 in RNA extractions from larvae that were used in this bioassay. The results that were generated through the course of this study, provided proof for the concept of the non-host production of infectious HaSV particles from S. cerevisiae. This work could serve as a foundation for future research on the development of an expression system for the large-scale production of this virus as a biopesticide.
- Full Text:
- Date Issued: 2002
- Authors: Venter, Philip Arno
- Date: 2002
- Subjects: Helicoverpa armigera Saccharomyces cerevisiae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3895 , http://hdl.handle.net/10962/d1003811
- Description: Lepidopteran insects like Helicoverpa armigera, more commonly known as the cotton bollworm, are economically important pests of a wide variety of crops throughout the world. The Helicoverpa armigera stunt virus (HaSV), a tetravirus with a bipartite single-stranded positive-sense RNA genome, has great potential as a biological pesticide against H. armigera. The larger genomic strand of this virus (RNA1) encodes the viral replicase, while the other (RNA2) encodes the 71 kDa capsid protein precursor (p71). 240 copies of p71 assemble into a procapsid with the concomitant encapsidation of the viral RNA. This is followed by a complex maturation event that is characterized by the autoproteolytic cleavage of p71 into the 64 kDa capsid protein (P64) and a 7 kDa peptide (p7). The rearrangements that occur during maturation results in the formation of mature HaSV capsids that can thereupon deliver RNA to other susceptible host cells. The principal objective of the research described in this study was to demonstrate that this virus could be assembled in Saccharomyces cerevisiae. S. cerevisiae expression vectors were constructed for the production of p71. This protein was detected in cell lysates from two different strains of S. cerevisiae, both containing either chromosomal or episomal copies of an expression cassette for P71. A number of factors relating to the expression of P71 (e.g. strains used, expression loci and expression rate) and the preparation of protein extracts from S. cerevisiae (e.g. the presence of various protease inhibitors and salt concentrations) were examined to attain optimal levels of soluble p71. A small fraction of the optimized soluble p71 was shown to be in the form of virus-like particles (VLPs), with a yield of ≤10⁷ VLPs from a 1.5l culture of P71⁺ cells. These particles were exclusively in the procapsid form, had a similar buoyant density to that of wild-type HaSV and could undergo maturation when the pH was reduced to 5. S. cerevisiae vectors were constructed for the episomal expression of the HaSV genomic RNAs. These vectors directed the transcription of RNA1 and RNA2 transcripts, which had similar sizes to those of the HaSV genomic RNAs. Mature HaSV particles were purified from cells, transgenic for P71, RNA1 and RNA2, by way of two different virus purification protocols that were developed during this study. RT-PCR analyses on RNA-extracts from these particles demonstrated that RNA transcripts, which were produced in trans with p71, could be encapsidated by HaSV capsids in S. cerevisiae. A droplet-feed bioassay on H. armigera larvae demonstrated that the S. cerevisiae-derived HaSV particles caused impaired larval development. This response was correlated with the detection of HaSV RNA2 in RNA extractions from larvae that were used in this bioassay. The results that were generated through the course of this study, provided proof for the concept of the non-host production of infectious HaSV particles from S. cerevisiae. This work could serve as a foundation for future research on the development of an expression system for the large-scale production of this virus as a biopesticide.
