Gendering children's lives: TV fiction for South African kids
- Boshoff, Priscilla A, Prinsloo, Jeanne
- Authors: Boshoff, Priscilla A , Prinsloo, Jeanne
- Date: 2008
- Language: English
- Type: text , book
- Identifier: vital:38264 , ISBN 9780868104508 , http://hdl.handle.net/10962/2476
- Description: Gendering children's lives: TV fiction for South African kids
- Full Text:
- Date Issued: 2008
- Authors: Boshoff, Priscilla A , Prinsloo, Jeanne
- Date: 2008
- Language: English
- Type: text , book
- Identifier: vital:38264 , ISBN 9780868104508 , http://hdl.handle.net/10962/2476
- Description: Gendering children's lives: TV fiction for South African kids
- Full Text:
- Date Issued: 2008
Engendering childhood: concerning the content of South African Television content
- Boshoff, Priscilla A, Prinsloo, Jeanne
- Authors: Boshoff, Priscilla A , Prinsloo, Jeanne
- Date: 2008
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/143560 , vital:38257 , ISBN , https://ischp.files.wordpress.com/2015/08/ischp_2015_abstract_booklet.pdf
- Description: The essays in this volume reflect a wide-range of issues and concerns related to children’s media culture in Africa. For example, several address the role of entertainment television in Addis Abba, Ghana, South Africa, Kenya, and Zambia and in the lives of Muslim children. Other essays introduce us to children-centered media from Ghana, South Africa, and Zimbabwe, and the innovative programs of PLAN-International. In addition to entertainment media and children-centered media, media education and digital media literacy are also discussed.
- Full Text:
- Date Issued: 2008
- Authors: Boshoff, Priscilla A , Prinsloo, Jeanne
- Date: 2008
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/143560 , vital:38257 , ISBN , https://ischp.files.wordpress.com/2015/08/ischp_2015_abstract_booklet.pdf
- Description: The essays in this volume reflect a wide-range of issues and concerns related to children’s media culture in Africa. For example, several address the role of entertainment television in Addis Abba, Ghana, South Africa, Kenya, and Zambia and in the lives of Muslim children. Other essays introduce us to children-centered media from Ghana, South Africa, and Zimbabwe, and the innovative programs of PLAN-International. In addition to entertainment media and children-centered media, media education and digital media literacy are also discussed.
- Full Text:
- Date Issued: 2008
Fungal remediation of winery and distillery wastewaters using Trametes pubescens MB 89 and the enhanced production of a high-value enzyme therein
- Authors: Strong, Peter James
- Date: 2008
- Subjects: Fungal remediation Distilleries -- Waste disposal Wine and wine making -- Waste disposal Bioremediation Laccase Enzymes -- Biotechnology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3932 , http://hdl.handle.net/10962/d1003991
- Description: In this study white-rot fungi were investigated for their efficiency at distillery wastewater remediation and the production of laccase as a valuable by-product. Distillery wastewaters are high in organic load and low in pH. The presence of phenolic compounds can lead to extremely colour-rich wastewaters and can be toxic to microorganisms. The presence of the inorganic ions may also affect biological treatment. White-rot fungi are unique among eukaryotic or prokaryotic microbes in possessing powerful oxidative enzyme systems that can degrade lignin to carbon dioxide. These ligninolytic enzymes, such as lignin peroxidase, manganese peroxidase and laccase, are capable of degrading a vast range of toxic, recalcitrant environmental pollutants and this makes the white-rot fungi strong candidates for the bioremediation of polluted soils and waters. The laccase enzyme alone has shown remediation potential in wastewaters such as beer production effluent, olive mill wastewater, alcohol distillery wastes, dye-containing wastewaters from the textile industry as well as wastewaters from the paper and pulp industry. It has been shown to be capable of remediating soils and waters polluted with chlorinated phenolic compounds, polyaromatic hydrocarbons, nitrosubstituted compounds and fungicides, herbicides and insecticides.
- Full Text:
- Date Issued: 2008
- Authors: Strong, Peter James
- Date: 2008
- Subjects: Fungal remediation Distilleries -- Waste disposal Wine and wine making -- Waste disposal Bioremediation Laccase Enzymes -- Biotechnology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3932 , http://hdl.handle.net/10962/d1003991
- Description: In this study white-rot fungi were investigated for their efficiency at distillery wastewater remediation and the production of laccase as a valuable by-product. Distillery wastewaters are high in organic load and low in pH. The presence of phenolic compounds can lead to extremely colour-rich wastewaters and can be toxic to microorganisms. The presence of the inorganic ions may also affect biological treatment. White-rot fungi are unique among eukaryotic or prokaryotic microbes in possessing powerful oxidative enzyme systems that can degrade lignin to carbon dioxide. These ligninolytic enzymes, such as lignin peroxidase, manganese peroxidase and laccase, are capable of degrading a vast range of toxic, recalcitrant environmental pollutants and this makes the white-rot fungi strong candidates for the bioremediation of polluted soils and waters. The laccase enzyme alone has shown remediation potential in wastewaters such as beer production effluent, olive mill wastewater, alcohol distillery wastes, dye-containing wastewaters from the textile industry as well as wastewaters from the paper and pulp industry. It has been shown to be capable of remediating soils and waters polluted with chlorinated phenolic compounds, polyaromatic hydrocarbons, nitrosubstituted compounds and fungicides, herbicides and insecticides.
- Full Text:
- Date Issued: 2008
Synthesis, photochemical and photophysical properties of gallium and indium phthalocyanine derivatives
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008
An investigation of the Ugandan publication Red Pepper: a case study from 2001-2004
- Authors: Opolot, Benedict
- Date: 2008
- Subjects: Red Pepper (Uganda) Sex in mass media -- Uganda Liberalism in mass media -- Uganda Homophobia -- Press coverage -- Uganda Mass media -- Political aspects -- Uganda Tabloid newspapers -- Uganda -- Case studies Newspapers -- Uganda -- 21st century Journalism -- Uganda
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3513 , http://hdl.handle.net/10962/d1007713
- Description: Red Pepper has been the subject of much discussion in Uganda, with some accounts describing it as a liberal mouthpiece, and others as pornography. This case study, therefore, sought to investigate Red Pepper as a media phenomenon in Uganda in the 21st century, specifically between 2001 and 2004. Employing quantitative and qualitative methodologies, it focused on the production process and the text. Although sexualised content dominate its pages, and news about issues such as the environment and education are near-absent, its managers describe the publication as legitimate, normative and consistent with liberal media standards. Accordingly, to interrogate Red Pepper in terms of its journalistic functions, selected debates associated with liberal approaches to news media, media political economy, tabloidisation, pornography and gendered relations were reviewed. The analysis entailed five phases. The first was a denotative or descriptive analysis, which focused on the publication's structure and content focus. This was followed by an interview with management, a broad content analysis to establish the incidence of predefined content categories expected of the tabloid, pornographic and liberal press and, lastly, a theme-based content analysis that sought to establish the potential meanings and framing of the dominant content categories of gossip and sexualised copy. Overall, the study found Red Pepper to be a misogynistic tabloid, having elements said to belong to pornography and homophobia. According to the findings, not only does Red Pepper fall short of a liberal understanding of a newspaper in terms of diversity of topics, provision of information and professional practice, it also does not fit the understanding of an alternative public sphere, mainly because it fails to challenge the patriarchal framing of sex, sexuality and gendered relations. This framing is undertaken deliberately as a means to securing economic rather than journalistic ideals to which the editors pay lip service. Consequently, the gossip and sexualised content are not problematised and as such discourses and power relations therein are not interrogated. Neither are inadequacies in local systems addressed nor corrective action mobilised as expected of some tabloids. All in all, the publication fronts superficial entertainment content that echoes particular gender constructions and patriarchal commonsense and entrenches the (undesirable) status quo which, ironically, it claims to challenge.
- Full Text:
- Date Issued: 2008
- Authors: Opolot, Benedict
- Date: 2008
- Subjects: Red Pepper (Uganda) Sex in mass media -- Uganda Liberalism in mass media -- Uganda Homophobia -- Press coverage -- Uganda Mass media -- Political aspects -- Uganda Tabloid newspapers -- Uganda -- Case studies Newspapers -- Uganda -- 21st century Journalism -- Uganda
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3513 , http://hdl.handle.net/10962/d1007713
- Description: Red Pepper has been the subject of much discussion in Uganda, with some accounts describing it as a liberal mouthpiece, and others as pornography. This case study, therefore, sought to investigate Red Pepper as a media phenomenon in Uganda in the 21st century, specifically between 2001 and 2004. Employing quantitative and qualitative methodologies, it focused on the production process and the text. Although sexualised content dominate its pages, and news about issues such as the environment and education are near-absent, its managers describe the publication as legitimate, normative and consistent with liberal media standards. Accordingly, to interrogate Red Pepper in terms of its journalistic functions, selected debates associated with liberal approaches to news media, media political economy, tabloidisation, pornography and gendered relations were reviewed. The analysis entailed five phases. The first was a denotative or descriptive analysis, which focused on the publication's structure and content focus. This was followed by an interview with management, a broad content analysis to establish the incidence of predefined content categories expected of the tabloid, pornographic and liberal press and, lastly, a theme-based content analysis that sought to establish the potential meanings and framing of the dominant content categories of gossip and sexualised copy. Overall, the study found Red Pepper to be a misogynistic tabloid, having elements said to belong to pornography and homophobia. According to the findings, not only does Red Pepper fall short of a liberal understanding of a newspaper in terms of diversity of topics, provision of information and professional practice, it also does not fit the understanding of an alternative public sphere, mainly because it fails to challenge the patriarchal framing of sex, sexuality and gendered relations. This framing is undertaken deliberately as a means to securing economic rather than journalistic ideals to which the editors pay lip service. Consequently, the gossip and sexualised content are not problematised and as such discourses and power relations therein are not interrogated. Neither are inadequacies in local systems addressed nor corrective action mobilised as expected of some tabloids. All in all, the publication fronts superficial entertainment content that echoes particular gender constructions and patriarchal commonsense and entrenches the (undesirable) status quo which, ironically, it claims to challenge.