- Full Text:
- Date Issued: 2002
Identification of Cowdria ruminantium proteins that induce specific cellular immune responses
- Authors: Van Kleef, Mirinda
- Date: 2002
- Subjects: Ruminants--Pathogens Heartwater
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4061 , http://hdl.handle.net/10962/d1004373
- Description: Cowdria ruminantium (Cowdria) is an obligate intracellular pathogen that causes heartwater in ruminants. Cellular immunity and the type I cytokine IFN-γ have been implicated in protective immunity to heartwater. The aim of this thesis was to identify proteins of the Welgevonden isolate of Cowdria that induce lymphocyte proliferation and IFN-γ production. Differential centrifugation was found to be the simplest and most efficient method of Cowdria purification. Cowdria organisms were fractionated into their constituent proteins of between 11 and 168 kDa by continuous flow electrophoresis. The resulting fractions were tested for their ability to stimulate lymphocyte proliferation in vitro. In an attempt to simulate the natural infective process, peripheral blood mononuclear cells (PBMC) were obtained from two cattle rendered immune by infection and treatment and assayed in proliferation assays with the proteins fractions. In a parallel study, four cattle were immunised with inactivated Cowdria to determine whether their lymphocytes responded similarly. Cowdria-specific proliferation was detected for only a brief period after immunisation by infection with live organisms. This response was only detected again two to three years later. In contrast, PBMC from animals immunised with inactivated organisms were continuously responsive for at least three years. Only Cowdria proteins with molecular masses of 11, 12, 14 to 17 and 19 to 23 kDa induced proliferative responses in PBMC obtained from all six animals. Cell surface phenotypic analysis of Cowdria specific T-cell lines indicated that CD4⁺ lymphocytes were enriched over time with a concomitant increase in antigen-specific proliferation and IFN-γ production. Proteins of molecular masses 13 to 18 kDa induced CD4⁺ lymphocyte proliferation and IFN-γ production by T-cell lines from all the animals tested. Antibodies raised in a chicken and in rabbits to these low molecular weight proteins had low titres and specificity. Two-dimensional electrophoresis indicated that proteins within a single molecular weight range comprised several components with different pIs, revealing the complexity of the Cowdria proteome. This complicates the search for potentially protective antigens. Nevertheless, since they cause proliferation and IFN-γ production by lymphocytes from immunised cattle, these low molecular weight proteins merit further investigation as potential vaccine antigens. , Author: Mirinda van Kleef neé Rossouw
- Full Text:
- Date Issued: 2002
- Authors: Van Kleef, Mirinda
- Date: 2002
- Subjects: Ruminants--Pathogens Heartwater
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4061 , http://hdl.handle.net/10962/d1004373
- Description: Cowdria ruminantium (Cowdria) is an obligate intracellular pathogen that causes heartwater in ruminants. Cellular immunity and the type I cytokine IFN-γ have been implicated in protective immunity to heartwater. The aim of this thesis was to identify proteins of the Welgevonden isolate of Cowdria that induce lymphocyte proliferation and IFN-γ production. Differential centrifugation was found to be the simplest and most efficient method of Cowdria purification. Cowdria organisms were fractionated into their constituent proteins of between 11 and 168 kDa by continuous flow electrophoresis. The resulting fractions were tested for their ability to stimulate lymphocyte proliferation in vitro. In an attempt to simulate the natural infective process, peripheral blood mononuclear cells (PBMC) were obtained from two cattle rendered immune by infection and treatment and assayed in proliferation assays with the proteins fractions. In a parallel study, four cattle were immunised with inactivated Cowdria to determine whether their lymphocytes responded similarly. Cowdria-specific proliferation was detected for only a brief period after immunisation by infection with live organisms. This response was only detected again two to three years later. In contrast, PBMC from animals immunised with inactivated organisms were continuously responsive for at least three years. Only Cowdria proteins with molecular masses of 11, 12, 14 to 17 and 19 to 23 kDa induced proliferative responses in PBMC obtained from all six animals. Cell surface phenotypic analysis of Cowdria specific T-cell lines indicated that CD4⁺ lymphocytes were enriched over time with a concomitant increase in antigen-specific proliferation and IFN-γ production. Proteins of molecular masses 13 to 18 kDa induced CD4⁺ lymphocyte proliferation and IFN-γ production by T-cell lines from all the animals tested. Antibodies raised in a chicken and in rabbits to these low molecular weight proteins had low titres and specificity. Two-dimensional electrophoresis indicated that proteins within a single molecular weight range comprised several components with different pIs, revealing the complexity of the Cowdria proteome. This complicates the search for potentially protective antigens. Nevertheless, since they cause proliferation and IFN-γ production by lymphocytes from immunised cattle, these low molecular weight proteins merit further investigation as potential vaccine antigens. , Author: Mirinda van Kleef neé Rossouw
- Full Text:
- Date Issued: 2002
Intelligent gripper design and application for automated part recognition and gripping
- Authors: Wang, Jianqiang
- Date: 2002
- Subjects: Automatic control , Robots, Industrial , Robotics
- Language: English
- Type: Thesis , Doctoral , DTech (Engineering)
- Identifier: vital:10816 , http://hdl.handle.net/10948/102 , Automatic control , Robots, Industrial , Robotics
- Description: Intelligent gripping may be achieved through gripper design, automated part recognition, intelligent algorithm for control of the gripper, and on-line decision-making based on sensory data. A generic framework which integrates sensory data, part recognition, decision-making and gripper control to achieve intelligent gripping based on ABB industrial robot is constructed. The three-fingered gripper actuated by a linear servo actuator designed and developed in this project for precise speed and position control is capable of handling a large variety of objects. Generic algorithms for intelligent part recognition are developed. Edge vector representation is discussed. Object geometric features are extracted. Fuzzy logic is successfully utilized to enhance the intelligence of the system. The generic fuzzy logic algorithm, which may also find application in other fields, is presented. Model-based gripping planning algorithm which is capable of extracting object grasp features from its geometric features and reasoning out grasp model for objects with different geometry is proposed. Manipulator trajectory planning solves the problem of generating robot programs automatically. Object-oriented programming technique based on Visual C++ MFC is used to constitute the system software so as to ensure the compatibility, expandability and modular programming design. Hierarchical architecture for intelligent gripping is discussed, which partitions the robot’s functionalities into high-level (modeling, recognizing, planning and perception) layers, and low-level (sensing, interfacing and execute) layers. Individual system modules are integrated seamlessly to constitute the intelligent gripping system.
- Full Text:
- Date Issued: 2002
- Authors: Wang, Jianqiang
- Date: 2002
- Subjects: Automatic control , Robots, Industrial , Robotics
- Language: English
- Type: Thesis , Doctoral , DTech (Engineering)
- Identifier: vital:10816 , http://hdl.handle.net/10948/102 , Automatic control , Robots, Industrial , Robotics
- Description: Intelligent gripping may be achieved through gripper design, automated part recognition, intelligent algorithm for control of the gripper, and on-line decision-making based on sensory data. A generic framework which integrates sensory data, part recognition, decision-making and gripper control to achieve intelligent gripping based on ABB industrial robot is constructed. The three-fingered gripper actuated by a linear servo actuator designed and developed in this project for precise speed and position control is capable of handling a large variety of objects. Generic algorithms for intelligent part recognition are developed. Edge vector representation is discussed. Object geometric features are extracted. Fuzzy logic is successfully utilized to enhance the intelligence of the system. The generic fuzzy logic algorithm, which may also find application in other fields, is presented. Model-based gripping planning algorithm which is capable of extracting object grasp features from its geometric features and reasoning out grasp model for objects with different geometry is proposed. Manipulator trajectory planning solves the problem of generating robot programs automatically. Object-oriented programming technique based on Visual C++ MFC is used to constitute the system software so as to ensure the compatibility, expandability and modular programming design. Hierarchical architecture for intelligent gripping is discussed, which partitions the robot’s functionalities into high-level (modeling, recognizing, planning and perception) layers, and low-level (sensing, interfacing and execute) layers. Individual system modules are integrated seamlessly to constitute the intelligent gripping system.
- Full Text:
- Date Issued: 2002
Non-governmental organizations, the state and the politics of rural development in Kenya with particular reference to Western Province
- Authors: Matanga, Frank Khachina
- Date: 2002
- Subjects: Non-governmental organizations -- Kenya , Rural development -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2803 , http://hdl.handle.net/10962/d1003013 , Non-governmental organizations -- Kenya , Rural development -- Kenya
- Description: In recent decades, Non-Governmental Organizations (NGOs) have increasingly taken on development and political roles in Africa. This has partly been attributed to the New Policy Agenda (NPA) mounted by the international donors. The NPA is predicated on neo-liberal thinking advocating for an enlarged development role for the private sector and a minimalist state. This relatively new shift in development thought has been motivated by the declining capacity of the African state to deliver development and guarantee a liberal political system. This study, therefore, set out to empirically examine whether NGOs are capable of effectively playing their new-found development and political roles. The study was based on Kenya with the Western Province constituting the core research area. The fact that the Kenyan state has been gradually disengaging from the development process has created a vacuum of which the NGOs have attempted to fill. Equally important has been the observation that, for the greater part of the post-colonial period, the state has been largely authoritarian and therefore prompting a segment of civil society to take on political roles in an effort to force it to liberalize and democratize. Urban NGOs in particular, have been the most confrontational to the state with some remarkable success. Unlike their urban counterparts, rural-based NGOs have tended to be more developmental and play a politics of collaboration with the state. Many of the latter NGOs, although playing a significant role in rural development, have been co-opted into patron-client networks. Factors that influence NGOs= posture towards the state include the nature of their leadership, the extent of their nternational connections, and the level of resources at their disposal. The study=s principal conclusion, is that, in as much as NGOs and overall civil society have provided a basis for development and opposition to the state, there is an urgent and growing need for them to shift from a position of dependency, whether domestic or international, to relative autonomy. Only then, will their contributions be sustainable in society.