- Full Text:
- Date Issued: 2008
The role of the school management in addressing the problem of drug abuse in the northern areas of Port Elizabeth
- Authors: Jacobs, Lee-Ann
- Date: 2008
- Subjects: High school students -- Substance use -- South Africa -- Port Elizabeth , School management and organization -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:9545 , http://hdl.handle.net/10948/675 , High school students -- Substance use -- South Africa -- Port Elizabeth , School management and organization -- South Africa -- Port Elizabeth
- Description: Drug abuse by teenagers is a problem encountered by educators in South African schools. This study focuses on the reasons for, and the consequences of teenage drug abuse in one school in the Northern Areas of Port Elizabeth. The main aim of this study was to formulate strategies which school managers can use to alleviate the problem of drug abuse among learners. A naturalistic approach was followed to conduct qualitative research. The research design used is a case study. Data-collection techniques consisted of semi-structured and unstructured interviews, observations and questionnaires. Respondents consisted of 150 learners, 5 parents, 10 educators from the school, 2 social workers and 1 auxiliary social worker, 2 priests involved in Youth Ministry, 1 adult involved in running a drug rehabilitation centre, and 1 ex-addict who is involved in arranging drug awareness campaigns and rehabilitation programs. This study found family aspects and family dynamics, personal aspects and the self-concept of the teenager, and societal or environmental aspects to be the main reasons for teenage drug abuse. Drugs have an adverse effect on the community within which the abuse is occurring. It also has a negative effect on the health, psychological state, behaviour and the family of the teenager. Strategies to alleviate the problem emphasise the role which the school can play in terms of drug education for educators, learners and parents; the role of the Government in allocating additional funds for drug education; the role which the church can play in terms of drug education and providing opportunities for positive interactions with peers; and the role which the media can play in influencing the decisions of teenagers.
- Full Text:
- Date Issued: 2008
- Authors: Jacobs, Lee-Ann
- Date: 2008
- Subjects: High school students -- Substance use -- South Africa -- Port Elizabeth , School management and organization -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:9545 , http://hdl.handle.net/10948/675 , High school students -- Substance use -- South Africa -- Port Elizabeth , School management and organization -- South Africa -- Port Elizabeth
- Description: Drug abuse by teenagers is a problem encountered by educators in South African schools. This study focuses on the reasons for, and the consequences of teenage drug abuse in one school in the Northern Areas of Port Elizabeth. The main aim of this study was to formulate strategies which school managers can use to alleviate the problem of drug abuse among learners. A naturalistic approach was followed to conduct qualitative research. The research design used is a case study. Data-collection techniques consisted of semi-structured and unstructured interviews, observations and questionnaires. Respondents consisted of 150 learners, 5 parents, 10 educators from the school, 2 social workers and 1 auxiliary social worker, 2 priests involved in Youth Ministry, 1 adult involved in running a drug rehabilitation centre, and 1 ex-addict who is involved in arranging drug awareness campaigns and rehabilitation programs. This study found family aspects and family dynamics, personal aspects and the self-concept of the teenager, and societal or environmental aspects to be the main reasons for teenage drug abuse. Drugs have an adverse effect on the community within which the abuse is occurring. It also has a negative effect on the health, psychological state, behaviour and the family of the teenager. Strategies to alleviate the problem emphasise the role which the school can play in terms of drug education for educators, learners and parents; the role of the Government in allocating additional funds for drug education; the role which the church can play in terms of drug education and providing opportunities for positive interactions with peers; and the role which the media can play in influencing the decisions of teenagers.
- Full Text:
- Date Issued: 2008
Thermal, spectroscopic and x-ray diffraction studies of copper(II) 1,2,4,5-Benzenetetracarboxylates and copper(II) oxalate a study of metal-organic frameworks
- Authors: Lamprecht, Emmanuel
- Date: 2008
- Subjects: Organometallic compounds Copper Oxalates -- Thermal properties Organic compounds -- Synthesis Spectrum analysis X-rays -- Diffraction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4389 , http://hdl.handle.net/10962/d1005054
- Description: Novel and known metal organic frameworks with copper(II), sodium and 1,2,4,5-benzenetetracarboxylate were prepared by ambient precipitation, solvothermal and gel-synthesis methods, and characterized by single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, and thermogravimetry with FTIR evolved-gas analysis. Some of these complexes were investigated for guest inclusion properties with water (the original guest species), methanol, ethanol and pyridine. The gel-synthesis products were the most interesting. The novel threedimensional metal-organic framework complex Cu₂ Na(OH)L·7H₂O (where L=1,2,4,5-benzenetetracarboxylate) -formed by gel-synthesis- is a covalent three-dimensional metal organic framework polymer with open channels containing both guest water molecules and water molecules coordinated to sodium. The structure collapsed on dehydration, but was essentially restored to the original structure on rehydration in moist air. On exposure of the dehydrated material to methanol and ethanol vapour, significant uptake of these solvents was observed, and the resolvated structures closely resembled that of the parent material. On heating in dry nitrogen, small amounts of methanol and ethanol remained until about 280 °C, when loss of the remaining guest triggered decomposition of the framework. The related complex, Cu₂¼(OH)½ L·7½H₂O (or possibly Cu₂⅓ (OH)⅔L·8H₂O) -formed by gel-synthesis- had a different physical appearance to Cu₂Na(OH)L·7H₂O above, but had nearly identical X-ray diffraction pattern, mid-infrared spectrum and thermal behaviour. The novel complex Cu₄Na₄L₃·14H₂O -formed by gel-synthesis- is a covalent three-dimensional metal-organic framework with small channels containing both guest water molecules and water coordinated to sodium and copper. Upon dehydration the structure collapsed, but on rehydration in moist air the original structure was partly restored. The dehydrated material did not absorb methanol. Known two-dimensional polymeric complexes [Cu₂L·6H₂O]·4H₂O and [Cu₂L·4H₂O]·2H₂O were also obtained by gel-synthesis, and were characterized and investigated for guest inclusion properties. The structures of these complexes collapsed on dehydration, and were only partly restored on rehydration in saturated water vapour. The dehydrated materials did not absorb methanol. The two-dimensional polymeric mixed-ligand complex Cu₂(pyridine)₄·6H₂O -formed very slowly by gel-synthesis- was characterized by TG-FTIR, and was shown to undergo a complicated decomposition involving the loss of water and pyridine, carbon dioxide and carbon monoxide in various stages. Solvothermal synthesis did not yield materials suitable for single-crystal X-ray diffraction studies or inclusion studies, producing only an anhydrous or hemihydrate complex with the formula Cu₂L·0.65H2O. Ambient precipitation syntheses did not yield materials suitable for singlecrystal diffraction studies, forming products approximately equivalent to the complexes [Cu₂L·6H₂O]·4H₂O and Cu₂¼(OH)½L·7 ½H₂O above. During the course of the above study it was discovered that, on changing the DSC purge from nitrogen to argon, the normally exothermic carboxylate decompositions appeared to become endothermic. The effects of the supposedly inert atmospheres of argon and nitrogen on the decomposition-mechanism of copper(II) oxalate -a well-studied copper carboxylate- were therefore studied by DSC, TG, TG-FTIR and XRPD. DSC experiments were performed in nitrogen and argon at different flow-rates, in various mixtures of nitrogen and argon, and at various heating rates. Regardless of the proportions of nitrogen and argon, the DSC residues consisted mainly of copper metal, a small amount of copper(I) oxide (cuprite) and, in some circumstances, traces of copper(II) oxide (tenorite). Also, regardless of whether TG-FTIR experiments were performed under argon or nitrogen, the gaseous decomposition products consisted mainly of carbon dioxide, with traces of carbon monoxide being detected over part of the decomposition period. Various explanations for the thermal behaviour are discussed, and it is possible that small amounts of O2 or monatomic oxygen were given off during the decomposition under argon. The design and implementation of a low-cost prototype X-ray proportional counter detector system, consisting of a hybrid analog-digital computer built using commonly available electronic components, is presented. This system was designed to replace ageing discrete-transistor designs still in use in earlier X-ray diffractometers. The prototype performs the functions of pulse-shaping, pulseheight discrimination, counting and scaling, and provides both digital and scaled analog outputs.
- Full Text:
- Date Issued: 2008
- Authors: Lamprecht, Emmanuel
- Date: 2008
- Subjects: Organometallic compounds Copper Oxalates -- Thermal properties Organic compounds -- Synthesis Spectrum analysis X-rays -- Diffraction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4389 , http://hdl.handle.net/10962/d1005054
- Description: Novel and known metal organic frameworks with copper(II), sodium and 1,2,4,5-benzenetetracarboxylate were prepared by ambient precipitation, solvothermal and gel-synthesis methods, and characterized by single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, and thermogravimetry with FTIR evolved-gas analysis. Some of these complexes were investigated for guest inclusion properties with water (the original guest species), methanol, ethanol and pyridine. The gel-synthesis products were the most interesting. The novel threedimensional metal-organic framework complex Cu₂ Na(OH)L·7H₂O (where L=1,2,4,5-benzenetetracarboxylate) -formed by gel-synthesis- is a covalent three-dimensional metal organic framework polymer with open channels containing both guest water molecules and water molecules coordinated to sodium. The structure collapsed on dehydration, but was essentially restored to the original structure on rehydration in moist air. On exposure of the dehydrated material to methanol and ethanol vapour, significant uptake of these solvents was observed, and the resolvated structures closely resembled that of the parent material. On heating in dry nitrogen, small amounts of methanol and ethanol remained until about 280 °C, when loss of the remaining guest triggered decomposition of the framework. The related complex, Cu₂¼(OH)½ L·7½H₂O (or possibly Cu₂⅓ (OH)⅔L·8H₂O) -formed by gel-synthesis- had a different physical appearance to Cu₂Na(OH)L·7H₂O above, but had nearly identical X-ray diffraction pattern, mid-infrared spectrum and thermal behaviour. The novel complex Cu₄Na₄L₃·14H₂O -formed by gel-synthesis- is a covalent three-dimensional metal-organic framework with small channels containing both guest water molecules and water coordinated to sodium and copper. Upon dehydration the structure collapsed, but on rehydration in moist air the original structure was partly restored. The dehydrated material did not absorb methanol. Known two-dimensional polymeric complexes [Cu₂L·6H₂O]·4H₂O and [Cu₂L·4H₂O]·2H₂O were also obtained by gel-synthesis, and were characterized and investigated for guest inclusion properties. The structures of these complexes collapsed on dehydration, and were only partly restored on rehydration in saturated water vapour. The dehydrated materials did not absorb methanol. The two-dimensional polymeric mixed-ligand complex Cu₂(pyridine)₄·6H₂O -formed very slowly by gel-synthesis- was characterized by TG-FTIR, and was shown to undergo a complicated decomposition involving the loss of water and pyridine, carbon dioxide and carbon monoxide in various stages. Solvothermal synthesis did not yield materials suitable for single-crystal X-ray diffraction studies or inclusion studies, producing only an anhydrous or hemihydrate complex with the formula Cu₂L·0.65H2O. Ambient precipitation syntheses did not yield materials suitable for singlecrystal diffraction studies, forming products approximately equivalent to the complexes [Cu₂L·6H₂O]·4H₂O and Cu₂¼(OH)½L·7 ½H₂O above. During the course of the above study it was discovered that, on changing the DSC purge from nitrogen to argon, the normally exothermic carboxylate decompositions appeared to become endothermic. The effects of the supposedly inert atmospheres of argon and nitrogen on the decomposition-mechanism of copper(II) oxalate -a well-studied copper carboxylate- were therefore studied by DSC, TG, TG-FTIR and XRPD. DSC experiments were performed in nitrogen and argon at different flow-rates, in various mixtures of nitrogen and argon, and at various heating rates. Regardless of the proportions of nitrogen and argon, the DSC residues consisted mainly of copper metal, a small amount of copper(I) oxide (cuprite) and, in some circumstances, traces of copper(II) oxide (tenorite). Also, regardless of whether TG-FTIR experiments were performed under argon or nitrogen, the gaseous decomposition products consisted mainly of carbon dioxide, with traces of carbon monoxide being detected over part of the decomposition period. Various explanations for the thermal behaviour are discussed, and it is possible that small amounts of O2 or monatomic oxygen were given off during the decomposition under argon. The design and implementation of a low-cost prototype X-ray proportional counter detector system, consisting of a hybrid analog-digital computer built using commonly available electronic components, is presented. This system was designed to replace ageing discrete-transistor designs still in use in earlier X-ray diffractometers. The prototype performs the functions of pulse-shaping, pulseheight discrimination, counting and scaling, and provides both digital and scaled analog outputs.
- Full Text:
- Date Issued: 2008
ATP mimics as glutamine synthetase inhibitors : an exploratory synthetic study
- Authors: Salisu, Sheriff Tomilola
- Date: 2008
- Subjects: Glutamine synthetase Tuberculosis -- Treatment Tuberculosis -- Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Drug development
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4408 , http://hdl.handle.net/10962/d1006715
- Description: Using a mechanism-based approach to drug discovery, efforts have been directed towards developing novel ATP mimics that can act as GS inhibitors. The purine-based systems, adenosine, adenine and allopurinol, were identified as possible scaffolds for potential ATP mimics, while various meta-disubstituted benzenoid compounds, 3-aminobenzonitrile, 3-aminophenol, resorcinol, 3-aminobenzyl alcohol, 3-hydroxybenzoic acid and 3-aminobenzoic acid have been explored as adenine analogues. These compounds were treated with different alkylating and acylating agents. Allylation of all the substrates was achieved using allyl bromide and N-9 alkylation of protected allopurinol was effected using a number of specially prepared Baylis-Hillman adducts. Acylation of the benzenoid precursors with chloroacetyl chloride, acetoxyacetyl chloride, acryloyl chloride and specially prepared 2,3,4,5,6-pentaacetylgluconoyl chloride afforded the corresponding mono- and /or diacylated products in varying yields (4-96%). Elaboration of the alkylated and acylated products has involved the reaction of hydroxy systems with diethyl chloro phosphate and chloro derivatives with triethyl phosphite in Arbuzov-type reactions to afford phosphorylated products. In all cases, products were fully characterized using 1- and 2-D NMR analysis and, where appropriate, high-resolution mass spectrometry. The application of Modgraph and ChemWindow NMR prediction programmes has been explored and the resulting data have been compared with experimental chemical shift assignments to confirm chemical structures and, in some cases, to establish the position of allylation or acylation. Experimental assignments were found to be generally comparable with the Modgraph data, but not always with the ChemWindow values. The docking of selected products in the 'active-site' of GS and their structural homology with ATP, both in their free and bound conformations have been studied using the ACCELERYS Cerius² platform. All the selected ATP mimics exhibit some form of interaction with the 'active-site' residues, and a number of them appear to be promising GS ligands.
- Full Text:
- Date Issued: 2008
- Authors: Salisu, Sheriff Tomilola
- Date: 2008
- Subjects: Glutamine synthetase Tuberculosis -- Treatment Tuberculosis -- Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Drug development
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4408 , http://hdl.handle.net/10962/d1006715
- Description: Using a mechanism-based approach to drug discovery, efforts have been directed towards developing novel ATP mimics that can act as GS inhibitors. The purine-based systems, adenosine, adenine and allopurinol, were identified as possible scaffolds for potential ATP mimics, while various meta-disubstituted benzenoid compounds, 3-aminobenzonitrile, 3-aminophenol, resorcinol, 3-aminobenzyl alcohol, 3-hydroxybenzoic acid and 3-aminobenzoic acid have been explored as adenine analogues. These compounds were treated with different alkylating and acylating agents. Allylation of all the substrates was achieved using allyl bromide and N-9 alkylation of protected allopurinol was effected using a number of specially prepared Baylis-Hillman adducts. Acylation of the benzenoid precursors with chloroacetyl chloride, acetoxyacetyl chloride, acryloyl chloride and specially prepared 2,3,4,5,6-pentaacetylgluconoyl chloride afforded the corresponding mono- and /or diacylated products in varying yields (4-96%). Elaboration of the alkylated and acylated products has involved the reaction of hydroxy systems with diethyl chloro phosphate and chloro derivatives with triethyl phosphite in Arbuzov-type reactions to afford phosphorylated products. In all cases, products were fully characterized using 1- and 2-D NMR analysis and, where appropriate, high-resolution mass spectrometry. The application of Modgraph and ChemWindow NMR prediction programmes has been explored and the resulting data have been compared with experimental chemical shift assignments to confirm chemical structures and, in some cases, to establish the position of allylation or acylation. Experimental assignments were found to be generally comparable with the Modgraph data, but not always with the ChemWindow values. The docking of selected products in the 'active-site' of GS and their structural homology with ATP, both in their free and bound conformations have been studied using the ACCELERYS Cerius² platform. All the selected ATP mimics exhibit some form of interaction with the 'active-site' residues, and a number of them appear to be promising GS ligands.
- Full Text:
- Date Issued: 2008
Novel camphor derivatives as potential asymmetric alkylation auxiliaries
- Authors: Skiti-Mama, Neliswa
- Date: 2008
- Subjects: Alkylation , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10372 , http://hdl.handle.net/10948/1077 , Alkylation , Chemistry, Organic
- Description: The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.
- Full Text:
- Date Issued: 2008
- Authors: Skiti-Mama, Neliswa
- Date: 2008
- Subjects: Alkylation , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10372 , http://hdl.handle.net/10948/1077 , Alkylation , Chemistry, Organic
- Description: The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.