- Full Text:
- Date Issued: 2002
- Authors: Matanga, Frank Khachina
- Date: 2002
- Subjects: Non-governmental organizations -- Kenya , Rural development -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2803 , http://hdl.handle.net/10962/d1003013 , Non-governmental organizations -- Kenya , Rural development -- Kenya
- Description: In recent decades, Non-Governmental Organizations (NGOs) have increasingly taken on development and political roles in Africa. This has partly been attributed to the New Policy Agenda (NPA) mounted by the international donors. The NPA is predicated on neo-liberal thinking advocating for an enlarged development role for the private sector and a minimalist state. This relatively new shift in development thought has been motivated by the declining capacity of the African state to deliver development and guarantee a liberal political system. This study, therefore, set out to empirically examine whether NGOs are capable of effectively playing their new-found development and political roles. The study was based on Kenya with the Western Province constituting the core research area. The fact that the Kenyan state has been gradually disengaging from the development process has created a vacuum of which the NGOs have attempted to fill. Equally important has been the observation that, for the greater part of the post-colonial period, the state has been largely authoritarian and therefore prompting a segment of civil society to take on political roles in an effort to force it to liberalize and democratize. Urban NGOs in particular, have been the most confrontational to the state with some remarkable success. Unlike their urban counterparts, rural-based NGOs have tended to be more developmental and play a politics of collaboration with the state. Many of the latter NGOs, although playing a significant role in rural development, have been co-opted into patron-client networks. Factors that influence NGOs= posture towards the state include the nature of their leadership, the extent of their nternational connections, and the level of resources at their disposal. The study=s principal conclusion, is that, in as much as NGOs and overall civil society have provided a basis for development and opposition to the state, there is an urgent and growing need for them to shift from a position of dependency, whether domestic or international, to relative autonomy. Only then, will their contributions be sustainable in society.
- Full Text:
- Date Issued: 2002
Nutrient digestibility in South African abalone (Haliotis Midae L.)
- Authors: Sales, James
- Date: 2002
- Subjects: Abalones -- Digestion Abalones -- Nutrition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5305 , http://hdl.handle.net/10962/d1005150
- Description: The evaluation of potential alternative protein sources for the formulation of least-cost optimal diets to satisfy the nutrient requirements of South African abalone (Haliotis midae) has been hampered by the absence of a suitable, practical, replicable and reliable digestibility technique. A suitable lowcost faeces collection technique was developed in this study to obtain suitable quantities of excreta for analysis from this species. Acid-insoluble ash was identified as a reliable, replicable and safe internal marker in comparison to chromic oxide and crude fibre for use in nutrient digestibility studies with H. midae. This was validated by the consistency and repeatability of the results and by comparison to total collection of faeces. The traditional substitution method used in digestibility studies with fish to evaluate protein digestibility of feed ingredients was found to be unsuitable for H. midae. Apparent protein digestibility values exceeding 100 % derived through this method could be attributed to associative effects between feed ingredients, differential diet and faecal nutrient leaching, and mathematical artifacts in calculations when using substitution versus single protein diets. An ingredient particle size of less than 450 μm in comparison to particle size classes of above 450 μm was shown to enhance nutrient (dry matter, organic matter, protein, fat) digestibility and minimise dry matter leaching from diets. The dietary inclusion level of both pre-gelatinised maize starch and a-cellulose did not influence (P > 0.05) apparent nutrient (protein, fat, fiber, starch) digestibility. Using the above digestibility protocol amino acid availability of all plants ingredients currently used in the South African animal industry was evaluated for H. midae. Soybean meal (96.86 %) and lupins (96.51 %) presented the highest apparent mean amino acid availability of all plant protein ingredients evaluated with H. midae. Canola meal (94.21 %), faba beans (92.87 %) sunflower meal (92.77 %), peanut meal (87.39 %) and cottonseed meal (85.15 %) presented higher apparent mean amino acid availability values than fish meal (82.75 %). Apparent protein digestibility was highly correlated (r = 0.99) with mean apparent amino acid availability, while true amino acid availability was 1.88 % units higher than apparent amino acid availability for all ingredients tested. Predicted apparent protein digestibility in compound diets was within 1.1-6.5 % of determined values. Calcium phosphate mono dibasic presented the lowest (P < 0.05) dietary phosphorus leaching (51.51 % maximum) and highest apparent phosphorus digestibility (66.27 %) in comparison to other inorganic phosphorus sources. Based on the method of direct experimentation to determine the optimal dietary protein level using graded levels of dietary protein 28.1-35.9 % dietary protein from good quality sources is recommended for maximum growth of juvenile H. midae. This study provides a scientifically sound research tool including a faecal collection technique, suitable marker and assay technique that could be use in further studies to improve least-cost diet formulation for H. midae. Future nutritional studies in H. midae should primarily concentrate on reducing dietary nutrient leaching and improving the intake of nutrients in order to properly evaluate responses of this species to different dietary regimes.