- Full Text:
- Date Issued: 2008
Studies in marine diterpene chemistry
- Van Wyk, Albert Wynand Wincke
- Authors: Van Wyk, Albert Wynand Wincke
- Date: 2008
- Subjects: Natural products Diterpenes Mollusks Marine metabolites Chemical oceanography
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4354 , http://hdl.handle.net/10962/d1005019
- Description: This thesis comprises both a natural product investigation and a synthetic component. The natural product investigations are presented in Chapters Two and Three. In Chapter Two the isolation and spectroscopic identification of the new isocopalane diterpene 12S,13R,14Sisocopalan- 13-ol-12,14-diacetate (2.1) and two known 3-(14S)-isocopal-12-ene-15-oyl-1- acetyl-sn-glycerol (2.2) and 3-(14S)-isocopal-12-ene-15-oyl-2-acetyl-sn-glycerol (2.3) from a single, large, unidentified sub-Antarctic nudibranch, collected near Marion Island, approximately 2000 km south of Cape Town are described. Chapter Three discusses the isolation, spectroscopic structure elucidation and anti-oesophageal cancer activity (3.1-3.4 only) of two known labdane diterpenes 6β,7α-diacetoxylabda-8,13E-dien-15-ol (3.1) and 2α,6β,7α-triacetoxylabda-8,13E-dien-15-ol (3.2) and one new 6β,7α,15-triacetoxylabda 8,13E-diene (3.3), as well as new 3α,11-dihydroxy-9,11-seco-cholest-4,7-dien-6,9-dione (3.4) and cholest 7-en-3,5,7-triol (3.5) from the endemic pulmonate mollusc, Trimusculus costatus. The absolute configuration of 3.2, and hence 3.1 and 3.3 (from biogenetic arguments) was determined through X-ray diffraction of a single crystal of the camphanate ester of 3.2. The absolute configuration of the secondary hydroxyl at C-3 of 3.4 was established using the Modified Mosher’s method. The synthetic component of the thesis commences in Chapter Four with the semi-synthesis of labdane diterpene nitriles 9α-cyano-15,16-epoxy-7β-hydroxylabda-13(16),14-dien-6-one (4.1), 9α-cyano-15,16-epoxy-7-hydroxylabda-7,13(16),14-trien-6-one (4.2) and 9α-cyano-15,16- epoxy-6β,7β dihydroxylabda-13(16),14-diene (4.3) from the terrestrial labdane diterpene, hispanolone (4.4). This work is an extension of previous synthetic studies directed towards the synthesis of T. costatus metabolites. Diterpenes 4.1-4.3 exhibited in planta activity against the economically important crop pathogens, Magnaporthea grisea and Puccinia recondita. Chapter Five describes the successful semi-synthesis of two isomeric marine molluscan labdane diterpene aldehyde metabolites, labd-13E-ene-8β-ol-15-al (5.1) and labd-13Z-ene- 8β-ol-15-al (5.2) from the commercially available, terrestrial plant derived, labdane diterpene manool (5.3). Diterpenes 5.1 and 5.2, originally isolated from the Mediterranean nudibranch,Pleurobranchaea meckelii and selected diterpenes arising from this synthesis were evaluated for their activity against an oesophageal cancer cell line (WHCO1). Chapter Six further develops the research discussed in Chapter Five, where ethyl 17-norabiet-13(15)-E-en-8β-ol- 16-oate (5.49) and ethyl 17-norabiet-13(15)-Z-en-8β-ol-16-oate (5.50) were first semisynthesized serendipitously. Based on their structural relationship to naturally occurring tricyclic diterpenes with anti-plasmodial activity, tricyclic diterpenes, 17-norpimaran-13α- ethoxy-8,16-olactone (6.6), 17-norisopimar-15-ene-8β,13β-diol (6.7), 17-norisopimarane- 8β,16-diol (6.8) and 17-norabiet-13(15)-ene-8β,16-diol (6.9) were semi-synthesized from the terrestrial labdane diterpene, 5.3, and critically evaluated for their antimalarial potential from parasite inhibition and haemolytic studies.
- Full Text:
- Date Issued: 2008
- Authors: Van Wyk, Albert Wynand Wincke
- Date: 2008
- Subjects: Natural products Diterpenes Mollusks Marine metabolites Chemical oceanography
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4354 , http://hdl.handle.net/10962/d1005019
- Description: This thesis comprises both a natural product investigation and a synthetic component. The natural product investigations are presented in Chapters Two and Three. In Chapter Two the isolation and spectroscopic identification of the new isocopalane diterpene 12S,13R,14Sisocopalan- 13-ol-12,14-diacetate (2.1) and two known 3-(14S)-isocopal-12-ene-15-oyl-1- acetyl-sn-glycerol (2.2) and 3-(14S)-isocopal-12-ene-15-oyl-2-acetyl-sn-glycerol (2.3) from a single, large, unidentified sub-Antarctic nudibranch, collected near Marion Island, approximately 2000 km south of Cape Town are described. Chapter Three discusses the isolation, spectroscopic structure elucidation and anti-oesophageal cancer activity (3.1-3.4 only) of two known labdane diterpenes 6β,7α-diacetoxylabda-8,13E-dien-15-ol (3.1) and 2α,6β,7α-triacetoxylabda-8,13E-dien-15-ol (3.2) and one new 6β,7α,15-triacetoxylabda 8,13E-diene (3.3), as well as new 3α,11-dihydroxy-9,11-seco-cholest-4,7-dien-6,9-dione (3.4) and cholest 7-en-3,5,7-triol (3.5) from the endemic pulmonate mollusc, Trimusculus costatus. The absolute configuration of 3.2, and hence 3.1 and 3.3 (from biogenetic arguments) was determined through X-ray diffraction of a single crystal of the camphanate ester of 3.2. The absolute configuration of the secondary hydroxyl at C-3 of 3.4 was established using the Modified Mosher’s method. The synthetic component of the thesis commences in Chapter Four with the semi-synthesis of labdane diterpene nitriles 9α-cyano-15,16-epoxy-7β-hydroxylabda-13(16),14-dien-6-one (4.1), 9α-cyano-15,16-epoxy-7-hydroxylabda-7,13(16),14-trien-6-one (4.2) and 9α-cyano-15,16- epoxy-6β,7β dihydroxylabda-13(16),14-diene (4.3) from the terrestrial labdane diterpene, hispanolone (4.4). This work is an extension of previous synthetic studies directed towards the synthesis of T. costatus metabolites. Diterpenes 4.1-4.3 exhibited in planta activity against the economically important crop pathogens, Magnaporthea grisea and Puccinia recondita. Chapter Five describes the successful semi-synthesis of two isomeric marine molluscan labdane diterpene aldehyde metabolites, labd-13E-ene-8β-ol-15-al (5.1) and labd-13Z-ene- 8β-ol-15-al (5.2) from the commercially available, terrestrial plant derived, labdane diterpene manool (5.3). Diterpenes 5.1 and 5.2, originally isolated from the Mediterranean nudibranch,Pleurobranchaea meckelii and selected diterpenes arising from this synthesis were evaluated for their activity against an oesophageal cancer cell line (WHCO1). Chapter Six further develops the research discussed in Chapter Five, where ethyl 17-norabiet-13(15)-E-en-8β-ol- 16-oate (5.49) and ethyl 17-norabiet-13(15)-Z-en-8β-ol-16-oate (5.50) were first semisynthesized serendipitously. Based on their structural relationship to naturally occurring tricyclic diterpenes with anti-plasmodial activity, tricyclic diterpenes, 17-norpimaran-13α- ethoxy-8,16-olactone (6.6), 17-norisopimar-15-ene-8β,13β-diol (6.7), 17-norisopimarane- 8β,16-diol (6.8) and 17-norabiet-13(15)-ene-8β,16-diol (6.9) were semi-synthesized from the terrestrial labdane diterpene, 5.3, and critically evaluated for their antimalarial potential from parasite inhibition and haemolytic studies.
- Full Text:
- Date Issued: 2008
Integer optimization for the selection of a twenty20 cricket team
- Authors: Lourens, Mark
- Date: 2008
- Subjects: Cricket -- Coaching , Teamwork (Sports) , Cricket players , Sports -- Research -- Methodology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10568 , http://hdl.handle.net/10948/1000 , http://hdl.handle.net/10948/d1009631 , Cricket -- Coaching , Teamwork (Sports) , Cricket players , Sports -- Research -- Methodology
- Description: During the last few years, much effort has been devoted to measuring the ability of sport teams, as well as that of the individual players. Much research has been on the game of cricket, and the comparison, or ranking, of players according to their abilities. This study continues preceding research using an optimization approach, namely, a binary integer programme, to select an SA domestic Pro20 cricket team.
- Full Text:
- Date Issued: 2008
- Authors: Lourens, Mark
- Date: 2008
- Subjects: Cricket -- Coaching , Teamwork (Sports) , Cricket players , Sports -- Research -- Methodology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10568 , http://hdl.handle.net/10948/1000 , http://hdl.handle.net/10948/d1009631 , Cricket -- Coaching , Teamwork (Sports) , Cricket players , Sports -- Research -- Methodology
- Description: During the last few years, much effort has been devoted to measuring the ability of sport teams, as well as that of the individual players. Much research has been on the game of cricket, and the comparison, or ranking, of players according to their abilities. This study continues preceding research using an optimization approach, namely, a binary integer programme, to select an SA domestic Pro20 cricket team.
- Full Text:
- Date Issued: 2008
Synthetic, spectrometric and computer modelling studies of novel ATP analogues
- Gxoyiya, Babalwa Siliziwe Blossom
- Authors: Gxoyiya, Babalwa Siliziwe Blossom
- Date: 2008
- Subjects: Spectrum analysis Tuberculosis -- Treatment Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Adenosine triphosphate -- Computer simulation Adenosine triphosphate -- Spectrometric imaging Glutamine synthetase Tuberculosis -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4386 , http://hdl.handle.net/10962/d1005051
- Description: This study has been concerned with the design and synthesis of A TP analogues with the potential to act as inhibitors of glutamine synthetase - a novel target for therapeutic intervention in the treatment of tuberculosis. Using a structural -analogy approach, various 3-indolylalkanoic acid, benzimidazole and pyrazolo[3,4-dJpyrimidine derivatives have been prepared and characterized. Alkylation of the heterocyclic bases using 4-(bromomethyl)-2,2-dimethyl-1 ,3-d ioxolane, 2-(bromomethoxy)ethyl acetate and 2-(chloroethoxy)ethanol in the presence of either NaH or BulOK afforded the corresponding N-alkylated derivatives of benzimidazole and 4-aminopyrazolo[3,4-dJpyrimidine (4-APP). Similar reactions with 3-indo lylalkanoic esters resulted in O-alkyl cleavage with the formation of new esters. Alkylation of benzimidazole with allyl bromide, 4-bromobutene and 2-methylbut-2-ene has also been shown to afford the corresponding l-alkenylbenzimidazoles in moderate to excellent yield (43-96%). Subsequent oxidation of these products using CTAP, gave the dihydroxy derivatives in poor to good yields (26-77%). Phosphorylation of various hydroxy derivatives of benzimidazole and 4-APP has been achieved using diethyl chlorophosphate to afford the corresponding monophosphate and 1,2-diphosphate esters. Glycosylation of each of the heterocyclic bases has been successfully achieved using 1,2,3,4,6-penta-O-acetyl-D-glucopyranose and SnCl4 in acetonitri le, while methanolysis of the resulting tetraacetates, using methanolic NaOMe, afforded the hydroxy derivatives in good yield (50-70%). Various 1- and 2-dimensional NMR spectroscopic methods (e.g., IH, 13C, lip, COSY, HSQC and HMBC) have been used to confirm the structures of the synthesized A IP analogues. The application of NMR prediction programmes has been explored, permitting assessment of their agreement with the experimental data and confirmation of assigned structures. High-resolution electron impact (EI) mass spectrometric data have been used to explore the mass fragmentation pathways exhibited by selected derivatives, and certain common fragmentations have been identified. Molecular modelling of selected products as potential glutamine synthetase ligands has been performed on the Accelrys Cerius2 platform, and interactive receptor-ligand docking studies have been conducted using the Ligand-Fit module. These studies have revealed possible hydrogen-boding interactions between the selected analogues and various amino acid residues in the glutamine synthetase active site.