- Full Text:
- Date Issued: 2002
- Authors: Sales, James
- Date: 2002
- Subjects: Abalones -- Digestion Abalones -- Nutrition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5305 , http://hdl.handle.net/10962/d1005150
- Description: The evaluation of potential alternative protein sources for the formulation of least-cost optimal diets to satisfy the nutrient requirements of South African abalone (Haliotis midae) has been hampered by the absence of a suitable, practical, replicable and reliable digestibility technique. A suitable lowcost faeces collection technique was developed in this study to obtain suitable quantities of excreta for analysis from this species. Acid-insoluble ash was identified as a reliable, replicable and safe internal marker in comparison to chromic oxide and crude fibre for use in nutrient digestibility studies with H. midae. This was validated by the consistency and repeatability of the results and by comparison to total collection of faeces. The traditional substitution method used in digestibility studies with fish to evaluate protein digestibility of feed ingredients was found to be unsuitable for H. midae. Apparent protein digestibility values exceeding 100 % derived through this method could be attributed to associative effects between feed ingredients, differential diet and faecal nutrient leaching, and mathematical artifacts in calculations when using substitution versus single protein diets. An ingredient particle size of less than 450 μm in comparison to particle size classes of above 450 μm was shown to enhance nutrient (dry matter, organic matter, protein, fat) digestibility and minimise dry matter leaching from diets. The dietary inclusion level of both pre-gelatinised maize starch and a-cellulose did not influence (P > 0.05) apparent nutrient (protein, fat, fiber, starch) digestibility. Using the above digestibility protocol amino acid availability of all plants ingredients currently used in the South African animal industry was evaluated for H. midae. Soybean meal (96.86 %) and lupins (96.51 %) presented the highest apparent mean amino acid availability of all plant protein ingredients evaluated with H. midae. Canola meal (94.21 %), faba beans (92.87 %) sunflower meal (92.77 %), peanut meal (87.39 %) and cottonseed meal (85.15 %) presented higher apparent mean amino acid availability values than fish meal (82.75 %). Apparent protein digestibility was highly correlated (r = 0.99) with mean apparent amino acid availability, while true amino acid availability was 1.88 % units higher than apparent amino acid availability for all ingredients tested. Predicted apparent protein digestibility in compound diets was within 1.1-6.5 % of determined values. Calcium phosphate mono dibasic presented the lowest (P < 0.05) dietary phosphorus leaching (51.51 % maximum) and highest apparent phosphorus digestibility (66.27 %) in comparison to other inorganic phosphorus sources. Based on the method of direct experimentation to determine the optimal dietary protein level using graded levels of dietary protein 28.1-35.9 % dietary protein from good quality sources is recommended for maximum growth of juvenile H. midae. This study provides a scientifically sound research tool including a faecal collection technique, suitable marker and assay technique that could be use in further studies to improve least-cost diet formulation for H. midae. Future nutritional studies in H. midae should primarily concentrate on reducing dietary nutrient leaching and improving the intake of nutrients in order to properly evaluate responses of this species to different dietary regimes.