- Full Text:
- Date Issued: 2008
- Authors: Gxoyiya, Babalwa Siliziwe Blossom
- Date: 2008
- Subjects: Spectrum analysis Tuberculosis -- Treatment Chemotherapy Adenosine triphosphate Adenosine triphosphate -- Synthesis Adenosine triphosphate -- Computer simulation Adenosine triphosphate -- Spectrometric imaging Glutamine synthetase Tuberculosis -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4386 , http://hdl.handle.net/10962/d1005051
- Description: This study has been concerned with the design and synthesis of A TP analogues with the potential to act as inhibitors of glutamine synthetase - a novel target for therapeutic intervention in the treatment of tuberculosis. Using a structural -analogy approach, various 3-indolylalkanoic acid, benzimidazole and pyrazolo[3,4-dJpyrimidine derivatives have been prepared and characterized. Alkylation of the heterocyclic bases using 4-(bromomethyl)-2,2-dimethyl-1 ,3-d ioxolane, 2-(bromomethoxy)ethyl acetate and 2-(chloroethoxy)ethanol in the presence of either NaH or BulOK afforded the corresponding N-alkylated derivatives of benzimidazole and 4-aminopyrazolo[3,4-dJpyrimidine (4-APP). Similar reactions with 3-indo lylalkanoic esters resulted in O-alkyl cleavage with the formation of new esters. Alkylation of benzimidazole with allyl bromide, 4-bromobutene and 2-methylbut-2-ene has also been shown to afford the corresponding l-alkenylbenzimidazoles in moderate to excellent yield (43-96%). Subsequent oxidation of these products using CTAP, gave the dihydroxy derivatives in poor to good yields (26-77%). Phosphorylation of various hydroxy derivatives of benzimidazole and 4-APP has been achieved using diethyl chlorophosphate to afford the corresponding monophosphate and 1,2-diphosphate esters. Glycosylation of each of the heterocyclic bases has been successfully achieved using 1,2,3,4,6-penta-O-acetyl-D-glucopyranose and SnCl4 in acetonitri le, while methanolysis of the resulting tetraacetates, using methanolic NaOMe, afforded the hydroxy derivatives in good yield (50-70%). Various 1- and 2-dimensional NMR spectroscopic methods (e.g., IH, 13C, lip, COSY, HSQC and HMBC) have been used to confirm the structures of the synthesized A IP analogues. The application of NMR prediction programmes has been explored, permitting assessment of their agreement with the experimental data and confirmation of assigned structures. High-resolution electron impact (EI) mass spectrometric data have been used to explore the mass fragmentation pathways exhibited by selected derivatives, and certain common fragmentations have been identified. Molecular modelling of selected products as potential glutamine synthetase ligands has been performed on the Accelrys Cerius2 platform, and interactive receptor-ligand docking studies have been conducted using the Ligand-Fit module. These studies have revealed possible hydrogen-boding interactions between the selected analogues and various amino acid residues in the glutamine synthetase active site.
- Full Text:
- Date Issued: 2008
Agathis bishopi (Nixon) (Hymenoptera: braconidae) its biology and usefulness as a biological control agent for false codling moth (FCM), Thaumatotibia leucotreta (Meyrick) (Lepidoptera: tortricidae), on citrus bishopi (Nixon) (Hymenoptera: braconidae) its biology and usefulness as a biological control agent for false codling moth (FCM), Thaumatotibia leucotreta (Meyrick) (Lepidoptera: tortricidae), on citrus
- Authors: Gendall, Kierryn Leigh
- Date: 2008
- Subjects: Cryptophlebia leucotreta -- Parasites , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Tortricidae , Braconidae , Citrus -- Diseases and pests
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5635 , http://hdl.handle.net/10962/d1005317 , Cryptophlebia leucotreta -- Parasites , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Tortricidae , Braconidae , Citrus -- Diseases and pests
- Description: The false codling moth, Thaumatotibia leucotreta (Meyrick) (Lepidoptera: Tortricidae), is one of the major pests of citrus in South Africa, the others being mealybug, Mediterranean fruit fly, bollworm and some mites. Due to problems such as the expense of pesticides, insects evolving pesticide resistance (Hogsette 1999), chemical residue on the skin of export fruit and the negative impact of pesticides on the environment, it became necessary to find alternative methods for pest control (Viggiani 2000). Agathis bishopi (Nixon) (Hymenoptera: Braconidae), a larval parasitoid of false codling moth known only from the Sundays River Valley area (Sishuba 2003), offers a means of control for the pest. A total of 11 389 navel oranges were collected from various orchards in the Addo/Kirkwood area, and false codling moth larvae infested 36.09% of the fruit. A single parasitoid species, A. bishopi, was reared from these larvae. In 2006 the highest parasitism rate, 11.43%, was recorded in May and in 2007, the highest parasitism rate, 13.27%, was in April. Agathis bishopi parasitizes larvae in instars 2 and 3, possibly due to the accessibility of these younger instars to the female parasitoid and possibly due to the length of the life cycle of this koinobiont. Second instar hosts yielded the highest number of parasitoids, and there was no emergence of parasitoids from fifth instar larvae. Females of A. bishopi live for 18.5 days (n = 20; S.E. = 3.1) and males for 8.25 days (n = 20; S.E. = 1.23). Females produce an average of 23 offspring in a lifetime, while female false codling moths produce about 800 eggs each. A high number of parasitoids will be required per hectare to reduce the population of false codling moth. Captive rearing of A. bishopi proved difficult due to viral and fungal contamination. Agathis bishopi has potential for use in an integrated pest management programme once the hurdle of mass-rearing has been overcome.
- Full Text:
- Date Issued: 2008
- Authors: Gendall, Kierryn Leigh
- Date: 2008
- Subjects: Cryptophlebia leucotreta -- Parasites , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Tortricidae , Braconidae , Citrus -- Diseases and pests
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5635 , http://hdl.handle.net/10962/d1005317 , Cryptophlebia leucotreta -- Parasites , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Tortricidae , Braconidae , Citrus -- Diseases and pests
- Description: The false codling moth, Thaumatotibia leucotreta (Meyrick) (Lepidoptera: Tortricidae), is one of the major pests of citrus in South Africa, the others being mealybug, Mediterranean fruit fly, bollworm and some mites. Due to problems such as the expense of pesticides, insects evolving pesticide resistance (Hogsette 1999), chemical residue on the skin of export fruit and the negative impact of pesticides on the environment, it became necessary to find alternative methods for pest control (Viggiani 2000). Agathis bishopi (Nixon) (Hymenoptera: Braconidae), a larval parasitoid of false codling moth known only from the Sundays River Valley area (Sishuba 2003), offers a means of control for the pest. A total of 11 389 navel oranges were collected from various orchards in the Addo/Kirkwood area, and false codling moth larvae infested 36.09% of the fruit. A single parasitoid species, A. bishopi, was reared from these larvae. In 2006 the highest parasitism rate, 11.43%, was recorded in May and in 2007, the highest parasitism rate, 13.27%, was in April. Agathis bishopi parasitizes larvae in instars 2 and 3, possibly due to the accessibility of these younger instars to the female parasitoid and possibly due to the length of the life cycle of this koinobiont. Second instar hosts yielded the highest number of parasitoids, and there was no emergence of parasitoids from fifth instar larvae. Females of A. bishopi live for 18.5 days (n = 20; S.E. = 3.1) and males for 8.25 days (n = 20; S.E. = 1.23). Females produce an average of 23 offspring in a lifetime, while female false codling moths produce about 800 eggs each. A high number of parasitoids will be required per hectare to reduce the population of false codling moth. Captive rearing of A. bishopi proved difficult due to viral and fungal contamination. Agathis bishopi has potential for use in an integrated pest management programme once the hurdle of mass-rearing has been overcome.
- Full Text:
- Date Issued: 2008
Studies directed towards the synthesis of chromone carbaldehyde-derived HIV-1 protease inhibitors
- Authors: Molefe, Duduzile Mabel
- Date: 2008
- Subjects: Protease Inhibitors , HIV infections , HIV (Viruses) , AIDS (Disease) , Proteolytic enzymes , Heterocyclic compounds -- Derivatives , Chemical kinetics , Nuclear magnetic resonance spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4526 , http://hdl.handle.net/10962/d1015542
- Description: A series of chromone-3-carbaldehydes have been prepared using Vilsmeier-Haack methodology while a corresponding series of chromone-2-carbaldeydes have been synthesized via the Kostanecki-Robinson reaction. Baylis-Hillman reactions have been conducted on both series of chromone carbaldehydes using three different catalysts, viz., 1,4-diazabicyclo(2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) and 3-hydroxyquinuclidine (3HQ), and acrylonitrile, methyl acrylate and methyl vinyl ketone as the activated alkenes. These reactions have typically (but not always!) afforded both normal Baylis-Hillman and dimeric products. Attention has also been given to the use of 1-methyl-2-pyrrolidine (1-NMP), an ionic liquid, to replace normal organic solvents, and it has been found that, in the presence of DABCO, chromone-3-carbaldehydes afford the dimeric products alone. Reactions of chromone-3-carbaldehydes with methyl vinyl ketone have yielded unexpected, novel adducts, which appear to arise from preferential attack at C(2) in the chromone nucleus. Research on chromone-2-carbaldeydes under Baylis-Hillman conditions has also resulted in the formation of some interesting products instead of the expected Baylis-Hillman adducts. The Baylis-Hillman products have been explored as substrates for aza-Michael reactions using various amino derivatives including protected amino acids in the presence of the tetrabutylammonium bromide (TBAB) and the ionic liquid, 3-butyl-1- methylimidazoleboranetetrafluoride (BmimBF₄), as catalysts. The aza-Michael products have been targeted as truncated ritonavir analogues for investigation as potential HIV -1 protease inhibitors, and representative compounds have been subjected to enzyme inhibition assays to explore the extent and type of inhibition. Lineweaver-Burk and Dixon plots have indicated competitive inhibition in one case as well as non-competitive inhibition in another, and the inhibition constants (Ki) have been compared with that of the ritonavir. Computer modelling studies have also been conducted on selected chromonecontaining derivatives, using the ACCELRYS Cerius² platform. Interactive docking of the chromone-containing ligands into the HIV -1 protease receptor site, using the Ligandfit module, has indicated the importance of hydrogen-bonding interactions mediated by bridging water molecules situated in the receptor cavity. NMR spectroscopy has been used to elucidate complex and competing mechanistic pathways involved in the Baylis-Hillman reactions of selected 2-nitrobenzaldehydes with MVK in the presence of DABCO - reactions which afford the normal BaylisHillman product, the MVK dimer and syn- and anti-Baylis-Hillman type diadducts. The kinetic data confirm the concomitant operation of two pathways and reveal that, in the initial stage of the reaction, the product distribution is kinetically controlled, whereas in the latter stage, thermodynamic control results in the consumption of the normal Baylis-Hillman product and predominance of the anti-diadduct.
- Full Text:
- Date Issued: 2008
- Authors: Molefe, Duduzile Mabel
- Date: 2008
- Subjects: Protease Inhibitors , HIV infections , HIV (Viruses) , AIDS (Disease) , Proteolytic enzymes , Heterocyclic compounds -- Derivatives , Chemical kinetics , Nuclear magnetic resonance spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4526 , http://hdl.handle.net/10962/d1015542
- Description: A series of chromone-3-carbaldehydes have been prepared using Vilsmeier-Haack methodology while a corresponding series of chromone-2-carbaldeydes have been synthesized via the Kostanecki-Robinson reaction. Baylis-Hillman reactions have been conducted on both series of chromone carbaldehydes using three different catalysts, viz., 1,4-diazabicyclo(2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) and 3-hydroxyquinuclidine (3HQ), and acrylonitrile, methyl acrylate and methyl vinyl ketone as the activated alkenes. These reactions have typically (but not always!) afforded both normal Baylis-Hillman and dimeric products. Attention has also been given to the use of 1-methyl-2-pyrrolidine (1-NMP), an ionic liquid, to replace normal organic solvents, and it has been found that, in the presence of DABCO, chromone-3-carbaldehydes afford the dimeric products alone. Reactions of chromone-3-carbaldehydes with methyl vinyl ketone have yielded unexpected, novel adducts, which appear to arise from preferential attack at C(2) in the chromone nucleus. Research on chromone-2-carbaldeydes under Baylis-Hillman conditions has also resulted in the formation of some interesting products instead of the expected Baylis-Hillman adducts. The Baylis-Hillman products have been explored as substrates for aza-Michael reactions using various amino derivatives including protected amino acids in the presence of the tetrabutylammonium bromide (TBAB) and the ionic liquid, 3-butyl-1- methylimidazoleboranetetrafluoride (BmimBF₄), as catalysts. The aza-Michael products have been targeted as truncated ritonavir analogues for investigation as potential HIV -1 protease inhibitors, and representative compounds have been subjected to enzyme inhibition assays to explore the extent and type of inhibition. Lineweaver-Burk and Dixon plots have indicated competitive inhibition in one case as well as non-competitive inhibition in another, and the inhibition constants (Ki) have been compared with that of the ritonavir. Computer modelling studies have also been conducted on selected chromonecontaining derivatives, using the ACCELRYS Cerius² platform. Interactive docking of the chromone-containing ligands into the HIV -1 protease receptor site, using the Ligandfit module, has indicated the importance of hydrogen-bonding interactions mediated by bridging water molecules situated in the receptor cavity. NMR spectroscopy has been used to elucidate complex and competing mechanistic pathways involved in the Baylis-Hillman reactions of selected 2-nitrobenzaldehydes with MVK in the presence of DABCO - reactions which afford the normal BaylisHillman product, the MVK dimer and syn- and anti-Baylis-Hillman type diadducts. The kinetic data confirm the concomitant operation of two pathways and reveal that, in the initial stage of the reaction, the product distribution is kinetically controlled, whereas in the latter stage, thermodynamic control results in the consumption of the normal Baylis-Hillman product and predominance of the anti-diadduct.
- Full Text:
- Date Issued: 2008
Enigmatic trace fossils from the Aeolian lower Jurassic Clarens formation, Southern Africa
- Authors: Bordy, Emese M
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6730 , http://hdl.handle.net/10962/d1007538
- Description: The Lower Jurassic aeolienites of the Clarens Formation in southern Africa contain unique sedimentary structures that are unlikely to be non-biogenic. They are also unlike any known modern or ancient trace fossils. Here, some nigmatic, horizontal,regularly-oriented sedimentary structures are described, which occur in association with other trace fossils as well as features that were previously nterpreted as nests of termites or termite-like ancient social nsects. These spectacular structures are exposed in enormous profusion as straight, ~5 mm cylinders with strong compass orientation, in parallel alignment with one another and to ancient horizontal bedding planes. Their fill is identical to that of the host rock: clean, well-sorted, very fine- to finegrained quartz-arenite. In cross-section, each structure is defined by a subtle, ~0.1 mm thin, concentric gap. Without comparable modern biogenic structures, the biological origin of the structures is uncertain. Their strong compass orientations are, however, also inconsistent with an inorganic origin, even though they may resemble pipey concretions generated by flowing groundwater. Nonetheless, this paper, based on spatiotemporal distribution patterns of the oriented structures, their locally high abundance and association with obvious trace fossils, as well as other sedimentological and palaeontological lines of evidence, argues that the compass structures may be products of ancient social invertebrates living in a resource-limited, semi-arid to arid environment. Furthermore, the compass structures as well as the accompanying structures of the predominantly aeolian Clarens Formation collectively imply the recurrence of favourable ecological parameters (e.g., moist ubstrates) related to episodic climate fluctuations in the Early Jurassic of southern Pangaea (i.e., southern Gondwana).
- Full Text:
- Date Issued: 2008
- Authors: Bordy, Emese M
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6730 , http://hdl.handle.net/10962/d1007538
- Description: The Lower Jurassic aeolienites of the Clarens Formation in southern Africa contain unique sedimentary structures that are unlikely to be non-biogenic. They are also unlike any known modern or ancient trace fossils. Here, some nigmatic, horizontal,regularly-oriented sedimentary structures are described, which occur in association with other trace fossils as well as features that were previously nterpreted as nests of termites or termite-like ancient social nsects. These spectacular structures are exposed in enormous profusion as straight, ~5 mm cylinders with strong compass orientation, in parallel alignment with one another and to ancient horizontal bedding planes. Their fill is identical to that of the host rock: clean, well-sorted, very fine- to finegrained quartz-arenite. In cross-section, each structure is defined by a subtle, ~0.1 mm thin, concentric gap. Without comparable modern biogenic structures, the biological origin of the structures is uncertain. Their strong compass orientations are, however, also inconsistent with an inorganic origin, even though they may resemble pipey concretions generated by flowing groundwater. Nonetheless, this paper, based on spatiotemporal distribution patterns of the oriented structures, their locally high abundance and association with obvious trace fossils, as well as other sedimentological and palaeontological lines of evidence, argues that the compass structures may be products of ancient social invertebrates living in a resource-limited, semi-arid to arid environment. Furthermore, the compass structures as well as the accompanying structures of the predominantly aeolian Clarens Formation collectively imply the recurrence of favourable ecological parameters (e.g., moist ubstrates) related to episodic climate fluctuations in the Early Jurassic of southern Pangaea (i.e., southern Gondwana).
- Full Text:
- Date Issued: 2008
A synopsis of the Afrotropical Tricorythidae
- Authors: Barber-James, Helen M
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:7003 , http://hdl.handle.net/10962/d1008362
- Description: The Tricorythidae of the Afrotropical Region is currently composed of five described genera, three of which are thought to be restricted to Madagascar (Madecassorythus Elouard and Oliarioniny, Ranorythus Oliarinony and Elouard, and Spinirythus Oliarinony and Elouard), one which is restricted to Africa (Dicercomyzon Demoulin), and one which is thought to be distributed on both landmasses (Tricorythus Eaton). Based on sexual dimorphism, manifest in the relative eye size of mature male and female nymphs and adults and on the structure of the genitalia of adult males, it is proposed that there are two additional genera in Africa, as yet undescribed. One of these genera is represented by a species currently placed in Tricorythus (T. discolor [Burmeister]). Several other undescribed species within South Africa have been identified as belonging to the group. A second lineage is represented by Tricorythus tinctus Kimmins, from Uganda, the only currently described species. There are also several more undescribed species of this group widespread in Africa.