- Full Text:
- Date Issued: 2002
Policy and practice : an activity systems' analysis of a further diploma in education (technology)
- Thomen, Eva Christine Salzmann
- Authors: Thomen, Eva Christine Salzmann
- Date: 2002
- Subjects: Action theory Teachers -- Training of -- South Africa Technology -- Study and teaching -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1854 , http://hdl.handle.net/10962/d1004525
- Description: This research examines, within the interpretive paradigm, how emerging educational policy in an in-service educator education programme, namely, a Further Diploma in Education (Technology), is implemented and practiced by educators in the classroom. Technology is a new learning area in the South African curriculum that aims to develop learners' technological skills and promote the practical application of Science and Mathematics. Technology is seen as a way of developing a productive workforce that can design, realise and evaluate technological problems in a global economy. Engestrom's version of Activity Theory was used as the conceptual framework. Activity Theory focuses on 'activity' as a unit of analysis that captures the individual in context. This research focuses on the lecturers' and the students' actions in the programme, and the educators' and the learners' actions in the classroom. The research design was an eclectic case study consisting of two embedded cases within a single larger case namely, in-service educator education. Multiple single cases were selected within the two embedded cases. Trustworthiness and authenticity were addressed through the triangulation of data using mUltiple sources and methods of data collection. Data were analysed and interpreted in a hermeneutic-like process that emerged through gradual induction over time. The findings of the research suggest that the in-service educator education programme did not promote the effective implementation of educational policy. Major challenges to the effective implementation of educational policy include: the formulation and implementation of an INSET programme during rapid educational policy change, the under-preparedness and language difficulties of the participating educators that constrained policy implementation in the INSET programme and the classroom, the role of organisational rules in shaping the activities in the INSET programme and the classroom, and the broader community'S contribution to resource constraints in the classroom. This research suggests that the participating educators are not likely to be major change agents in the transformation of education in South Africa. This concurs with other research findings that suggest that educator education is a weak intervention incapable of overcoming the shortcomings of the educators' own personal schooling or the impact of work experience.
- Full Text:
- Date Issued: 2002
- Authors: Thomen, Eva Christine Salzmann
- Date: 2002
- Subjects: Action theory Teachers -- Training of -- South Africa Technology -- Study and teaching -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1854 , http://hdl.handle.net/10962/d1004525
- Description: This research examines, within the interpretive paradigm, how emerging educational policy in an in-service educator education programme, namely, a Further Diploma in Education (Technology), is implemented and practiced by educators in the classroom. Technology is a new learning area in the South African curriculum that aims to develop learners' technological skills and promote the practical application of Science and Mathematics. Technology is seen as a way of developing a productive workforce that can design, realise and evaluate technological problems in a global economy. Engestrom's version of Activity Theory was used as the conceptual framework. Activity Theory focuses on 'activity' as a unit of analysis that captures the individual in context. This research focuses on the lecturers' and the students' actions in the programme, and the educators' and the learners' actions in the classroom. The research design was an eclectic case study consisting of two embedded cases within a single larger case namely, in-service educator education. Multiple single cases were selected within the two embedded cases. Trustworthiness and authenticity were addressed through the triangulation of data using mUltiple sources and methods of data collection. Data were analysed and interpreted in a hermeneutic-like process that emerged through gradual induction over time. The findings of the research suggest that the in-service educator education programme did not promote the effective implementation of educational policy. Major challenges to the effective implementation of educational policy include: the formulation and implementation of an INSET programme during rapid educational policy change, the under-preparedness and language difficulties of the participating educators that constrained policy implementation in the INSET programme and the classroom, the role of organisational rules in shaping the activities in the INSET programme and the classroom, and the broader community'S contribution to resource constraints in the classroom. This research suggests that the participating educators are not likely to be major change agents in the transformation of education in South Africa. This concurs with other research findings that suggest that educator education is a weak intervention incapable of overcoming the shortcomings of the educators' own personal schooling or the impact of work experience.
- Full Text:
- Date Issued: 2002
Processes of transformation in a group psychotherapy intervention for single mothers
- Authors: Spiro, Monica
- Date: 2002
- Subjects: Single mothers -- Psychological aspects Group psychotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3100 , http://hdl.handle.net/10962/d1004375
- Description: South African and international statistics indicate that single mother families account for a large and growing proportion of the population. The economic, practical, and emotional stresses of single mothering have been documented and the experience of isolation that often accompanies their circumstances is noted in the literature. Group therapy has been utilised as a treatment plan with single mothers to provide social support and to help the women cope with stress. This thesis examines the experience of single mothers who attended a slow, open group therapy intervention for single mothers at the Child Guidance Clinic, University of Cape Town. The study is located in a feminist social constructionist tradition that recognises the multiplicity of social realities. It places the women's experiences at the foreground of the investigation so as to allow for insight into the socially constructed and first-order reality of the respondents. The research investigates the women's subjective experiences of single parenting; their experiences in the group and its impact on them; and their perceptions of group processes that may have facilitated transformation in their lives. Ten members of the single mother groups were selected for in-depth interviews. Five of the most recent graduates were interviewed and five more participants were selected as the five longest standing members currently participating in the groups. The participants' length of stay in the group at the time of interview varied between eight months and five years. The women were drawn from a range of race, class, cultural and educational backgrounds. The data was collected using individual semi-structured in -depth interviews. A constructivist grounded theory approach was employed to analyse the data. Results revealed the value of the group therapy intervention as a transformative experience for these women who face the challenges of being single parents. The participants highlighted the interpersonal factor of the group intervention as central to their experience and identified this relational aspect as the unique site of their emotional growth. The five interpersonal factors that were identified are: non-judgemental acceptance; support; commonality of experience; reciprocity; and challenge and confrontation between group members. Their accounts of personal changes brought about by participation in the group reflect internal intrapsychic transformations, which are understood in terms of increased se lf-acceptance, enhanced self-esteem, and improved self-confidence. Furthermore, their accounts of personal transformations include a reorganisation of their relational patterns from their immediate to their larger social context. The centrality of relational processes in this research reinforces contemporary theory of women's psychology, particularly theory emerging from the Stone Center, which offers a view of women's psychological growth as occurring in and through participation and engagement with others to achieve more mature and satisfying forms of relating. The accounts of personal and collective transformation provide further insight in to the concept of relational empowerment as it occurs in these groups and offer an understanding of the potentially restorative value of group therapy for single mothers. Future therapeutic interventions are considered and the need for further research in the field is discussed.
- Full Text:
- Date Issued: 2002
- Authors: Spiro, Monica
- Date: 2002
- Subjects: Single mothers -- Psychological aspects Group psychotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3100 , http://hdl.handle.net/10962/d1004375
- Description: South African and international statistics indicate that single mother families account for a large and growing proportion of the population. The economic, practical, and emotional stresses of single mothering have been documented and the experience of isolation that often accompanies their circumstances is noted in the literature. Group therapy has been utilised as a treatment plan with single mothers to provide social support and to help the women cope with stress. This thesis examines the experience of single mothers who attended a slow, open group therapy intervention for single mothers at the Child Guidance Clinic, University of Cape Town. The study is located in a feminist social constructionist tradition that recognises the multiplicity of social realities. It places the women's experiences at the foreground of the investigation so as to allow for insight into the socially constructed and first-order reality of the respondents. The research investigates the women's subjective experiences of single parenting; their experiences in the group and its impact on them; and their perceptions of group processes that may have facilitated transformation in their lives. Ten members of the single mother groups were selected for in-depth interviews. Five of the most recent graduates were interviewed and five more participants were selected as the five longest standing members currently participating in the groups. The participants' length of stay in the group at the time of interview varied between eight months and five years. The women were drawn from a range of race, class, cultural and educational backgrounds. The data was collected using individual semi-structured in -depth interviews. A constructivist grounded theory approach was employed to analyse the data. Results revealed the value of the group therapy intervention as a transformative experience for these women who face the challenges of being single parents. The participants highlighted the interpersonal factor of the group intervention as central to their experience and identified this relational aspect as the unique site of their emotional growth. The five interpersonal factors that were identified are: non-judgemental acceptance; support; commonality of experience; reciprocity; and challenge and confrontation between group members. Their accounts of personal changes brought about by participation in the group reflect internal intrapsychic transformations, which are understood in terms of increased se lf-acceptance, enhanced self-esteem, and improved self-confidence. Furthermore, their accounts of personal transformations include a reorganisation of their relational patterns from their immediate to their larger social context. The centrality of relational processes in this research reinforces contemporary theory of women's psychology, particularly theory emerging from the Stone Center, which offers a view of women's psychological growth as occurring in and through participation and engagement with others to achieve more mature and satisfying forms of relating. The accounts of personal and collective transformation provide further insight in to the concept of relational empowerment as it occurs in these groups and offer an understanding of the potentially restorative value of group therapy for single mothers. Future therapeutic interventions are considered and the need for further research in the field is discussed.
- Full Text:
- Date Issued: 2002