- Full Text:
- Date Issued: 2008
- Authors: Barber-James, Helen M
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:7003 , http://hdl.handle.net/10962/d1008362
- Description: The Tricorythidae of the Afrotropical Region is currently composed of five described genera, three of which are thought to be restricted to Madagascar (Madecassorythus Elouard and Oliarioniny, Ranorythus Oliarinony and Elouard, and Spinirythus Oliarinony and Elouard), one which is restricted to Africa (Dicercomyzon Demoulin), and one which is thought to be distributed on both landmasses (Tricorythus Eaton). Based on sexual dimorphism, manifest in the relative eye size of mature male and female nymphs and adults and on the structure of the genitalia of adult males, it is proposed that there are two additional genera in Africa, as yet undescribed. One of these genera is represented by a species currently placed in Tricorythus (T. discolor [Burmeister]). Several other undescribed species within South Africa have been identified as belonging to the group. A second lineage is represented by Tricorythus tinctus Kimmins, from Uganda, the only currently described species. There are also several more undescribed species of this group widespread in Africa.
- Full Text:
- Date Issued: 2008
Camphor derivatives in asymmetric synthesis: a synthetic, mechanistic and theoretical study
- Authors: Lobb, Kevin Alan
- Date: 2008
- Subjects: Chemistry, Organic -- Research Esters Organic compounds -- Synthesis Alkylation Chemical reactions -- Computer simulation Chemical kinetics Camphor Cinnamomum
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4414 , http://hdl.handle.net/10962/d1006770
- Description: A series of 3,3-ethylenedioxy-exo- and endo- bornyl esters have been prepared and subjected to α-benzylation using lithium diisopropylamide and benzyl bromide. In the exo-series of esters the diastereofacial selectivity of benzylation was found to improve (up to 34% d.e.) as the steric bulk of the O-alkyl group increased, whereas in the endo-series, a surprising decrease in stereoselectivity was observed as the steric bulk increased – an observation attributed to flexibility of the metal-coordinated endo-enolate system, compared to the relative rigidity of the exo analogues. The conformational options for each series was explored at the density functional theory level. Reductive cyclization of a range of specially prepared N-carbobenzyloxy-amino acid esters has been shown to afford the corresponding derivatives, contrary to previous reports that the cyclization is limited to the glycine derivative. The cyclization sequence has been explored in detail, and the yield has been shown to be critically dependent on the stereochemistry of the α-amino acid moiety. Moreover, it seems that reductive cyclization occurs more readily with the endo- rather than the exo-bornyl N-CBZ-amino acid esters. Molecular modelling of relevant transition states at the DFT levels indicates that L-amino acid-derived systems should cyclize preferably in the exo-series and D-amino acid-derived systems should cyclize preferably in the endo series. Studies of alkylation of an iminolactone system have reported an interesting anomaly - exo-methylation is observed while endo-alkylation predominates for larger alkyl groups. This has been studied in detail at the DFT level, and the anomaly is attributed to thermodynamic control in the methyl case, whereas kinetic control is the norm in this system. Preliminary computer modelling of the intramolecular rearrangement of a 3,3-xylylbornyl system at the HF/STO-3G level raised doubts concerning the structure assigned by Evans to one of the rearrangement products, prompting an X-ray crystallographic analysis and leading to the revision of its structure from a pinene to a camphene derivative. The previously elusive spiro[bornane-3,2’-indan]-2-exo-tosylate has been successfully isolated, and the kinetics of its ready decomposition to the two camphene products has been followed by 1H NMR spectroscopy. The endo-tosylate analogue, on the other hand, was found to be remarkably stable. Kinetic data obtained for rearrangement of this exo-bornyl tosylate have indicated the operation of tandem autocatalytic and pseudo-first-order transformations leading sequentially to the two isomeric camphene products. An extensive coset analysis of all possible rearrangement processes of the initially-formed cation formed from decomposition of the exo-tosylate has afforded a graph containing 336 classical cations (modelled at the AM1 and B3LYP levels) and 526 transition-state complexes (modelled at the AM1 level). This analysis afforded a viable 4-step classical mechanism connecting the first camphene product with the second. A more realistic study, involving non-classical carbocations, has afforded a graph of all possible (classical and non-classical) cations that could be formed by rearrangment of the initiallyformed cation. The resulting graph confirms that the only energetically feasible path corresponds to the classical mechanism, but simply involves two steps, including a novel, concerted Wagner-Meerwein – 6,2-hydride shift – Wagner-Meerwein rearrangement.
- Full Text:
- Date Issued: 2008
- Authors: Lobb, Kevin Alan
- Date: 2008
- Subjects: Chemistry, Organic -- Research Esters Organic compounds -- Synthesis Alkylation Chemical reactions -- Computer simulation Chemical kinetics Camphor Cinnamomum
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4414 , http://hdl.handle.net/10962/d1006770
- Description: A series of 3,3-ethylenedioxy-exo- and endo- bornyl esters have been prepared and subjected to α-benzylation using lithium diisopropylamide and benzyl bromide. In the exo-series of esters the diastereofacial selectivity of benzylation was found to improve (up to 34% d.e.) as the steric bulk of the O-alkyl group increased, whereas in the endo-series, a surprising decrease in stereoselectivity was observed as the steric bulk increased – an observation attributed to flexibility of the metal-coordinated endo-enolate system, compared to the relative rigidity of the exo analogues. The conformational options for each series was explored at the density functional theory level. Reductive cyclization of a range of specially prepared N-carbobenzyloxy-amino acid esters has been shown to afford the corresponding derivatives, contrary to previous reports that the cyclization is limited to the glycine derivative. The cyclization sequence has been explored in detail, and the yield has been shown to be critically dependent on the stereochemistry of the α-amino acid moiety. Moreover, it seems that reductive cyclization occurs more readily with the endo- rather than the exo-bornyl N-CBZ-amino acid esters. Molecular modelling of relevant transition states at the DFT levels indicates that L-amino acid-derived systems should cyclize preferably in the exo-series and D-amino acid-derived systems should cyclize preferably in the endo series. Studies of alkylation of an iminolactone system have reported an interesting anomaly - exo-methylation is observed while endo-alkylation predominates for larger alkyl groups. This has been studied in detail at the DFT level, and the anomaly is attributed to thermodynamic control in the methyl case, whereas kinetic control is the norm in this system. Preliminary computer modelling of the intramolecular rearrangement of a 3,3-xylylbornyl system at the HF/STO-3G level raised doubts concerning the structure assigned by Evans to one of the rearrangement products, prompting an X-ray crystallographic analysis and leading to the revision of its structure from a pinene to a camphene derivative. The previously elusive spiro[bornane-3,2’-indan]-2-exo-tosylate has been successfully isolated, and the kinetics of its ready decomposition to the two camphene products has been followed by 1H NMR spectroscopy. The endo-tosylate analogue, on the other hand, was found to be remarkably stable. Kinetic data obtained for rearrangement of this exo-bornyl tosylate have indicated the operation of tandem autocatalytic and pseudo-first-order transformations leading sequentially to the two isomeric camphene products. An extensive coset analysis of all possible rearrangement processes of the initially-formed cation formed from decomposition of the exo-tosylate has afforded a graph containing 336 classical cations (modelled at the AM1 and B3LYP levels) and 526 transition-state complexes (modelled at the AM1 level). This analysis afforded a viable 4-step classical mechanism connecting the first camphene product with the second. A more realistic study, involving non-classical carbocations, has afforded a graph of all possible (classical and non-classical) cations that could be formed by rearrangment of the initiallyformed cation. The resulting graph confirms that the only energetically feasible path corresponds to the classical mechanism, but simply involves two steps, including a novel, concerted Wagner-Meerwein – 6,2-hydride shift – Wagner-Meerwein rearrangement.
- Full Text:
- Date Issued: 2008
The potential roles of interactions between STAT3, Hsp90, and Hop in the maintenance of self-renewal in mouse embryonic stem cells
- Authors: Setati, Mokgadi Michael
- Date: 2008
- Subjects: Embryonic stem cells , Leukemia inhibitory factor , Cellular signal transduction , Heat shock proteins , Molecular chaperones
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3981 , http://hdl.handle.net/10962/d1004040 , Embryonic stem cells , Leukemia inhibitory factor , Cellular signal transduction , Heat shock proteins , Molecular chaperones
- Description: Self-renewal of mouse embryonic stem (mES) cells is dependent upon the presence of leukemia inhibitory factor (LIF). LIF induces tyrosine phosphorylation and nuclear translocation of STAT3 (signal transducer and activator of transcription 3) which is thought to promote self-renewal by inducing key target genes. The molecular chaperone heat shock protein 90 (Hsp90) is involved in signal transduction pathways and regulates STAT3 activity in different cell types. However, the role of Hsp90 in regulating STAT3 activity in mES cells has not previously been investigated. The aim of this study was to investigate if Hsp90 interacts with STAT3 in mES cells and to determine if this interaction is important for the maintenance of self-renewal. It was found that when mES cells were cultured for 24.0 hours in the absence of LIF, the expression levels of total STAT3, tyrosine-phosphorylated STAT3 (pYSTAT3), and the pluripotency marker, Nanog, were down regulated. However, the expression level of Hsp90 was found to be slightly up-regulated over the same period. Significantly, it was found that the amount of STAT3 in differentiating mES cells available for binding to Hsp90 was decreased upon down-regulation of STAT3 by LIF withdrawal. Therefore, STAT3-Hsp90 interactions in mES cells were dependent on the presence of LIF, which suggested that the reduction in STAT3-Hsp90 interaction may have resulted from the low levels of STAT3. Despite a dramatic reduction in the expression levels of pYSTAT3 upon 24.0 hours of culture of mES cells in the presence of the STAT3 tyrosine phosphorylation inhibitor, cucurbitanin I, there was no obvious reduction in the levels of total STAT3, Oct-3/4 or Nanog. These results suggested that the levels of unphosphorylated STAT3 rather than pYSTAT3, maybe more important in the maintenance of mES cells self-renewal.
- Full Text:
- Date Issued: 2008
- Authors: Setati, Mokgadi Michael
- Date: 2008
- Subjects: Embryonic stem cells , Leukemia inhibitory factor , Cellular signal transduction , Heat shock proteins , Molecular chaperones
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3981 , http://hdl.handle.net/10962/d1004040 , Embryonic stem cells , Leukemia inhibitory factor , Cellular signal transduction , Heat shock proteins , Molecular chaperones
- Description: Self-renewal of mouse embryonic stem (mES) cells is dependent upon the presence of leukemia inhibitory factor (LIF). LIF induces tyrosine phosphorylation and nuclear translocation of STAT3 (signal transducer and activator of transcription 3) which is thought to promote self-renewal by inducing key target genes. The molecular chaperone heat shock protein 90 (Hsp90) is involved in signal transduction pathways and regulates STAT3 activity in different cell types. However, the role of Hsp90 in regulating STAT3 activity in mES cells has not previously been investigated. The aim of this study was to investigate if Hsp90 interacts with STAT3 in mES cells and to determine if this interaction is important for the maintenance of self-renewal. It was found that when mES cells were cultured for 24.0 hours in the absence of LIF, the expression levels of total STAT3, tyrosine-phosphorylated STAT3 (pYSTAT3), and the pluripotency marker, Nanog, were down regulated. However, the expression level of Hsp90 was found to be slightly up-regulated over the same period. Significantly, it was found that the amount of STAT3 in differentiating mES cells available for binding to Hsp90 was decreased upon down-regulation of STAT3 by LIF withdrawal. Therefore, STAT3-Hsp90 interactions in mES cells were dependent on the presence of LIF, which suggested that the reduction in STAT3-Hsp90 interaction may have resulted from the low levels of STAT3. Despite a dramatic reduction in the expression levels of pYSTAT3 upon 24.0 hours of culture of mES cells in the presence of the STAT3 tyrosine phosphorylation inhibitor, cucurbitanin I, there was no obvious reduction in the levels of total STAT3, Oct-3/4 or Nanog. These results suggested that the levels of unphosphorylated STAT3 rather than pYSTAT3, maybe more important in the maintenance of mES cells self-renewal.
- Full Text:
- Date Issued: 2008
Understanding and improving the residual efficacy of the cryptophlebia leucotreta granulovirus (Cryptogran)
- Authors: Kirkman, Wayne
- Date: 2008
- Subjects: Cryptophlebia leucotreta , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Citrus -- Diseases and pests
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5794 , http://hdl.handle.net/10962/d1005482 , Cryptophlebia leucotreta , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Citrus -- Diseases and pests
- Description: False codling moth (FCM), Thaumatotibia (=Cryptophlebia) leucotreta (Meyr) (Lepidoptera: Tortricidae), is one of the most important pests on citrus. The Cryptophlebia leucotreta granulovirus (CrleGV) has been developed into a successful biological control agent, registered under the name Cryptogran, and is currently the preferred product for the control of FCM on citrus in South Africa. A prerequisite to the continued success of Cryptogran as a means of controlling false codling moth is to understand the factors affecting field persistence of the virus, and to find ways to improve it. The aim of this study was to gain a clearer understanding of the product and the abiotic and biotic factors affecting its persistence in the field, and to investigate methods to improve this persistence. The effect of UV-irradiation on the virus was determined, and various products were tested as UV protectants in laboratory bioassays. Lignin was the most effective additive, and was tested in several field trials, where it also enhanced the efficacy of Cryptogran. Laboratory trials indicated that Cryptogran is rainfast. Cryptogran applications early in the season had a longer period of residual activity than sprays applied closer to harvest. Daytime applications were less effective that evening sprays. Sprays applied coinciding with peaks in pheromone moth trap catches were more effective than those applied between peaks. Biotic factors influencing persistence were investigated. Residual efficacy was longer when treatments were applied to blocks than as single tree treatments. Attempts were made to quantify the effect of the navel end of a navel orange on the field persistence of Cryptogran. Cryptogran was shown to be compatible with many agricultural chemicals used on citrus. Economic thresholds and various cost-benefit analyses are discussed. A list of practical recommendations to growers was drawn up, and possibilities for future research are presented.
- Full Text:
- Date Issued: 2008
- Authors: Kirkman, Wayne
- Date: 2008
- Subjects: Cryptophlebia leucotreta , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Citrus -- Diseases and pests
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5794 , http://hdl.handle.net/10962/d1005482 , Cryptophlebia leucotreta , Cryptophlebia leucotreta -- Control , Pests -- Biological control , Citrus -- Diseases and pests
- Description: False codling moth (FCM), Thaumatotibia (=Cryptophlebia) leucotreta (Meyr) (Lepidoptera: Tortricidae), is one of the most important pests on citrus. The Cryptophlebia leucotreta granulovirus (CrleGV) has been developed into a successful biological control agent, registered under the name Cryptogran, and is currently the preferred product for the control of FCM on citrus in South Africa. A prerequisite to the continued success of Cryptogran as a means of controlling false codling moth is to understand the factors affecting field persistence of the virus, and to find ways to improve it. The aim of this study was to gain a clearer understanding of the product and the abiotic and biotic factors affecting its persistence in the field, and to investigate methods to improve this persistence. The effect of UV-irradiation on the virus was determined, and various products were tested as UV protectants in laboratory bioassays. Lignin was the most effective additive, and was tested in several field trials, where it also enhanced the efficacy of Cryptogran. Laboratory trials indicated that Cryptogran is rainfast. Cryptogran applications early in the season had a longer period of residual activity than sprays applied closer to harvest. Daytime applications were less effective that evening sprays. Sprays applied coinciding with peaks in pheromone moth trap catches were more effective than those applied between peaks. Biotic factors influencing persistence were investigated. Residual efficacy was longer when treatments were applied to blocks than as single tree treatments. Attempts were made to quantify the effect of the navel end of a navel orange on the field persistence of Cryptogran. Cryptogran was shown to be compatible with many agricultural chemicals used on citrus. Economic thresholds and various cost-benefit analyses are discussed. A list of practical recommendations to growers was drawn up, and possibilities for future research are presented.
- Full Text:
- Date Issued: 2008
Nuclear translocation of the phosphoprotein Hop (Hsp70/Hsp90 organizing protein) occurs under heat shock, and its proposed nuclear localization signal is involved in Hsp90 binding
- Daniel, Sheril, Bradley, Graeme, Longshaw, Victoria M, Söti, Csaba, Csermely, Peter, Blatch, Gregory L
- Authors: Daniel, Sheril , Bradley, Graeme , Longshaw, Victoria M , Söti, Csaba , Csermely, Peter , Blatch, Gregory L
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6472 , http://hdl.handle.net/10962/d1005951 , http://dx.doi.org/10.1016/j.bbamcr.2008.01.014
- Description: The Hsp70–Hsp90 complex is implicated in the folding and regulation of numerous signaling proteins, and Hop, the Hsp70–Hsp90 Organizing Protein, facilitates the association of this multichaperone machinery. Phosphatase treatment of mouse cell extracts reduced the number of Hop isoforms compared to untreated extracts, providing the first direct evidence that Hop was phosphorylated in vivo. Furthermore, surface plasmon resonance (SPR) spectroscopy showed that a cdc2 kinase phosphorylation mimic of Hop had reduced affinity for Hsp90 binding. Hop was predominantly cytoplasmic, but translocated to the nucleus in response to heat shock. A putative bipartite nuclear localization signal (NLS) has been identified within the Hsp90-binding domain of Hop. Although substitution of residues within the major arm of this proposed NLS abolished Hop–Hsp90 interaction as determined by SPR, this was not sufficient to prevent the nuclear accumulation of Hop under leptomycin-B treatment and heat shock conditions. These results showed for the first time that the subcellular localization of Hop was stress regulated and that the major arm of the putative NLS was not directly important for nuclear translocation but was critical for Hop–Hsp90 association in vitro. We propose a model in which the association of Hop with Hsp90 and the phosphorylated status of Hop both play a role in the mechanism of nucleo-cytoplasmic shuttling of Hop.
- Full Text:
- Date Issued: 2008
- Authors: Daniel, Sheril , Bradley, Graeme , Longshaw, Victoria M , Söti, Csaba , Csermely, Peter , Blatch, Gregory L
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6472 , http://hdl.handle.net/10962/d1005951 , http://dx.doi.org/10.1016/j.bbamcr.2008.01.014
- Description: The Hsp70–Hsp90 complex is implicated in the folding and regulation of numerous signaling proteins, and Hop, the Hsp70–Hsp90 Organizing Protein, facilitates the association of this multichaperone machinery. Phosphatase treatment of mouse cell extracts reduced the number of Hop isoforms compared to untreated extracts, providing the first direct evidence that Hop was phosphorylated in vivo. Furthermore, surface plasmon resonance (SPR) spectroscopy showed that a cdc2 kinase phosphorylation mimic of Hop had reduced affinity for Hsp90 binding. Hop was predominantly cytoplasmic, but translocated to the nucleus in response to heat shock. A putative bipartite nuclear localization signal (NLS) has been identified within the Hsp90-binding domain of Hop. Although substitution of residues within the major arm of this proposed NLS abolished Hop–Hsp90 interaction as determined by SPR, this was not sufficient to prevent the nuclear accumulation of Hop under leptomycin-B treatment and heat shock conditions. These results showed for the first time that the subcellular localization of Hop was stress regulated and that the major arm of the putative NLS was not directly important for nuclear translocation but was critical for Hop–Hsp90 association in vitro. We propose a model in which the association of Hop with Hsp90 and the phosphorylated status of Hop both play a role in the mechanism of nucleo-cytoplasmic shuttling of Hop.
- Full Text:
- Date Issued: 2008